Crystalline polypropylene resin composition and amide compounds

[0002] The present invention relates to a crystalline polypropylene resin composition containing an amide compound capable of acting as a nucleating agent for predominant formation of the β-crystal form and to a novel amide compound which is of use as a nucleating agent for the formation of the β-crystal form.

[0003] It is known that crystalline polypropylene may occur in α, β, γ and δ crystal forms as well as in the smectic crystal form which is formed on quenching of melted polypropylene. The β-crystal form (hereinafter referred to as “β-form”) differs from the a-form which is found in the conventional natural pellet in that it is lower in melting point and in density, not to speak of differences in the mode of crystallization and of fracture, thus being of interest from application points of view (Kobunshi Kagaku 30, 694-698, (1973)).

[0004] For the production of crystalline polypropylene containing the β-form, a process comprising crystallizing molten polypropylene on a temperature gradient and a process comprising blending with a small amount of a nucleating agent (hereinafter referred to as “β-nucleating agent”) are known. Since the former process is time-consuming and provides only a low yield, the latter process employing a β-nucleating agent is more advantageous for all practical purposes.

[0005] As such a β-nucleating agent, γ-quinacridone is well-known (Polymer Letters, 6, 539-546, (1968)). However, this nucleating agent has the drawback that it imparts a red tint to the product and requires special apparatus and operation for blending it with the polymer.

[0006] The object of the present invention is to provide a novel β-nucleating agent insuring an efficient production of a product containing β-crystalline polypropylene in a large amount and much improved in the aspect of product color because of substantial absence of coloring property, and to provide a practically useful crystalline polypropylene resin composition containing said β-nucleating agent.

[0007] The inventors of the present invention discovered, after extensive research to provide a β-nucleating agent that would solve the above-mentioned problems, that a class of amide compounds having a specific chemical structure can accomplish the above object and that some of said amide compounds are novel compounds which are not described before in the published literature. The present invention has been achieved on the basis of the above findings.

[0008] The crystalline polypropylene resin composition of the present invention is characterized in that, in addition to a crystalline polypropylene resin, it contains at least one β-nucleating agent selected from the group consisting of amide compounds of the formula (1), amide compounds of the formula (2) and amide compounds of the formula (3) to be described below in an amount effective for increasing the content of the β-crystal form:

[0009] (1) an amide compound of the formula:

[0010] R²—NHCO—R¹—CONH—R³  (1)

[0011] wherein R¹is a residue of a C_3-20saturated or unsaturated aliphatic dicarboxylic acid, a residue of a C_6-30saturated or unsaturated alicycic dicarboxylic acid or a residue of a C_8-30aromatic dicarboxylic acid; R²and R³are the same or different and each represents a C_3-12cycloalkyl group, a C_3-12cycloalkenyl group, or a group of the formula

[0012] wherein R⁴is a hydrogen atom, a C_1-12straight- or branched-chain alkyl group, a C_2-12straight- or branched-chain alkenyl group, a C_6-10cycloalkyl group or a phenyl group; R⁵is a C_1-12straight- or branched-chain alkyl group, a C_2-12straight- or branched-chain alkenyl group, a C_6-10cycloalkyl group or a phenyl group; and R⁶and R⁷each represents a C_1-4straight- or branched-chain alkylene group; with the proviso that when R⁴is a hydrogen atom, a C_1-12alkyl group or a C_6-10cycloalkyl group, R¹is a residue of a C₆or C₈saturated aliphatic dicarboxylic acid,

[0013] (2) an amide compound of the formula:

[0014] R⁹—CONH—R⁸—NHCO—R¹⁰  (2)

[0015] wherein R⁸is a residue of a C_4-28alicyclic diamine, a residue of a C_4-14heterocyclic diamine or a residue of a C_6-28aromatic diamine; R⁹and R¹⁰are the same or different and each represents a C_3-12cycloalkyl group, a C_3-12cycloalkenyl group, or a group of the formula

[0016] wherein R¹¹is a hydrogen atom, a C_1-12straight- or branched-chain alkyl group, a C_2-12straight- or branched-chain alkenyl group, a C_6-10cycloalkyl group or a phenyl group; R¹²is a C_1-12straight- or branched-chain alkyl group, a C_2-12alkenyl group, a C_6-10cycloalkyl group or a phenyl group; and R¹³and R¹⁴each represents a C_1-4straight- or branched-chain alkylene group; with the proviso that R⁸is not

[0017] (3) an amide compound of the formula:

[0018] R¹⁶—CONH—R¹⁵—CONH—R¹⁷  (3)

[0019] wherein R¹⁵is a residue of a C_2-29saturated or unsaturated aliphatic amino acid, a residue of a C_7-13saturated or unsaturated alicyclic amino acid or a residue of a C_7-15aromatic amino acid; R¹⁶and R¹⁷are the same or different and R¹⁶has the same meaning as R⁹or R¹⁰in the formula (2) and R¹⁷has the same meaning as R²or R³in the formula (1).

