DE69511273T2 - Polybutene-1 resin composition and method for accelerating crystal conversion - Google Patents

Description

Polybutene-1 resin composition and method for accelerating crystal transformation

The present invention relates to a polybutene-1 resin composition, and more particularly to a polybutene-1 resin composition capable of giving a molded article in which the crystal transformation peculiar to polybutene-1 resins, particularly the phase transformation from Form-II (tetragonal crystal modification) to Form-I (hexagonal crystal modification), is accelerated or enhanced.

Furthermore, the present invention relates to a polybutene-1 resin composition which can give a molded article in which specific crystal modifications, particularly Form-II and Form-III, are predominantly formed from the melt and then Form-II is converted to Form-I in a short period of time to give a molded article having crystals of Form-I and Form-III.

The present invention also relates to a process for accelerating the phase transition from Form II to Form I.

The present invention also relates to a process for the simple production of shaped articles containing crystals of Form I and Form III.

Since polybutene-1 resins are excellent in creep resistance, stress crack resistance, impact resistance, heat resistance and chemical resistance as well as flexible, their use has developed vigorously along with the use of polyethylene resins and polypropylene resins.

The polybutene-1 resin is a useful resin which has been widely used due to the excellent properties mentioned above. In particular, the resin can be molded into various pipes, filaments and films by extrusion molding, into cups and containers by injection molding, and into various bottles by blow molding.

However, the polybutene-1 resin forms various crystal modifications or crystal forms, and when the melt of the resin is cooled to the melting point or a lower temperature, the unstable Form-II or tetragonal crystal modification (hereinafter referred to as "F-II") is first formed and then gradually undergoes solid phase transformation to the Form-I or hexagonal crystal modification (hereinafter referred to as "FI") over time. The formation of F-II involves a higher degree of supercooling and the crystallization rate is low, which leads to a delay in the molding cycle. Furthermore, the conversion of F-II to FI occurs at a low rate and thus takes a longer time to complete the conversion, usually about one week to 10 days.

The crystal modification or crystal form having excellent properties considered to be commercially usable is F-I. On the other hand, there is a crystal modification having a low melting point (Form-III, hereinafter referred to as "F-III") which is probably rhombic and is obtained by precipitation from a solution thereof or by pouring the solution thereof.

The crystallization behavior peculiar to the polybutene-1 resin causes various problems in the molding process. For example, when extrusion molding is carried out, the molded pipes or sheets must be left at room temperature for a long period of time, partly because the F-II formed immediately after the molding process is flexible and the molded articles may deform when subjected to an external force such as during transportation, and partly because it is difficult to obtain molded articles having prescribed dimensions due to the difference in the degree of shrinkage among the molded articles when a large temperature fluctuation occurs during conversion. Thus, it is preferable that the molded articles be left in a warehouse substantially free from temperature fluctuation shortly after the completion of the molding process. The period of storage depends on the molding conditions, the shape and the volume of the molded product, but is usually several days. Thus, extrusion molding of polybutene-1 resin is very inefficient.

Furthermore, molecular orientation is likely to occur during injection molding, leading to anisotropy in strength, and the molded article may shrink by 1 to 2% after standing at room temperature, thereby becoming deformed or warped.

Consequently, the molding process of polybutene-1 resin requires that the conversion of F-II to F-I, which begins immediately after molding, be accelerated.

Known methods for accelerating crystallization of a melt of the polybutene-1 resin during the molding process include adding, for example, stearic acid amide, 1-naphthaleneacetamide, benzamide or N,N'-ethylenebisstearamide (US Patent Nos. 4,320,209, 4,322,503 and 4,645,792).

However, the compounds disclosed in these US patents do not produce the satisfactory crystallization acceleration effect and all of these patents disclose do not accelerate the crystallization rate from a melt of the polybutene-1 resin and do not teach the acceleration of the conversion of F-II to FI.

A known method for accelerating the conversion of F-II to F-I is the addition of polypropylene, polyethylene or sorbitol derivative. However, of these additives, polypropylene and polyethylene must be added in large amounts and this is likely to result in poor properties and the sorbitol derivative usually shows only insufficient effect.

Known methods further include a method which comprises dipping the molded product in an organic solvent immediately after molding and a method which comprises applying external stress such as pressure or stretching to the molded article immediately after molding.

However, immersion in an organic solvent is not practically advantageous because it requires special equipment and the solvent must be removed by drying and collecting after treatment. The application of external stress cannot be applied to an object with a complicated shape.

Increasing the production of the F-I fraction immediately after molding is effective for shortening the period of completion of the crystal phase transformation, inhibiting shrinkage of the molded article, preventing deformation or warpage of the molded article, and other purposes. However, no method for this has been proposed in essence.

In addition, an attempt has been made to impart low-temperature heat-sealing properties to the polybutene-1 resin by, for example, blending the polybutene-1 resin with an ethylene-propylene random copolymer. However, this raises a problem that the low-temperature heat-sealing properties deteriorate with the passage of time under the influence of crystal transformation of the polybutene-1 resin which occurs after the production of films.

Therefore, there is a demand for a polybutene-1 resin composition which can give a molded article exhibiting excellent low-temperature heat-sealing properties which would not deteriorate with the passage of time.

An object of the present invention is to provide a new and useful polybutene-1 resin composition which solves the above-mentioned problems in molding processability and gives a molded article in which the transformations of F-II to F-I proceed at a high rate and which produces F-I in a higher amount immediately after molding.

Another object of the present invention is to provide a polybutene-1 resin composition which gives a molded article exhibiting excellent low-temperature heat-sealing properties.

Under the circumstances, the present inventors conducted extensive studies to solve the above-mentioned problems and found that the contemplated results can be achieved by adding an amide compound of a certain structure to a polybutene-1 resin. The present invention has been completed on the basis of this new finding.

Thus, the polybutene-1 resin composition of the present invention comprises a polybutene-1 resin and one or more amide compounds selected from polycarboxylic acid type amide compounds represented by formula (1), polyamine type amide compounds represented by formula (2) and amino acid type amide compounds represented by formula (3):

(1) Polycarboxylic acid type amide compounds represented by the formula

R¹-(CONH-R²)k (1),

in which k is an integer from 2 to 6, preferably 2 to 4;

R¹ is a residue of a saturated or unsaturated aliphatic polycarboxylic acid with 2 to 30, preferably 3 to 16, carbon atoms, a residue of a saturated or unsaturated alicyclic polycarboxylic acid with 6 to 30, preferably 8 to 16, carbon atoms or a residue of an aromatic polycarboxylic acid with 8 to 36, preferably 8 to 22, carbon atoms; and

R² is an alkyl radical having 1 to 18, preferably 1 to 8, carbon atoms, an alkenyl radical having 2 to 18, preferably 2 to 8, carbon atoms, a cycloalkyl radical having 3 to 12, preferably 4 to 8, carbon atoms, a cycloalkenyl radical having 3 to 12, preferably 4 to 8, carbon atoms, a phenyl group, a naphthyl group, an anthryl group, a radical represented by the formula (a), (b), (c) or (d)

(in which R³, R⁵, R⁶ and R⁻ are the same or different and each represents an alkyl radical having 1 to 18, preferably 1 to 8, carbon atoms, an alkenyl radical having 2 to 18, preferably 2 to 8, carbon atoms, an alkoxy radical having 1 to 8, preferably 1 to 4, carbon atoms, a cycloalkyl radical having 3 to 12, preferably 4 to 8, carbon atoms, a phenyl group or a halogen atom,

R⁴ and R⁴ are the same or different and each represent a straight- or branched-chain alkylene radical having 1 to 4 carbon atoms,

i and n each represent an integer from 1 to 5, preferably 1 to 3, and

m and j each represent an integer from 0 to 5, preferably 0 to 3);

(2) Polyamine type amide compounds represented by the formula

R9 -(NHCO-R10 )p (2),

in which R⁹ is a residue of a saturated or unsaturated alicyclic polyamine with 3 to 25, preferably 6 to 13, carbon atoms or a residue of an aromatic polyamine with 6 to 25, preferably 6 to 17, carbon atoms,

R¹⁰ has the same meaning as R² in formula (1), and

p is an integer from 2 to 6, preferably 2 or 3, and

(3) Amide compounds of the amino acid type represented by the formula

(R¹²-NHCO)q-R¹¹-(NHCO-R¹³)r (3),

in which R¹¹ is a residue of a saturated aliphatic amino acid having 2 to 25, preferably 2 to 12, carbon atoms, a residue of an unsaturated aliphatic amino acid having 3 to 25, preferably 3 to 12, carbon atoms, a residue of a saturated or unsaturated alicyclic amino acid having 7 to 15, preferably 7 to 9, carbon atoms or a residue of an aromatic amino acid having 7 to 25, preferably 7 to 11, carbon atoms,

R¹² and R¹³ each have the same meaning as R² in formula (1) and are the same or different, and

q and r each represent an integer from 1 to 5, preferably 1 or 2, and the sum of q plus r is 2 to 6, preferably 2 to 4.

When the resin composition of the present invention is molded, the obtained molded product immediately after molding comprises F-I and F-II, and when the molded product is left at a temperature of about 0 to about 50°C, F-II quickly converts to F-I.

Thus, the present invention further provides a process for accelerating the crystal phase transformation of a polybutene-1 resin Form-II (tetragonal crystal modification) to Form-I (hexagonal crystal modification), the process comprising the steps of:

a) molding the polybutene-1 resin composition containing the polybutene-1 resin and at least one amide compound of the above formulas (1), (2) and (3) to obtain a molded product comprising Form-II and

b) maintaining the molded product at a temperature of about 0 to 50ºC, preferably 10 to 40ºC, to convert Form II to Form I.

The above-mentioned amide compounds may, as mentioned above, sometimes be added to polybutene-1 resin to produce Form-III. For example, when sulfonyldibenzoic acid dianilide such as 4,4'-sulfonyldibenzoic acid dianilide is added to polybutene-1 resin, a considerable amount of Form-III as well as Form-II is formed from the melt of the polybutene-1 resin composition. Furthermore, in a short period of time, the resulting Form-II is converted to Form-I to give a molded product comprising Form-I and a considerable amount of Form-III.

In this case, the relative proportions of the F-I and F-III crystal phases in the resulting molded article may vary depending on the molding conditions and the amount of the amide compound, but the amount of Form-I is usually about 1 to 99% by weight, particularly about 20 to 70% by weight, and the amount of Form-III is about 99 to 1% by weight, preferably about 80 to 30% by weight, based on the total amount of Form-I and Form-III.

Thus, the present invention provides a process for producing a molded article comprising Form I and Form III crystal modifications, the process comprising the steps of:

a) molding a polybutene-1 resin composition containing a polybutene-1 resin and sulfonyldibenzoic acid dianilide to obtain a molded product comprising Form-II and Form-III, and

b) maintaining the molded product at a temperature of about 0 to 50ºC, preferably about 10 to 40ºC, to convert Form II to Form I.

Now, it is possible to improve the low-temperature heat-sealing properties and the low-temperature heat-sealing properties after film production by using the above-mentioned resin composition of the present invention and stabilize the molded product produced therefrom because the molded product comprises, in addition to the crystals of F-I, crystals of F-III which have a melting point lower than the melting points of F-II and F-I and which undergo substantially no phase transformation at room temperature.

Until now, the use of F-III fraction-containing polybutene-1 resin composition or molded product was considered commercially disadvantageous because it was assumed It has been found that crystallization or precipitation from solution is the only method for producing F-III.

In this specification, F-I and F-II are identified by the X-ray diffraction method described by T. Oda et al. in Kobunshi Ronbunshu, 31, 2, 129-134 (1974), and F-III is identified by melting point and infrared spectra, it being known that the melting point and infrared spectra of F-I and F-II are different as described by Bert H. et al., J. Polym. Sci., Part C, 6, 43-51 (1964).

Polybutene-1 resin

The polybutene-1 resin for use in the present invention is a polymer mainly comprising butene-1, and specific examples thereof include a butene-1 homopolymer. Also usable are a copolymer comprising ethylene, propylene or like α-olefin (particularly C₄-C₈ α-olefin) as a minor comonomer, for example, butene-1-ethylene copolymer and butene-1-propylene copolymer.

Particularly preferred is a butene-1-ethylene copolymer. Such copolymers preferably comprise at least 60 weight percent, preferably at least 70 weight percent, more preferably at least 80 weight percent butene-1, based on the total amount of comonomers. In general, the butene-1-ethylene copolymer is preferred.

The stereoregularity of the homopolymer and the copolymer of butene-1 is preferably isotactic and syndiotactic, but the intended effect of the invention can also be produced when the atactic fraction is contained in a small amount.

The catalyst that can be used for producing such polymers includes not only Ziegler-Natta catalyst that is usually used, but also a combination of a catalyst such as that in which a transition metal compound (e.g., titanium halides such as titanium trichloride or titanium tetrachloride) is supported on a carrier mainly composed of magnesium halide such as magnesium chloride is combined with an alkylaluminum compound (e.g., triethylaluminum or diethylaluminum chloride) and a Kaminsky catalyst is also usable.

The melt flow rate (hereinafter referred to as "MFR" for short; measured according to JIS K 7210) (190°C, 2.16 kgf) of the crystalline polybutene-1 resin thus obtained can be suitably selected according to the molding method used, and is generally about 0.01 to 50 g/10 min., and preferably about 0.03 to 20 g/10 min.

Also suitable in the present invention are polymer mixtures comprising at least one of the above-mentioned homopolymer and copolymers of butene-1 and a minor proportion of a thermoplastic resin and/or an elastomer such as polyethylene, polypropylene, polyisobutylene and poly-4-methylpentene-1. These polymer blends typically comprise about 60 to 99 weight percent, preferably about 70 to 95 weight percent, of at least one member selected from the group consisting of homopolymer and copolymers of butene-1 and about 1 to 40 weight percent, preferably 5 to 30 weight percent, of at least one member selected from the group consisting of the above-mentioned thermoplastic resins and elastomers.