[0020] The present invention also provides a method for increasing the proportion of the β-crystal form in a crystalline polypropylene resin molded product which comprises molding the composition comprising a crystalline polypropylene resin and containing at least one amide compound of the above formulas (1), (2) and (3) in an amount effective for increasing the proportion of the β-crystal form.

[0021] Among these amide compounds of the formulas (1), (2) and (3), the compounds of the formula (1) and those of the formula (2) are preferred. Particularly preferred are amide compounds of the formula (1) wherein R¹is —(CH₂)₄—,

[0022] and R²and R³are the same or different and each represents a C_6-8cycloalkyl group or represents a phenyl group substituted by a C_1-4alkyl or cyclohexyl group, and amide compounds of the formula (2) wherein R⁸is

[0023] and R⁹and R¹⁰are the same or different and each is a cyclohexyl group or a phenyl group.

[0024] Processes for the production of amide compounds of the formulas (1), (2) and (3) are described below.

[0025] Amide compounds of the formula (1)

[0026] The amide compound of the formula (1) can be easily prepared by subjecting an aliphatic, alicyclic or aromatic dicarboxylic acid of the the formula:

[0027] HOOC—R¹—COOH  (1a)

[0028] wherein R¹is as defined hereinbefore to amidation reaction with an alicyclic or aromatic monoamine of the formula:

[0029] R²—NH₂or R³—NH₂

[0030] wherein R²and R³are as defined hereinbefore.

[0031] This amidation reaction can be carried out in a conventional manner and any one of the following processes may be mentioned as typical examples. Incidentally, where R²and R³in the formula (1) are dissimilar to each other, a substantially equimolar mixture of the corresponding two kinds of monoamines is employed.

[0032] (i) In an inert solvent, said dicarboxylic acid is reacted with said monoamine at a temperature of about 60 to 200° C. for about 2 to 8 hours. The monoamine is generally used in an amount of about 2 to 10 equivalents per one equivalent of the dicarboxylic acid. In this process, an activator is preferably used to accelerate the reaction. The activator that can be used includes phosphorus pentaoxide, polyphosphoric acid, phosphorus pentaoxide-methanesulfonic acid, phosphorous ester (e.g. triphenyl phosphite)-pyridine, phosphorous ester-metal salt (e.g. lithium chloride), triphenylphosphine-hexachloroethane and so on. Generally, about one mole of the activator is used per mole of the dicarboxylic acid.

[0033] (ii) In an inert solvent, dichloride of said dicarboxylic acid is reacted with said monoamine at a temperature of about 0 to 100° C. for about 1 to 5 hours. The monoamine is used generally in an amount of 2 to 3 equivalents per one equivalent of the dicarboxylic acid dichloride.

[0034] (iii) In an inert solvent, a diester, particularly a di(C_1-3)alkyl ester, of said dicarboxylic acid is reacted with said monoamine in the presence of a catalyst at about 0-150° C. for about 3 to 10 hours. The monoamine is used generally in an amount of about 2 to 20 equivalents per one equivalent of the dicarboxylic acid diester. The catalyst may be an acid or basic catalyst that is conventionally used in ester-amide interchange reactions, and is preferably a basic catalyst. Thus, there may be mentioned lithium, sodium, potassium; alkali metal hydrides such as lithium hydride, sodium hydride, potassium hydride, etc.; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide etc.; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.; and alkali metal amides such as sodium amide, lithium dipropylamide, etc., among others. The catalyst is used generally in an equimolar amount relative to said dicarboxylic acid.

[0035] The inert solvent which can be used for the above processes (i), (ii) and (iii) include, among others, benzene, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0036] As the dicarboxylic acid of the formula (1a) for use in said processes (i), (ii) and (iii), there may be mentioned the aliphatic, alicyclic or aromatic dicarboxylic acid corresponding to R¹. Thus, R¹is preferably a residue formed by elimination of the two carboxyl groups of one of the following aliphatic, alicylic and aromatic dicarboxylic acids.

[0037] The aliphatic dicarboxylic acid specifically includes C_3-20, preferably C_3-14saturated or unsaturated aliphatic dicarboxylic acids, such as 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 and so on.

[0038] The alicyclic dicarboxylic acid specifically includes C_6-30, preferably C_8-12saturated or unsaturated alicyclic dicarboxylic acids such as 1,2-cyclohexane di-carboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid and so on.

[0039] The aromatic dicarboxylic acid specifically includes C_8-30, preferably C_8-22aromatic dicarboxylic acids such as p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic 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 and so on.

[0040] On the other hand, the monoamine to be used in processes (i), (ii) and (iii) is the alicyclic or aromatic amonoamine corresponding to R²or R³, i.e., R²—NH₂or R³—NH₂.