Amide compounds

Among the amide compounds represented by formulas (1), (2) and (3), the compound of formula (1) is generally preferred.

In the formula (1), R¹ is preferably a residue of a saturated aliphatic polycarboxylic acid having 3 to 16 carbon atoms, a residue of a saturated alicyclic polycarboxylic acid having 7 to 16 carbon atoms, or a residue of an aromatic polycarboxylic acid having 8 to 22 carbon atoms.

Likewise, k in formula (1) is preferably 2 or 3, more preferably 3.

Among the amide compounds of formula (1) in which k is 2, those of formula (1) are particularly preferred in which R¹ is a residue of a saturated aliphatic dicarboxylic acid having 4 to 10 carbon atoms, a residue of a saturated alicyclic dicarboxylic acid having 7 to 10 carbon atoms or a residue of an aromatic dicarboxylic acid having 8 to 17 carbon atoms, and R² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a residue formed by removing the amino group from an amine of formula (4) described later (in which R¹⁴ is an alkyl group having 1 to 8 carbon atoms or a halogen atom and s is an integer of 1 to 3), a residue formed by removing the amino group from an amine of formula (6) described later (in which R¹⁷ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and u is an integer of 1 to 3) or a group formed by removing the amino group from an amine of the formula (7) described later (in which R¹⁷ is an alkylene group having 1 to 3 carbon atoms, R¹⁷ is an alkyl group having 1 to 4 carbon atoms or a halogen atom and v is an integer of 0 to 3).

Among the amide compounds of formula (1) in which k is 2, more preferred are those of formula (1) in which R¹ is a residue obtained by removing all carboxyl residues from the dicarboxylic acid selected from p-phenylenediacetic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and 4,4-sulfonyldibenzoic acid (particularly preferred is a residue obtained by removing all carboxylic acid residues from 1,4-cyclohexanedicarboxylic acid), and R² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, phenyl group, a group formed by removing the amino group from an amine of the formula (4) described later (in which R¹⁴ is an alkyl group having 1 to 4 carbon atoms and s is an integer of 1 to 3), a group formed by removing the amino group from an amine of the formula (6) described later (in which R¹⁷ is an alkyl group having 1 to 4 carbon atoms and u is an integer of 1 to 3), or a group formed by removing the amino group from an amine of the formula (7) described later (in which R¹⁸ is a methylene group, R¹⁹⁸ is an alkyl group having 1 to 4 carbon atoms and v is an integer of 0 to 3) arises, is.

Among the amide compounds of formula (1) in which k is 3, those of formula (1) in which R¹ is a residue of a saturated aliphatic tricarboxylic acid having 6 to 10 carbon atoms, a residue of a saturated alicyclic tricarboxylic acid having 8 to 12 carbon atoms or a residue of an aromatic tricarboxylic acid having 9 to 12 carbon atoms, and R² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a residue formed by removing the amino group from an amine of formula (4) described later (in which R¹⁴ is an alkyl group having 1 to 8 carbon atoms or a halogen atom and s is an integer of 1 to 3), a residue formed by removing the amino group from an amine of formula (6) described later (in which R¹⁷ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and u is an integer of 1 to 3) or a group formed by removing the amino group from an amine of the formula (7) described later (in which R¹⁷ is an alkylene group having 1 to 3 carbon atoms, R¹⁷ is an alkyl group having 1 to 4 carbon atoms or a halogen atom and v is an integer of 0 to 3).

Among the amide compounds of the formula (1) in which k is 3, more preferable are those of the formula (1) in which R¹ is a group formed by removing all carboxylic acid groups from a tricarboxylic acid selected from trimesic acid, tricarballylic acid and 1,3,5-pentanetricarboxylic acid (particularly a group formed by removing all carboxylic acid groups from trimesic acid), and R² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, a phenyl group, a group formed by removing the amino group from an amine of the formula (4) described later (in which R¹⁴ is an alkyl group having 1 to 4 carbon atoms and s is an integer of 1 to 3), a group formed by removing the amino group from an amine of the formula (6) described later (in which R¹⁹⁷ is an alkyl group having 1 to 4 carbon atoms and u is an integer of 1 to 3), or a residue obtained by removing the amino group from an amine of the formula (7) described later (in which R¹⁸ is a methylene group, R¹⁸ is an alkyl radical having 1 to 4 carbon atoms and v is an integer from 0 to 3).

Preferred compounds of formula (2) are those of formula (2) in which p is 2 or 3, R9 is a residue of a saturated alicyclic di- or triamine having 6 to 13 carbon atoms or a residue of an aromatic di- or triamine having 6 to 13 carbon atoms, and R10 is an alkyl group having 2 to 9 carbon atoms, a cycloalkyl group having 6 or 7 carbon atoms, a phenyl group, a group formed by removing the carboxylic acid group from an acid of the formula (8) described later (in which R²⁰ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and w is an integer of 1 to 3), a group formed by removing the carboxylic acid group from an acid of the formula (10) described later (in which R²³ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and y is an integer of 1 to 3), or a group formed by removing the carboxylic acid group from an acid of the formula (11) described later (in which R²⁴ is an alkylene group having 1 to 3 carbon atoms, R²⁵ is a Alkyl radical with 1 to 4 carbon atoms or a halogen atom and z is an integer from 0 to 3).

More preferred compounds of formula (2) are those of formula (2) wherein p is 2, R9 is a residue formed by removing all amino groups from a diamine selected from p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4-diaminodiphenyl sulfone, 1,4-diaminocyclohexane and 4,4'-diaminodicyclohexylmethane, and R10 is an alkyl group having 2 to 5 carbon atoms, a cyclohexyl group, phenyl group, a group formed by removing the carboxylic acid group from an acid of the formula (8) described later (in which R²⁰ is an alkyl group having 1 to 4 carbon atoms and w is an integer of 1 to 3), a group formed by removing the carboxylic acid group from an acid of the formula (10) described later (in which R²³ is an alkyl group having 1 to 4 carbon atoms and y is an integer of 1 to 3), or a group formed by removing the carboxylic acid group from an acid of the formula (11) described later (in which R²⁴ is a methylene group, R²⁵ is an alkyl group having 1 to 4 carbon atoms and z is an integer of 0 to 3).

The preferred compounds of the formula (3) are those of the formula (3) in which R¹¹ is a residue of a saturated aliphatic amino acid having 2 to 8 carbon atoms, a residue of a saturated alicyclic amino acid having 7 to 9 carbon atoms or a residue of an aromatic amino acid having 7 to 11 carbon atoms, and R¹² and R¹³ each represent an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a group obtained by removing the amino group from an amine of the formula (4) described later (in which R¹⁴ is an alkyl group having 1 to 8 carbon atoms or a halogen atom, and s is an integer of 1 to 3), a group formed by removing the amino group from an amine of the formula (6) described later (in which R¹⁹7; is an alkyl group having 1 to 6 carbon atoms or a halogen atom, and u is an integer of 1 to 3), or a group formed by removing the amino group from an amine of the formula (7) described later (in which R¹⁹8; is an alkylene group having 1 to 3 carbon atoms, R¹⁹9; is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and v is an integer of 0 to 3), and q is 1 or 2, r is 1 or 2, and the sum of q and r is 2 or 3.