[0041] The alicyclic monoamine particularly includes C₃-C₁₂cycloalkylamines, C₃-C₁₂cycloalkenylamines,

[0042] (wherein R⁵is as defined above),

[0043] (wherein R⁷is as defined above) and the like, and specifically includes, among others, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-propylcyclohexylamine, 2-isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-isopropylcyclohexylamine, 2-tert-butylcyclohexylamine, 4-n-butylcyclohexylamine, 4-isobutylcyclohexylamine, 4-sec-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 4-n-amylcyclohexylamine, 4-isoamylcyclohexylamine, 4-sec-amylcyclohexylamine, 4-tert-amylcyclohexylamine, 4-hexylcyclohexylamine, 4-heptylcyclohexylamine, 4-octylcyclohexylamine, 4-nonylcyclohexylamine, 4-decylcyclohexylamine, 4-undecylcyclohexylamine, 4-dodecylcyclohexylamine, 4-cyclohexylcyclohexylamine, 4-phenylcyclohexylamine, cycloheptylamine, cyclododecylamine, cyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine, γ-cyclohexylpropylamine and so on.

[0044] The aromatic monoamine particularly includes

[0045] (where(wherein R⁴is as defined above),

[0046] (wherein R⁶is as defined above) and the like, and specifically includes, among others, aniline, o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-cumidine, m-cumidine, p-cumidine, o-tert-butylaniline, p-n-butyl-aniline, p-isobutylaniline, p-sec-butylaniline, p-tert-butylaniline, p-n-amylaniline, p-isoamylaniline, p-sec-amylaniline, p-tert-amylaniline, p-hexylaniline, p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline, p-undecylaniline, p-dodecylaniline, p-cyclohexylaniline, o-aminodiphenyl, m-aminodiphenyl, p-aminodiphenyl, p-aminostyrene, benzylamine, α-phenylethylamine, β-phenylethylamine, α-phenylpropylamine, β-phenylpropylamine and γ-phenylpropylamine.

[0047] Among the amide compounds of the formula (1), the compounds which can be specifically represented by the following formula (4) are novel compounds not heretofore described in the literature.

[0048] R¹⁹—NHCO—R¹⁸—CONH—R²⁰  (4)

[0049] wherein R¹⁸means

[0050] R¹⁹and R²⁰may be the same or different and each means a C_5-12cycloalkyl group.

[0051] These novel amide compounds can be produced basically by the conventional amidation reactions and particularly by the above-described processes (i), (ii) and (iii). Thus, any one of the following methods can be used,

[0052] (a) A naphthalenedicarboxylic acid or biphenyldicarboxylic acid of the formula HOOC—R¹⁸—COOH (hereinafter referred to as “dicarboxylic acid A”) is reacted with 2 to 10 equivalents of a monoamine in an inert solvent at about 60 to 200° C. for about 2 to 8 hours.

[0053] In order to accelerate this reaction, said activator is preferably employed.

[0054] (b) Dichloride of said dicarboxylic acid A is reacted with 2 to 3 equivalents of a monoamine in an inert solvent at about 0-100° C. for about 1 to 5 hours.

[0055] (c) A di(C_1-3) alkyl ester of dicarboxylic acid A is reacted with 2 to 20 equivalents of a monoamine in an inert solvent in the presence of an acid or basic catalyst, which is conventionally used in ester-amide interchange reactions as mentioned hereinbefore, and preferably in the presence of said basic catalyst, at about 0 to 150° C. for about 3 to 10 hours.

[0056] The inert solvent which is employed in the above processes (a), (b) and (c) may be identical with the inert solvent mentioned hereinbefore for processes (i), (ii) and (iii).

[0057] The monoamine for use in the above processes is the monoamine corresponding to the formula R¹⁹—NH₂or R²⁰—NH₂. Particularly preferred are C_5-12cycloalkylamines such as cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine and so on.

[0058] The compounds obtained by the above processes (i), (ii) and (iii) or processes (a), (b) and (c) can each be isolated and purified by the conventional procedures such as chromatography, reprecipitation, recrystallization, fractional crystallization, and so on.

[0059] Among the amide compounds of the formula (1), those which are more effective include N,N′-dicyclohexylterephthalamide, N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide, N,N′-dicyclooctyl-2,6-naphthalenedicarboxamide, N,N′-dicyclohexyl-1,4-cyclohexanedicarboxamide, N,N′-dicyclohexyl-4,4′-biphenyldicarboxamide, N,N′-bis(p-methylphenyl)hexanediamide, N,N′-bis(p-ethylphenyl)hexanediamide, N,N′-bis(4-cyclohexylphenyl)hexanediamide, N,N′-diphenylhexanediamide, N,N′-diphenyloctanediamide and so on.

[0060] Among these, N,N′-dicyclohexylterephthalamide, N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide and N,N′-dicyclohexyl-4,4′-biphenyldicarboxamide can provide higher proportion of β-crystal form under quenching condition.

[0061] Amide compounds of the formula (2)

[0062] The amide compound of the formula (2) can be easily produced by subjecting an alicyclic, heterocyclic or aromatic diamine of the formula:

[0063] NH₂—R⁸—NH₂  (2a)

[0064] wherein R⁸is as defined hereinbefore and an alicyclic or aromatic monocarboxylic acid of the formula:

[0065] R⁹—COOH or R¹⁰—COOH

[0066] to amidation reaction in the conventional manner.

[0067] This amidation reaction can be conducted in various conventional ways, but typically any one of the following processes may be mentioned.

[0068] (i′) The above-mentioned diamine is reacted with the monocarboxylic acid in an inert solvent at about 60 to 200° C. for about 2 to 8 hours. The monocarboxylic acid is used generally in an amount of about 2 to 10 equivalents per one equivalent of the diamine. In this process, too, the activator mentioned for process (i) is preferably employed in order to accelerate the reaction. The activator is used generally in an equimolar amount with respect to the diamine.

[0069] (ii′) The above diamine is reacted with the acid chloride of said monocarboxylic acid in an inert solvent at about 0 to 100° C. for about 1 to 5 hours. The monocarboxylic acid chloride is used generally in an amount of 2 to 3 equivalents per one equivalent of the diamine.

[0070] (iii′) The above diamine is reacted with an ester, particularly a C_1-3alkyl ester, of said monocarboxylic acid in an inert solvent in the presence of a catalyst at about 0 to 150° C. for about 3 to 10 hours. The monocarboxylic acid ester is generally used in an amount of about 2 to 20 equivalents per one equivalent of the diamine. The catalyst may be selected from among the acid and basic catalysts for conventional ester-amide interchange reactions as mentioned for said process (iii) and is preferably a basic catalyst.

[0071] When R⁹and R¹⁰in the formula (2) are dissimilar, a substantially equimolar mixture of 2 kinds of corresponding monocarboxylic acids (or a substantially equimolar mixture of 2 kinds of corresponding monocarboxylic acid chlorides or a substantially equimolar mixture of 2 kinds of corresponding monocarboxylic acid esters) is employed.

[0072] The inert solvent for use in said processes (i′), (ii′) and (iii′) can be the same as the solvent mentioned for processes (i), (ii) and (iii) for production of the compound of the formula (1).

[0073] The compound obtained by the above processes can be isolated and purified by the conventional procedures such as chromatography, reprecipitation, recrystallization, fractional crystallization and so on.

[0074] In the above processes (i′), (ii′) and (iii′), the diamine of the formula (2a) is the alicyclic, heterocyclic or aromatic diamine corresponding to R⁸. Thus, R⁸is preferably a residue formed by elimination of the two amino groups of one of the following alicyclic, heterocyclic and aromatic diamines.

[0075] Thus, the alicyclic diamine includes C_4-28, preferably C_6-15alicyclic diamines such as 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexyl, 4,4′-diamino-3,3′-dimethyldicyclohexyl, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,31-dimethyldicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and additionally includes isophoronediamine, menthenediamine and so on.

[0076] The heterocyclic diamine includes 5- or 6-membered heterocyclic diamines containing 1 or 2 nitrogen or sulfur atoms in the ring structure and having 4 to 14 carbon atoms, such as 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, o-tolidinesulfone and so on.

[0077] The aromatic diamine includes those containing 6 to 28, preferably 6 to 15 carbon atoms, such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, 2,4-diaminomesitylene, 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,-diaminodiphenylether, 3,4′-diaminodiphenylether, 4,4′-thiodianiline, 2,2′-dithiodianiline, 4,4′-dithiodianiline, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobenzanilide, 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 and so on.

[0078] As preferred examples of the alicyclic monocarboxylic acid represented by R⁹—COOH or R¹⁰—COOH, there may be mentioned C₄-C₁₃cycloalkanecarboxylic acids, C₄-C₁₃cycloalkenecarboxylic acids,

[0079] (wherein R¹²is as defined above),

[0080] (wherein R¹⁴is as defined above), etc., and examples thereof are cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentane-carboxylic acid, 3-methylcyclopentanecarboxylic acid, 1-phenylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-phenylcyclohexanecarboxylic acid, 1-phenylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-cycloheptenecarboxylic acid, 1-methylcycloheptanecarboxylic acid, 4-methylcycloheptanecarboxylic acid, cyclohexylacetic acid and so on.

[0081] As preferred examples of the aromatic monocarboxylic acid represented by R⁹—COOH or R¹⁰—COOH, there may be mentioned

[0082] (wherein R¹¹is as defined above),

[0083] (wherein R¹³is as defined above), etc., and examples thereof are benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, p-ethylbenzoic acid, p-propylbenzoic acid, p-butylbenzoic acid, p-tert-butylbenzoic acid, p-pentylbenzoic acid, p-hexylbenzoic acid, o-phenylbenzoic acid, p-phenylbenzoic acid, p-cyclohexylbenzoic acid, phenylacetic acid, phenylpropionic acid, phenylbutyric acid and so on.