The more preferred compounds of formula (3) are those of formula (3) wherein R¹¹ is a residue formed by removing all amino group(s) and all carboxylic acid group(s) from an amino acid selected from β-aminopropionic acid, 8-aminocaprylic acid, aspartic acid, glutamic acid, p-aminomethylcyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, p-aminobenzoic acid, 5-amino-1-naphthoic acid, p-aminophenylacetic acid and 3,5-diaminobenzoic acid, R¹² and R¹³ each represent an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, phenyl group, a residue formed by removing the amino group from the amine of formula (4) described later (in which R¹⁴ is an alkyl group having 1 to 4 carbon atoms and s is an integer of 1 to 3), a group formed by removing the amino group from an amine of the formula (6) described later (in which R¹⁹7; is an alkyl group having 1 to 4 carbon atoms and u is an integer of 1 to 3), or a group formed by removing the amino group from an amine of the formula (7) described later (in which R¹⁹8; is a methylene group, R¹⁹9; is an alkyl group having 1 to 4 carbon atoms and v is an integer of 0 to 3), and q is 1 or 2, r is 1 or 2, and the sum of q and r is 2 or 3.

Processes for preparing amide compounds of formulas (1), (2) and (3) are described below.

(1) Polycarboxylic acid type amide compound of formula (1)

The polycarboxylic acid type amide compound of formula (1) can be easily prepared by amidation of an aliphatic, alicyclic or aromatic polycarboxylic acid of formula (1a) or the reactive derivative thereof such as an anhydride, a chloride or an ester with one or more aliphatic, alicyclic or aromatic monoamines of formula (1b):

R¹(COOH)k

(1a),

where R¹ and k are as defined above,

R²-NH₂ (1b),

where R² is as defined above,

getting produced.

The amidation reaction can be carried out in a conventional manner, and the following processes (i) to (iii) can be mentioned as typical examples.

(i) In an inert solvent, the polycarboxylic acid is reacted with the monoamine at about 60 to 200°C for about 2 to 10 hours. The monoamine is generally used in an amount of about 1 to 10 equivalents per one equivalent of the polycarboxylic acid.

In this process, an activator is preferably used to accelerate the reaction. The activator that can be used includes phosphorus pentoxide, polyphosphoric acid, phosphorus pentoxide-methanesulfonic acid, phosphorus ester (e.g., triphenylphosphite)-pyridine, phosphorus ester metal salt (e.g., lithium chloride), and triphenylphosphine hexachloroethane. Generally, about one equivalent of the activator is used per equivalent of the polycarboxylic acid.

(ii) In an inert solvent, a chloride of the polycarboxylic acid is reacted with the monoamine at about 0 to 100°C for about 1 to 5 hours. The monoamine is generally used in an amount of 1 to 5 equivalents per one equivalent of the polycarboxylic acid chloride.

(iii) In an inert solvent, an ester, particularly a polyalkyl(C1-3)ester of the polycarboxylic acid is reacted with the monoamine in the presence or absence of a catalyst at about 0 to 250°C for about 3 to 50 hours. The monoamine is generally used in an amount of about 1 to 20 equivalents per one equivalent of the polycarboxylic acid polyester.

The catalyst may be an acidic or basic catalyst commonly used in ester-amide exchange reactions, and is preferably a basic catalyst. Thus, lithium, sodium, potassium, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, and alkali metal amides such as sodium amide and lithium dipropylamide may be mentioned.

The catalyst is generally used in an equimolar amount based on the polycarboxylic acid.

The inert solvent which can be used for the above-mentioned processes (i), (ii) and (iii) includes benzene, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, acetonitrile, N,N- dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone.

The compounds obtained by the above processes (i), (ii) and (iii) are purified by conventional recovery and purification techniques such as chromatography, reprecipitation, recrystallization and fractional crystallization.

As the polycarboxylic acid of formula (1a) for use in the processes (i), (ii) and (iii), there may be mentioned the aliphatic, alicyclic or aromatic polycarboxylic acid corresponding to R¹. Thus, R¹ is preferably a residue formed by removing all carboxylic acid groups from any of the following aliphatic, alicyclic and aromatic polycarboxylic acids having 2 to 6 carboxylic acid groups.

The aliphatic polycarboxylic acid includes those having 2 to 30, preferably 3 to 16, more preferably 4 to 10 carbon atoms, such as oxalic 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, hereinafter referred to as "BTC"), 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, triethylenetetraaminehexaacetic acid, nitrilotripropionic acid, 1,6-hexanediaminetetraacetic acid and N-(2-carboxyethyl)iminodiacetic acid.

The alicyclic polycarboxylic acid includes those having 6 to 30, preferably 8 to 16 carbon atoms, such as 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 (hereinafter referred to as "SMCD"), bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid, cyclohexanehexacarboxylic acid, 5,6,9,10-tetracarboxytricyclo[6.2.2.02,7]dodeca-2,11-diene, which may have a lower alkyl group as a substituent (such as a methyl group in the 3-, 8-, 11- or 12-position), 1,2-cyclohexanediaminetetraacetic acid, 2,3,5-tricarboxycyclopentylacetic 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[4.2.2.02,5]-decane- 9-ene-3,4,7,8-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid (hereinafter referred to as "TDA") which may have a lower alkyl group as a substituent (such as a methyl group at the 1-, 5-, 6- or 7-position) and 2,3,4,5,6,7,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid.

The aromatic polycarboxylic acid includes those having 8 to 36, preferably 8 to 22, more preferably 8 to 17, carbon atoms, such as p-phenylenediacetic acid, p-phenylenediethanolic 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, benzenetricarboxylic acid such as trimesic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid (hereinafter referred to as "DSTC"), diphenylmethanetetracarboxylic acid, perylenetetracarboxylic acid, Naphthalenetetracarboxylic acid, 4,4'-dinaphthalic acid, benzidine-3,3'-dicarboxyl-N,N'-tetraacetic acid, diphenylpropanetetracarboxylic acid, anthracenetetracarboxylic acid, phthalocyaninetetracarboxylic acid, ethylene glycol trimellitic acid diester, benzenehexacarboxylic acid and glycerol trimellitic acid triester.

On the other hand, the monoamine of formula (1b) to be used in processes (i), (ii) and (iii) is the aliphatic, alicyclic or aromatic monoamine corresponding to R².

The aliphatic monoamine includes an alkylamine having 1 to 18, preferably 1 to 8, more preferably 3 to 6, carbon atoms and an alkenylamine having 2 to 18, preferably 2 to 8, carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, 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, octadecenylamine and allylamine.