[0084] The more desirable species of the diamide compound of the formula (2) which can be obtained from said diamine and monocarboxylic acid include N,N′-1,4-phenylenebis-cyclohexanecarboxamide, N,N′-1,5-naphthalenebis-benzamide, N,N′-1,4-cyclohexanebis-benzamide, N,N′-1,4-cyclohexanebis-cyclohexanecarboxamide and so on.

[0085] It should be noted that the desired effect cannot be obtained when the amide compound of the formula (2) is a compound synthesized by using xylylenediamine as the aromatic diamine. Such compounds of the formula (2) wherein R⁸is —CH₂—C₆H₄—CH₂—are excluded from the scope of the present invention.

[0086] Amide compounds of the formula (3)

[0087] The amide compound of the formula (3) can be easily prepared by subjecting an aliphatic, alicyclic or aromatic amino acid of the formula (3a)

[0088] NH₂—R¹⁵—COOH  (3a)

[0089] wherein R¹⁵is as defined hereinbefore, a monocarboxylic acid chloride of the formula R¹⁶—COCl (wherein R¹⁶is as defined hereinbefore) and a monoamine of the formula R¹⁷—NH₂(wherein R¹⁷is as defined hereinbefore) to an amidation reaction.

[0090] This amidation reaction can be conducted, for example by reacting said amino acid of the formula (3a) with 1 to 2 equivalents of said monocarboxylic acid chloride in an inert solvent at about 0 to 100° C. for about 1 to 5 hours, then adding 1 to 5 equivalents, based on the reaction product, of said monoamine and conducting the reaction, preferably in the presence of the activator mentioned for process (i), at a temperature of about 60 to 200° C. for about 2 to 8 hours. The inert solvent may be any of the solvents mentioned hereinbefore in connection with process (i) for the production of said compound of the formula (1).

[0091] The compound obtained by the above process is purified by the conventional isolation and purification procedures such as chromatography, reprecipitation, recrystallization, fractional crystallization and so on.

[0092] The amino acid (3a) to be used in the above process is the aliphatic, alicyclic or aromatic amino acid corresponding to R¹⁵. Thus, R¹⁵is preferably a residue formed by elimination of one amino group and one carboxyl group from one of the aliphatic, alicyclic and aromatic amino acids mentioned below.

[0093] As preferred examples of said aliphatic amino acid, there may be mentioned C_2-29, more preferably C_2-13, saturated or unsaturated aliphatic amino acids such as 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, 11-aminoundecanoic acid, 12-aminododecanoic acid and so on.

[0094] The alicyclic amino acid includes C_7-13saturated or unsaturated alicyclic amino acids such as 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid and so on.

[0095] The aromatic amino acid specifically includes C_7-15aromatic amino acids such as 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-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, 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 and so on.

[0096] The monoamine (R¹⁷—NH₂) as a starting compound for the amide compound of the formula (3) is identical with the monoamine (R²—NH₂or R³—NH₂) used as a starting compound for the amide compound of the formula (1), and similarly the monocarboxylic acid chloride (R¹⁶COCl) is one derived from the monocarboxylic acid which is identical with the monocarboxylic acid (R⁹COOH or R¹⁰COOH) used as a starting compound for the amide compound of the formula (2).

[0097] Among various species of the amide compound of the formula (3), N-cyclohexyl-4-(N-cyclohexylcarbonylamino)-benzamide and N-phenyl-5-(N-benzoylamino)pentanamide, for instance, are particularly effective.

[0098] The β-nucleating agent of the formula (1), (2) or (3) can be added to polypropylene resin at an optional stage, i.e. either during the polymerization reaction or after the polymer has been prepared.

[0099] The amount of said β-nucleating agent to be added is not critical insofar as the desired effect can be obtained. Generally, it is used in an amount effective for increasing the content of the β-crystal form. Especially, based on 100 parts by weight of polypropylene resin, about 0.0001 to 5 parts by weight, preferably about 0.001 to 1 part by weight, of the β-nucleating agent is employed. If the proportion of the β-nucleating agent is less than 0.0001 part by weight, formation of the β-crystal form may not be sufficient, while the use of the β-nucleating agent in excess of 5 parts by weight may not be rewarded with a commensurate effect and be uneconomical.

[0100] Thus, the β-nucleating agent of the invention is capable of causing a crystalline polypropylene resin to undergo transition to the β-crystal form at a very low level of addition and a molded product having a I-form content of about 20 to 97%, particularly 40 to 97%, more preferably about 50 to 90% can be obtained under the conventional molding conditions.