The alicyclic monoamine includes cycloalkylamines and cycloalkenylamines each having 3 to 12, preferably 4 to 8, more preferably 5 or 6, carbon atoms, such as cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, Cyclooctylamine and cyclododecylamine and compounds represented by formulas (4) and (5).

wherein R¹⁴ is an alkyl radical having 1 to 18, preferably 1 to 8, more preferably 1 to 4, carbon atoms, an alkenyl radical having 2 to 18, preferably 2 to 8, more preferably 2 to 4, carbon atoms, an alkoxy radical having 1 to 8, preferably 1 to 4, carbon atoms, a cycloalkyl radical having 3 to 12, preferably 4 to 8, more preferably 5 or 6, carbon atoms, a phenyl group or a halogen atom such as chlorine and bromine, and s is an integer from 1 to 5, preferably 1 to 3.

The alicyclic monoamine of formula (4) includes monosubstituted alicyclic monoamines such as methylcyclohexylamine, ethylcyclohexylamine, propylcyclohexylamine, isopropylcyclohexylamine, tert-butylcyclohexylamine, n-butylcyclohexylamine, isobutylcyclohexylamine, sec-butylcyclohexylamine, n-amylcyclohexylamine, isoamylcyclohexylamine, sec-amylcyclohexylamine, tert-amylcyclohexylamine, hexylcyclohexylamine, heptylcyclohexylamine, octylcyclohexylamine, nonylcyclohexylamine, decylcyclohexylamine, undecylcyclohexylamine, dodecylcyclohexylamine, cyclohexylcyclohexylamine and phenylcyclohexylamine;

disubstituted alicyclic monoamines such as dimethylcyclohexylamine, diethylcyclohexylamine, dipropylcyclohexylamine, diisopropylcyclohexylamine, di-n-butylcyclohexylamine, di-sec-butylcyclohexylamine, di-tert-butylcyclohexylamine, di-n-amylcyclohexylamine, di-tert-amylcyclohexylamine and dihexylcyclohexylamine;

trisubstituted alicyclic monoamines such as trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, triisopropylcyclohexylamine, tri-n-butylcyclohexylamine, tri-sec-butylcyclohexylamine and tri-tert-butylcyclohexylamine; alkoxy-substituted aliphatic monoamines such as methoxycyclohexylamine, ethoxycyclohexylamine, dimethoxycyclohexylamine, diethoxycyclohexylamine, di-n-butoxycyclohexylamine, di-sec-butoxycyclohexylamine, di-tert-butoxycyclohexylamine, trimethoxycyclohexylamine and tri-n-butoxycyclohexylamine; and halogen-substituted alicyclic monoamines such as chlorocyclohexylamine, dichlorocyclohexylamine, methylchlorocyclohexylamine, trichlorocyclohexylamine, bromocyclohexylamine, dibromocyclohexylamine and tribromocyclohexylamine.

wherein R¹⁵ is a straight- or branched-chain alkylene radical having 1 to 4 carbon atoms, R¹⁵6 has the same meaning as R¹⁵4 in formula (4), t is an integer from 0 to 5, preferably 0 to 3.

The alicyclic monoamine of formula (5) includes cyclohexylmethylamine, methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, dimethoxycyclohexylmethylamine, chlorocyclohexylmethylamine, dichlorocyclohexylmethylamine, α-cyclohexylethylamine, β-cycloh exylethylamine, methoxycyclohexylethylamine, dimethoxycyclohexylethylamine, chlorocyclohexylethylamine, dichlorocyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine, γ-cyclohexylpropylamine and methylcyclohexylpropylamine.

The aromatic monoamine includes aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene and 2-aminoanthracene and compounds represented by formulas (6) and (7).

wherein R¹⁷ is an alkyl group having 1 to 18, preferably 1 to 8, more preferably 1 to 4, carbon atoms, an alkenyl group having 2 to 18, preferably 2 to 8, more preferably 2 to 4, carbon atoms, an alkoxyl group having 1 to 8, preferably 1 to 4, carbon atoms, a cycloalkyl group having 3 to 12, preferably 4 to 8, more preferably 5 or 6, carbon atoms, a phenyl group or a halogen atom such as chlorine, bromine and the like, and u is an integer from 1 to 5, preferably 1 to 3.

The aromatic monoamine of formula (6) includes toluidine, ethylaniline, propylaniline, cumidine, tert-butylaniline, n-butylaniline, isobutylaniline, sec-butylaniline, n-amylaniline, isoamylaniline, sec-amylaniline, tert-amylaniline, hexylaniline, heptylaniline, octylaniline , nonylaniline, decylaniline, undecylaniline, dodecylaniline, cyclohexylaniline, aminodiphenyl, aminostyrene, dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, triethylaniline, tripropylaniline, tri-tert -butylaniline, anisidine, ethoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, Tri-n-butoxyaniline, chloroaniline, dichloroaniline, trichloroaniline, bromoaniline, dibromoaniline and tribromoaniline.

wherein R¹⁸ has the same meaning as R¹⁵ in formula (5), R¹⁹9 has the same meaning as R¹⁸ in formula (6), v is an integer from 0 to 5, preferably 0 to 3.

The aromatic monoamine of formula (7) includes benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, chlorobenzylamine, dichlorobenzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine, dimethoxyphenylethylamine, chlorophenylethylamine, dichlorophenylethylamine, α-Ph enylpropylamine, β-phenylpropylamine, γ-phenylpropylamine and methylphenylpropylamine.

Among the amide compounds of formula (1) are compounds in which R¹ is a residue formed by removing all carboxylic acid groups of the polycarboxylic acid selected from p-phenylenediacetic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimesic acid, tricarballylic acid, DSTC (diphenylsulfonetetracarboxylic acid), TDA (3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid), BTC (1,2,3,4-butanetetracarboxylic acid) and 4,4'-sulfonyldibenzoic acid.

Particularly preferred are amide compounds of the formula (1) in which R¹ is a residue formed by removing all carboxylic acid groups from trimesic acid.

Of these, the compounds of formula (1) are recommended, in which R² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a group formed by removing the amino group from an amine of formula (4) in which R¹⁴ is an alkyl group having 1 to 8 carbon atoms or a halogen atom and s is an integer from 1 to 3, a group formed by removing the amino group from an amine of formula (6) in which R¹⁷ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and u is an integer from 1 to 3, or a group formed by removing the amino group from an amine of formula (7) in which R¹⁴ is is an alkylene radical having 1 to 3 carbon atoms, R¹⁹9 is an alkyl radical having 1 to 4 carbon atoms or a halogen atom and v is an integer from 0 to 3.

More preferred are the compounds of formula (1) in which R² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, phenyl group, a group which is formed by removing the amino group from an amine of formula (4) in which R¹⁴ is an alkyl group having 1 to 4 carbon atoms and s is an integer from 1 to 3, a group which is formed by removing the amino group from an amine of formula (6) in which R¹⁷ is an alkyl group having 1 to 4 carbon atoms and u is an integer from 1 to 3, or a group which is formed by removing the amino group from an amine of formula (7) in which R¹⁸ is a methylene group, R¹⁹ is an alkyl radical having 1 to 4 carbon atoms and v is an integer from 0 to 3.