[0101] The term ‘polypropylene resin’ as used in this specification and claim means not only a polypropylene homopolymer but also a polymer composed predominantly of propylene, particularly a polymer composed of not less than 50% by weight, preferably not less than 80% by weight, of propylene. As examples of the latter polymer, there may be mentioned propylene-ethylene random copolymer, propylene-ethylene block copolymer, polymer blends of said polypropylene resin with a small proportion of a thermoplastic resin, such as high-density polyethylene, polybutene-1, poly-4-methylpentene-1 or the like.

[0102] The catalyst which can be used for the production of such polymers includes not only Ziegler-Natta catalyst which is commonly employed but also a combination catalyst, such as one wherein a transition metal compound (e.g. titanium halides such as titanium trichloride, titanium tetrachloride, etc.) supported on a support composed mainly of magnesium halide, such as magnesium chloride, is combined with an alkylaluminum compound (e.g. triethylaluminum, diethylaluminum chloride, etc.).

[0103] The melt flow rate (hereinafter referred to briefly as “MFR”; measured in accordance with JIS K 6758-1981) of the crystalline polypropylene resin can be appropriately selected according to the molding method to be employed and is generally about 0.1 to 100 g/10 min. and preferably about 0.5 to 50 g/10 min.

[0104] If required, the resin composition of the present invention may contain a variety of additives such as a stabilizer (e.g. epoxy compounds), an antioxidant (e.g. phenol compounds, phosphite compounds), an ultraviolet absorber (benzophenone compounds, benzotriazole compounds), a neutralizer, a nucleating agent, an antistatic agent, an antiblocking agent, a lubricant (e.g. aliphatic hydrocarbons, higher fatty acids, and the alkali metal salts or alkaline earth metal salts thereof, fatty acid esters, higher fatty acid amides, rosin derivatives), a colorant, an elastomer, and a mineral (e.g. talc, hydrotalcite), each within a range not interfering with the effect of the invention.

[0105] The crystalline polypropylene resin composition of the invention is preferably produced by mixing said β-nucleating agent and polypropylene resin, with or without addition of said additives, in an ordinary mixer, such as a Henschel mixer, and if necessary, pelletizing the resulting mixture using an ordinary pelletizer, such as a single-screw extruder, in the per se known manner.

[0106] The resulting crystalline polypropylene resin composition of the invention can be molded by various known techniques. Thus, injection molding, extrusion molding, compression molding and other molding techniques utilizing the conventional molding machines can be employed. Molding conditions may be those commonly employed. Typical preferred molding conditions may be as follows. Injection molding: resin temperature about 200 to 300° C., preferably about 240 to 280° C.; mold temperature about 30 to 120° C., preferably about 50 to 80° C. Extrusion molding: resin temperature about 200 to 300° C., preferably about 240 to 280° C.; chill roll temperature about 40 to 140° C., preferably about 60 to 120° C. Compression molding: temperature of melted resin about 200 to 300° C., preferably about 240 to 280° C.; cooling temperature about 30 to 120° C., preferably about 50 to 100° C.

[0107] Molded product, which contains much higher proportion of β-crystal form than before and which is satisfactory in the aspect of color, can be easily obtained by molding under the above-mentioned molding condition the resin composition of the invention prepared with use of the above-mentioned mixing method. Compared with the conventional polypropylene pellet which does not substantially contain β-crystals but is predominantly composed of α-crystals, the polypropylene molded product has lower melting point and requires a less force for deformation under heating. Therefore, the molded products contributes a great deal to improved secondary processability and mechanical characteristics. The products encompass a wide variety of forms such as packages, sheet, film and so on.

[0108] With the resin composition of the present invention, the ratio of α- to β-forms in the final product can be controlled as desired by suitably selecting molding conditions such as cooling conditions. For example, the proportion of R-form is increased as a higher cooling temperature is employed. Thus, it is possible to control the ratio of α- to β-forms by appropriately selecting cooling condition under the above molding condition. This characteristic is beneficial particularly in the surface roughening of biaxially oriented film. The film having such a roughened surface displays excellent antiblocking property, printability and adhesion, etc. and is of great use in the fields of packaging film, printing paper, tracing paper, oil-immersion type plastic capacitors and so on.

[0109] Moreover, the resin composition containing a naphthalenedicarboxylic acid di(C_3-12)cycloalkylamide, which is among the amide compounds of the invention, is extremely useful for improving the impact strength of moldings and can exhibit excellent utility in a variety of applications such as automotive and electrical parts, etc.

[0110] The following examples and comparative examples are intended to describe the invention in further detail. In these examples and comparative examples, the β-form content, modulus in flexure and impact strength were determined by the following methods.

[0111] (1) Determination of β-form content

[0112] A sample (5-10 mg), cut from the sheet obtained in each Example and Comparative Example by punching, is set in the sample holder of a differential scanning calorimeter (DSC) and melted by heating in a nitrogen gas atmosphere at 230° C. for 5 minutes. The temperature is then decreased at a rate of 20° C./min to near room temperature and, then, increased again at a rate of 20° C./min. From the peak areas of the α- and β-crystal forms on the DSC thermogram thus obtained, the β-form content (area %) is calculated by means of the following equation.

[0113] β-form content (%)=100×A_β/(A_α+A_β)

[0114] where A₆₀means the peak area of α-form and A_βmeans the peak area of β-form.

[0115] (2) Determination of modulus in flexure

[0116] The modulus was determined in accordance with JIS K 7203. The testing temperature was 25° C. and the testing speed was 10 mm/min.

[0117] (3) Impact strength (duPont method)

[0118] In accordance with the falling weight impact test method described in JIS K 7211, the 50% destruction energy for a 2 mm-thick sheet at 23° C. was determined.

[0119] To 100 parts by weight of a propylene homopolymer powder (MFR=14 g/10 min) was added 0.05 part by weight of N,N′-dicyclohexylterephthalamiide and the mixture was milled in a Henschel mixer and pelletized with a 20 mm-diameter single-screw extruder. The resulting pellets were subjected to compression-molding by melting the pellets at 230° C. for 10 minutes and then placing it in a mold of 60° C. and maintaining it therein for 5 minutes for solidification to give a 0.5 mm-thick sheet. The β-form content of the resulting sheet was 93% and the sheet showed no coloration.

[0120] Except that N,N′-dicyclohexyl-1,4-cyclohexanedicarboxamide was used as the β-nucleating agent, the procedure of Example 1 was otherwise repeated to provide a sheet. The β-form content of this sheet was 42% and the sheet showed no coloration.

[0121] Except that N,N′-dicylohexyl-2,6-naphthalenedicarboxamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 97% and the sheet showed no coloration.

[0122] Except that N,N′-dicylohexyl-4,4′-biphenyldicarboxamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 59% and the sheet showed no coloration.

[0123] Except that N,N′-bis(p-methylphenyl)hexanediamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 89% and the sheet showed no coloration.

[0124] Except that N,N′-bis(p-ethylphenyl)hexanediamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 64% and the sheet showed no coloration.

[0125] Except that N,N′-bis (4-cyclohexylphenyl)hexanediamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 82% and the sheet showed no coloration.

[0126] Except that 0.05 part by weight of N,N′-1,4-phenylenebis-cyclohexanecarboxamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 84% and the sheet showed no coloration.

[0127] Except that N,N′-1,5-naphthalenebis-benzamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 44% and the sheet showed no coloration.

[0128] Except that N,N′-1,4-cyclohexanebis-benzamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 92% and the sheet showed no coloration.

[0129] Except that N,N′-1,4-cyclohexanebis-cyclohexanecarboxamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 85% and the sheet showed no coloration.

[0130] Except that N-cyclohexyl-4-(N-cyclohexylcarbonylamino)benzamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 42% and the sheet showed no coloration.

[0131] Except that N-phenyl-5-(N-benzoylamino)pentanamide was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 38% and the sheet showed no coloration.

[0132] Except that polypropylene homopolymer (MFR=4.3 g/10 min) was used as the polypropylene, the procedure of Example 1 was repeated to provide a sheet. The β-form content of this sheet was 95% and the sheet showed no coloration.

[0133] Except that N,N′-dicyclohexylterephthalamide was not added, the procedure of Example 1 was repeated to provide a sheet and its β-form content was determined. This sheet contained only a trace amount of β-form. The sheet showed no coloration.

[0134] Except that γ-quinacridone was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. However, under the particular conditions used, the sheet contained only a trace amount of β-form. The sheet had a red color.

[0135] To 100 parts by weight of a propylene homopolymer powder (MFR=14 g/10 min) was added 0.2 part by weight of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide and the mixture was milled in a Henschel mixer and pelletized with a 20 mm-diameter single-screw extruder. The resulting pellets were injection-molded at a resin temperature of 240° C. and a mold temperature of 50° C. to provide a test piece. The modulus in flexure of the above test piece was 151 kgf/mm². The duPont impact strength was 41 kgf·cm.

[0136] Except that N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide was not added, the procedure of Example 15 was otherwise repeated to provide a sheet. This sheet had a modulus in flexure of 139 kgf/mm2 and a duPont impact strength of 3 kgf·cm.