Among the amide compounds of formula (1), in particular p-phenylenediacetic acid dianilide, p-phenylenediacetic acid dicyclohexylamide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, terephthalic acid dianilide, terephthalic acid dibenzylamide, 1,4-cyclohexanedicarboxylic acid dianilide, adipic acid bis(2,6-dimethylanilide), tricarballylic acid tris(2-methylcyclohexylamide), butanetetracarboxylic acid tetracyclohexylamide, butanetetracarboxylic acid tetrabenzylamide, trimesic acid tris(t-butylamide), trimesic acid tricyclohexylamide, trimesic acid tris(2-methylcyclohexylamide), trimesic acid tribenzylamide and 4,4'-sulfonyldibenzoic acid dianilide are proposed.

Particularly preferred among them are trimesic acid tris(t-butylamide), trimesic acid tricyclohexylamide, trimesic acid tris(2-methylcyclohexylamide) and trimesic acid tribenzylamide.

(2) Polyamine type amide compound of formula (2)

The polyamine type amide compound of formula (2) can be easily prepared by amidation of an alicyclic or aromatic polyamine of formula (2a) with one or more aliphatic, alicyclic or aromatic monocarboxylic acids of formula (2b) or the reactive derivatives thereof such as chlorides or esters:

R⁹-(NH₂)p (2a),

where R⁹ and p are as defined above,

R¹⁰-COOH (2b),

where R¹⁰ is as defined above,

be produced by a conventional process.

The amidation reaction is carried out in various conventional manners and the following methods may be mentioned as typical examples.

(i') In an inert solvent, the polyamine is reacted with the monocarboxylic acid at a temperature of about 60 to 200°C for about 2 to 10 hours. The monocarboxylic acid is generally used in an amount of about 1 to 10 equivalents per one equivalent of polyamine.

In this process, the activators exemplified in process (i) above are preferably used to accelerate the reaction. Generally, about one equivalent of activator is used per one equivalent of polyamine.

(ii') In an inert solvent, the polyamine is reacted with a chloride of the monocarboxylic acid at a temperature of about 0 to 100°C for about 1 to 5 hours. The monocarboxylic acid chloride is generally used in an amount of 1 to 3 equivalents per one equivalent of the polyamine.

(iii') In an inert solvent, the polyamine is reacted with an ester (particularly an alkyl (C13) ester) of the monocarboxylic acid in the presence or absence of a catalyst at about 0 to 250°C for about 3 to 50 hours. The monocarboxylic acid ester is generally used in an amount of about 1 to 20 equivalents per equivalent of the polyamine. The catalyst may be an acidic or basic catalyst exemplified in the above process (iii) which is commonly used in ester-amide exchange reactions and is preferably a basic catalyst.

The inert solvents which can be used for the above processes (i'), (ii') and (iii') are the same as those exemplified in the above processes (i), (ii) and (iii) for preparing the compound of formula (1).

The compounds obtained by the above processes can each be purified by conventional isolation and purification methods such as chromatography, reprecipitation, recrystallization and fractional crystallization. The polyamine of formula (2a) for use in processes (i'), (ii') and (iii') is an alicyclic or aromatic polyamine corresponding to R⁹. Thus, R⁹ is preferably a residue formed by removing all amino groups from one of the below alicyclic or aromatic polyamines having 2 to 6 amino groups.

The alicyclic polyamine includes those having 3 to 25, preferably 6 to 13 carbon atoms, such as 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, menthenediamine, melamine, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane and 1,2,4,5-tetraaminocyclohexane.

The aromatic polyamine includes those having 6 to 25, preferably 6 to 17, particularly 6 to 13, 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, 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'-diaxninodiphenylmethane 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'-dimethyldibenzyl, 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'-diaminodiphenylsulfone, 4,4'-dia minodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, o-toluidine sulfone, 2,7-diaminofluorene, 3,7-diamino-2-methoxyfluorene, bis-p-aminophenylaniline, 1,3-bis(4-aminophenylpropyl)benzene, 1,4-bis(4-am inophenylpropyl)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-tetra aminobenzene, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, para-rosaniline, 2,4,6-triaminophenol, 3,3'-diaminobenzidine, tris(4-aminophenyl)methane and 2,4,6-triaminopyrimidine.

On the other hand, the aliphatic monocarboxylic acid of the formula (2b) includes a saturated aliphatic carboxylic acid having 2 to 19, preferably 2 to 9, more preferably 2 to 5, carbon atoms and an unsaturated aliphatic carboxylic acid having 3 to 19, preferably 3 to 9, carbon atoms, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, acrylic acid, crotonic acid, oleic acid, elaidic acid, sorbic acid, linoleic acid, linolenic acid and pivalic acid.

The alicyclic monocarboxylic acid of the formula (2b) includes a saturated or unsaturated alicyclic monocarboxylic acid having 4 to 13, preferably 5 to 9, more preferably 6 or 7, carbon atoms, such as cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, methylcyclopentanecarboxylic acid, phenylcyclopentanecarboxylic acid, butylcyclohexenecarboxylic acid and methylcycloheptanecarboxylic acid, and compounds represented by the formulas (8) and (9).

wherein R²⁰ has the same meaning as R¹⁴ in formula (4) and w is an integer from 1 to 5, preferably 1 to 3.

The alicyclic monocarboxylic acid of the formula (8) includes, for example, methylcyclohexanecarboxylic acid, ethylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, pentylcyclohexanecarboxylic acid, hexylcyclohexanecarboxylic acid, phenylcyclohexanecarboxylic acid, chlorocyclohexanecarboxylic acid, bromocyclohexanecarboxylic acid, dimethylcyclohexanecarboxylic acid, di-tert-butylcyclohexanecarboxylic acid, Methoxycyclohexanecarboxylic acid, ethoxycyclohexanecarboxylic acid, dimethoxycyclohexanecarboxylic acid, diethoxycyclohexanecarboxylic acid, dichlorocyclohexanecarboxylic acid, trimethylcyclohexanecarboxylic acid, trimethoxycyclohexanecarboxylic acid and triethoxycyclohexanecarboxylic acid.

wherein R²¹ has the same meaning as R¹⁵ in formula (5), R²² has the same meaning as R²⁰ in formula (8) and x is an integer from 0 to 5, preferably 0 to 3.

The alicyclic monocarboxylic acid of the formula (9) includes, for example, cyclohexylacetic acid, methylcyclohexylacetic acid, methoxycyclohexylacetic acid, cyclohexylpropionic acid and cyclohexylbutyric acid.

The aromatic monocarboxylic acid includes benzoic acid, 1-naphthoic acid, 9-carboxyanthracene and compounds represented by formulas (10) and (11).

wherein R²³ has the same meaning as R¹⁷ in formula (6) and y is an integer from 1 to 5, preferably 1 to 3.

The aromatic monocarboxylic acid of the formula (10) includes, for example, methylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, p-tert-butylbenzoic acid, pentylbenzoic acid, hexylbenzoic 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 and triethoxybenzoic acid.

wherein R²⁴ has the same meaning as R²¹ in formula (9), R²⁵ has the same meaning as R²³ in formula (10) and z is an integer from 0 to 5, preferably 0 to 3.

The aromatic monocarboxylic acid of the formula (11) includes, for example, phenylacetic acid, methylphenylacetic acid, methoxyphenylacetic acid, phenylpropionic acid and phenylbutyric acid.

Among the amide compounds represented by formula (2), compounds of formula (2) in which R9 is a residue obtained by removing all amino groups from p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4-diaminodiphenyl sulfone, 1,4-diaminocyclohexane or 4,4'-diaminodicyclohexylmethane or alternatively from tris(4-aminophenyl)methane, 3,3'- diaminobenzidine and melamine are recommended.

Among them, preferred are the compounds of formula (2) in which R¹⁰ is an alkyl group having 2 to 9 carbon atoms, a cycloalkyl group having 6 or 7 carbon atoms, a phenyl group, a group formed by removing the carboxylic acid group from an acid of formula (8) in which R²⁰ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and w is an integer of 1 to 3, a group formed by removing the carboxylic acid group from an acid of formula (10) in which R²³ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and y is an integer of 1 to 3, or a group formed by removing the carboxylic acid group from an acid of formula (11) in which R²⁴ is is an alkylene radical having 1 to 3 carbon atoms, R²⁵ is an alkyl radical having 1 to 4 carbon atoms or a halogen atom and z is an integer from 0 to 3.

More preferred among them are the compounds of formula (2) wherein R¹⁰ is an alkyl group having 2 to 5 carbon atoms, a cyclohexyl group, a phenyl group, a group formed by removing the carboxylic acid group from an acid of formula (8) in which R²⁰ is an alkyl group having 1 to 4 carbon atoms and w is an integer of 1 to 3, a group formed by removing the carboxylic acid group from an acid of formula (10) in which R²³ is an alkyl group having 1 to 4 carbon atoms and y is an integer of 1 to 3, or a group formed by removing the carboxylic acid group from an acid of formula (11) in which R²⁴ is a methylene group, R²⁵ is is an alkyl radical having 1 to 4 carbon atoms and z is an integer from 0 to 3.

As compounds of formula (2), N,N'-dibenzoyl-1,4-diaminocyclohexane, N,N'-dicyclohexanecarbonyl-p-phenylenediamine, N,N'-dibenzoyl-1,5-diaminonaphthalene and N,N'-bis(p-methylbenzoyl)-1,4-diaminocyclohexane are highly recommended.

(3) Amino acid type amide compound of formula (3)

The amino acid type amide compound of formula (3) can be readily prepared by amidation of an aliphatic, alicyclic or aromatic amino acid of formula (3a), one or more aliphatic, alicyclic or aromatic monoamines of Formula (3b) and chloride or chlorides of one or more aliphatic, alicyclic or aromatic monocarboxylic acids of formula (3c):

(HOOC)q-R¹¹-(NH₂)r (3a),

where R¹¹, q, r and the sum of q and r are as defined above,

R¹²-NH₂ (3b),

where R¹² is as defined above, and

R¹³-COOH (3c),

where R¹³ is as defined above,

getting produced.

The amidation reaction can be carried out, for example, by reacting the amino acid of formula (3a) with about 1 equivalent, based on the amino groups of the amino acid, of the 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 carboxylic acid groups in the reaction product, of the monoamine and carrying out the reaction, preferably in the presence of the activator mentioned above with respect to process (i), at about 60 to 200°C for about 2 to 10 hours. The inert solvent can be one of the solvents mentioned above in connection with process (i) for the preparation of the compound of formula (1).

The compound obtained by the above process is purified by conventional recovery and purification methods such as chromatography, reprecipitation, recrystallization and fractional crystallization.

The amino acid of formula (3a) is an aliphatic, alicyclic or aromatic amino acid corresponding to R¹¹. Thus, R¹¹ is a residue obtained by removing all amino groups and all carboxylic acid groups from any of the following aliphatic, alicyclic and aromatic amino acids, the number of amino groups and carboxylic acid groups in total being 2 to 6.

The aliphatic amino acid includes those having a total of 2 to 6, preferably 2 to 4, carboxylic acid groups and amino groups and having 2 to 25, preferably 2 to 12, more preferably 2 to 5, carbon atoms, 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-methylbutyric 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, aspartamic acid, cysteine, glutamic acid, glutamine, ornithine, creatine, S-(carboxymethyl)cysteine and aminomalonic acid.

The alicyclic amino acid includes those having a total of 2 to 6, preferably 2 to 4, carboxylic acid groups and amino groups and having 7 to 15, preferably 7 to 9, carbon atoms, such as 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid and 1-amino-1,3-cyclohexanedicarboxylic acid.

The aromatic amino acid includes those having a total of 2 to 6, preferably 2 to 4, carboxylic acid groups and amino groups and having 7 to 25, preferably 7 to 15, more preferably 7 to 11, carbon atoms, 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, 3,5-diaminobenzoic acid and 4,4'-diamino-3,3'-dicarboxydiphenylmethane.

The monoamines for use as a starting material for the amide compounds of formula (3) are the same as the monoamines for use as starting material for the amide compounds of formula (1). The monocarboxylic acids for use as another starting material are the same as the monocarboxylic acids for use as a starting material for the amide compounds of formula (2).

Among the amide compound of formula (3), compounds are particularly recommended in which R¹¹ is a radical obtained by removing all amino groups and all carboxylic acid groups, from β-aminopropionic acid, 8-aminocaprylic acid, aspartic acid, glutamic acid, p-aminomethylcyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, p-aminobenzoic acid, 5-amino-1-naphthoic acid, p-aminophenylacetic acid or 3,5-diaminobenzoic acid.

Among them, preferred are the compounds of formula (3) in which R¹² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a group formed by removing the amino group from an amine of formula (4) in which R¹⁴ is an alkyl group having 1 to 8 carbon atoms or a halogen atom and s is an integer of 1 to 3, a group formed by removing the amino group from an amine of formula (6) in which R¹⁷ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and u is an integer of 1 to 3, or a group formed by removing the amino group from an amine of formula (7) in which R¹⁴ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and u is an integer of 1 to 3. is an alkylene group having 1 to 3 carbon atoms, R¹⁹9 is an alkyl group having 1 to 4 carbon atoms or a halogen atom and v is an integer from 0 to 3, R¹³ is an alkyl group having 2 to 9 carbon atoms, a cycloalkyl group having 6 or 7 carbon atoms, a phenyl group, a group obtained by removing the carboxylic acid group from an acid of the formula (8) in which R²⁰ is is an alkyl group having 1 to 6 carbon atoms or a halogen atom and w is an integer from 1 to 3, is a group formed by removing the carboxylic acid group from an acid of the formula (10) in which R²³ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and y is an integer from 1 to 3, or is a group formed by removing the carboxylic acid group from an acid of the formula (11) in which R²⁴ is an alkylene group having 1 to 3 carbon atoms, R²⁵ is an alkyl group having 1 to 4 carbon atoms or a halogen atom and z is an integer from 0 to 3, q is 1 or 2, r is 1 or 2 and the sum of q and r is 2 or 3.