[0137] A 300 ml four-necked flask equipped with a stirrer, thermometer, condenser and gas inlet was charged with 6.48 g (0.03 mole) of 2,6-naphthalenedicarboxylic acid, 5.61 g (0.066 mole) of cyclopentylamine, 20.46 g (0.066 mol) of triphenyl phosphite, 25 g of pyridine and 100 g of N-methylpyrrolidone, and the reaction was carried out in a nitrogen gas atmosphere at 100° C. for 3 hours, with stirring. After cooling, the reaction mixture was poured in 700 ml of isopropyl alcohol/water (1:1) for reprecipitation and washing. The mixture was stirred for 2 hours and the precipitate was then recovered by filtration and dried under reduced pressure at 110° C. to provide 9.03 g (yield 86%) of N,N′-dicyclopentyl-2,6-naphthalenedicarboxamide. This compound was a white powder melting at 375.4° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0138] Except that 6.53 g (0.066 mole) of cyclohexylamine was used as the monoamine, the procedure of Example 16 was otherwise repeated to provide 9.64 g (yield 85%) of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide. This compound was a white powder melting at 384.2° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0139] Except that the above compound was used as the β-nucleating agent, the procedure of Example 1 was otherwise repeated to provide a sheet. The β-form content of this sheet was 97% and the sheet showed no coloration.

[0140] Except that 8.38 g (0.066 mole) of cyclooctylamine was used as the monoamine, the procedure of Example 16 was otherwise repeated to provide 9.63 g (yield 74%) of N,N′-dicyclooctyl-2,6-naphthalenedicarboxamide. This compound was a white powder melting at 320.8° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0141] Except that 12.08 g (0.066 mole) of cyclododecylamine was used as the monoamine, the procedure of Example 16 was repeated to provide 13.3 g (yield 81%) of N,N′-dicyclododecyl-2,6-naphthalenedicarboxamide. This compound was a white powder melting at 321.8° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0142] Except that 6.48 g (0.03 mole) of 2,7-naphthalenedicarobxylic acid was used as the dicarboxylic acid, the procedure of Example 17 was otherwise repeated to provide 8.39 g (yield 74%) of N,N′-dicyclohexyl-2,7-naphthalenedicarboxamide. This compound was a white powder melting at 337.1° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0143] Except that 7.26 g (0.03 mole) of 4,4′-biphenyldicarboxylic acid was used as the dicarboxylic acid, the procedure of Example 16 was otherwise repeated to provide 8.12 g (yield 72%) of N,N′-dicyclopentyl-4,4′-biphenyldicarboxamide. This compound was a white powder melting at 355.0° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0144] Except that 6.53 g (0.066 mole) of cyclohexylamine was used as the monoamine, the procedure of Example 21 was otherwise repeated to provide 9.94 g (yield 82%) of N,N′-dicyclohexyl-4,4′-biphenyldicarboxamide. This compound was a white powder melting at 370.8° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0145] Except that the above compound was used as the β-nucleating agent, the procedure of Example 1 was otherwise repeated to provide a sheet. The β-form content of this sheet was 59% and the sheet showed no coloration.

[0146] Except that 8.38 g (0.066 mole) of cyclooctylamine was used as the monoamine, the procedure of Example 21 was otherwise repeated to provide 10.8 g (yield 78%) of N,N′-dicyclooctyl-4,4′-biphenyldicarboxamide. This compound was a white powder melting at 320.2° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0147] Except that 12.08 g (0.066 mole) of cyclododecylamine was used as the monoamine, the procedure of Example 21 was otherwise repeated to provide 17.16 g (yield 82%) of N,N′-dicyclododecyl-4,4′-biphenyldicarboxamide. This compound was a white powder melting at 346.7° C. (decomp.). The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0148] A reactor was charged with 8.37 g (0.03 mole) of 2,2′-biphenyldicarboxylic acid dichloride, 11.88 g (0.12 mole) of cyclohexylamine and 120 g of chlorobenzene and the reaction was carried out in a nitrogen gas atmosphere at 80° Cc for 2.5 hours. After cooling, the reaction mixture was poured in 1000 ml of hexane for reprecipitation and washing. The precipitate was washed with 600 ml of a 0.5% aqueous sodium hydroxide solution and further with purified water thoroughly. The precipitate was collected by filtration and dried under reduced pressure at 110° C. to provide 6.08 g (yield 50%) of N,N′-dicycohexyl-2,2′-biphenyldicarboxamide. This compound was a white powder melting at 229.2-229.8° C. The elemental analysis and characteristic infrared absorptions are shown in Table 1.

[0149] Table 2 below shows the structure each of the β-nucleating agents used in Examples 1-25.

[0150] Except that N,N′-diphenylhexanediamide (Example 26) or N,N′-diphenyloctanediamide (Example 27) was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The β-form contents of the resulting sheets are shown in Table 3 below.

[0151] Except that each of the amide compounds listed in Table 3 below (i.e., N,N′-diphenyl-butanediamide; N,N′-diphenyl-pentanediamide, N,N′-diphenyl-heptanediamide, N,N′-diphenyl-nonanediamide, N,N′-diphenyl-decanediamide and N,N′-diphenyl-terephthalamide) was used as the β-nucleating agent, the procedure of Example 1 was repeated to provide a sheet. The Inform contents of the resulting sheets are shown in Table 3 below.