Among them, more preferable are the compounds of formula (3) in which R¹² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, phenyl group, a group formed by removing the amino group from an amine of formula (4) in which R¹⁴ is an alkyl group having 1 to 4 carbon atoms and s is an integer of 1 to 3, a group formed by removing the amino group from an amine of formula (6) in which R¹⁷ is an alkyl group having 1 to 4 carbon atoms and u is an integer of 1 to 3, or a group formed by removing the amino group from an amine of formula (7) in which R¹⁸ is a methylene group, R¹⁹⁴ is a phenyl group. is an alkyl group having 1 to 4 carbon atoms and v is an integer from 0 to 3, and R¹³ is an alkyl group having 2 to 5 carbon atoms, a cyclohexyl group, phenyl group, a group formed by removing the carboxylic acid group from an acid of the formula (8) in which R²⁰ is an alkyl group having 1 to 4 carbon atoms and w is an integer from 1 to 3, a group formed by removing the carboxylic acid group from an acid of the formula (10) in which R²³ is an alkyl group having 1 to 4 carbon atoms and y is an integer from 1 to 3, or a radical formed by removing the carboxylic acid group from an acid of formula (11) in which R²⁴ is a methylene group, R²⁵ is an alkyl radical having 1 to 4 carbon atoms and z is an integer from 0 to 3, q is 1 or 2, r is 1 or 2 and the sum of q and r is 2 or 3.

Examples of the more preferred compounds of formulas (1), (2) and (3) are p-phenylenediacetic acid dianilide, p-phenylenediacetic acid dicyclohexylamide, tricarballylic acid tris(2-methylcyclohexylamide), adipic acid bis(2,6-dimethylanilide), butanetetracarboxylic acid tetracyclohexylamide, butanetetracarboxylic acid tetrabenzylamide, trimesic acid tris(t-butylamide), trimesic acid tricyclohexylamide, trimesic acid tris(2-methylcyclohexylamide), trimesic acid tribenzylamide, 1,4-cyclohexanedicarboxylic acid dianilide, N,N'-dibenzoyl-1,4-diaminocyclohexane, N,N'-dicyclohexanecarbonyl-p-phenylenediamine, N,N'- dibenzoyl-1,5-diaminonaphthalene, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, terephthalic acid dianilide, terephthalic acid dibenzylamide and p-(N-butylcarbonylamino)benzoic acid butylamide.

Polybutene-1 resin composition

The amide compounds of formulas (1) to (3) can be added during the polymerization of the polybutene-1 resin or added to the resin prepared above.

The amount of the amide compound for use in the present invention is about 0.001 to 10, preferably about 0.05 to 5, particularly 0.1 to 1, part by weight based on 100 parts by weight of the polybutene-1 resin. If the proportion of the amide compound is below 0.001 part by weight, the effect of accelerating the crystal transformation would not be obtained, while the use of the amide compound in excess of 10 parts by weight is not worthwhile for the same effect.

To the polybutene-1 resin composition of the present invention, known polyolefin resin modifiers may be added in the range that does not adversely affect the effects of the present invention according to the purpose and use.

The polyolefin resin modifiers include the additives described in "Self-Restrictive Requirements on Food-Contacting Articles Polyolefins And Certain Polymers, Third Edition" (September 1988), item "Polybutene-1", such as stabilizers, ultraviolet light absorbers, antioxidants, surfactants, lubricants, fillers, foaming agents, foaming aids, plasticizers, crosslinking agents, crosslinking promoters, antistatic agents, neutralizing agents, antiblocking agents agents, antifogging agents, flame retardants, dispersants and processing aids.

More specific examples are epoxy compounds such as epoxidized soybean oil and the like, phosphorus compounds such as tris(mixed mono- and dinonylphenyl)phosphite, sulfur compounds such as 3,3'-thiodipropionic acid dialkyl (any alkyl group having 12 to 18 carbon atoms) esters, phenol compounds such as tert-butyl group-substituted hydroxytoluenes, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, tocopherol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane,

Benzophenone compounds, benzotriazole compounds such as 2-(2'-hydroxy-3'- tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, phosphite compounds, non-ionic surfactants such as glyceryl fatty acid esters, sorbitan fatty acid esters (6 to 22 carbon atoms), polyoxyethylene(4 to 50 mol)alkyl(7 or more carbon atoms)phenyl ethers and N,N- bis(2-hydroxyethyl)fatty(8 to 18 carbon atoms)amines, aliphatic hydrocarbons such as liquid paraffin and hydrogenated polybutene, higher fatty acids with 8 to 22 carbon atoms, metal (Al, Ca, Mg and Zn) salts of higher fatty acids with 8 to 22 carbon atoms or ricinoleic acid, triglycerides, acetylated monoglycerides, waxes, silicone oils such as dimethylpolysiloxane and Methylphenylpolysiloxane, oxides such as magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, chromium oxide, iron oxide and zinc oxide,

Hydroxides such as magnesium hydroxide and aluminium hydroxide, carbonates such as calcium carbonate, sulphates such as barium sulphate,

Silicates, such as aluminosilicates (Ca), calcium aluminosilicate, clay, diatomaceous earth, kaolin, talc, mica, hydrotalcite, zeolite, perlite, glass fibers, colorants, such as titanium yellow, cobalt blue and ultramarine,

Metals such as aluminum,

Sulfides, such as zinc sulfide and

Polymers such as nylon, terephthalic acid trimethylhexamethylenediamine condensate, polyethylene terephthalate and polybutylene terephthalate.

The polybutene-1 resin composition thus obtained is excellent in crystallization (i.e., it crystallizes rapidly from the melt) and, when molded, gives a molded product comprising FI and F-II and then undergoes crystal transformation of F-II to FI at a high rate to give a molded article comprising FI when left to stand. In addition, the polybutene-1 resin composition of the present invention produces a large amount of FI. Therefore, the polybutene-1 resin composition of the present invention has excellent molding processability.

Furthermore, when certain amide compounds according to the present invention, particularly sulfonyldibenzoic acid dianilides such as 4,4'-sulfonyldibenzoic acid dianilide are used, a molded article comprising F-II and F-III is easily obtained by a conventional melt molding process, although it is not generally known that F-III is obtained by a melt molding process. When the obtained molded product is left to stand, F-II in the molded product quickly converts to F-I, thereby obtaining a molded article comprising F-I and F-III crystals.

In this case, the relative proportions of the F-I and F-III crystal phases of the resulting final molded article may vary depending on, for example, the molding conditions and the amount of the amide compound, but the amount of Form-I is usually about 1 to 99% by weight, particularly about 20 to 70% by weight, and the amount of Form-III is about 99 to 1% by weight, preferably about 80 to 30% by weight, based on the total amount of Form-I and Form-III.

The amount of sulfonyldibenzoic acid dianilides such as 4,4'-sulfonyldibenzoic acid dianilide used for the purpose of producing F-III is basically within the range specified above, that is, about 0.001 to 10, preferably about 0.05 to 5, especially 0.1 to 1 part by weight, based on 100 parts by weight of the polybutene-1 resin.

The final molded article produced from the resin composition of the present invention comprises (a) a crystal phase Form-I and an amorphous phase or (b) Form-I and -III and amorphous phase. In each case, the ratio of the amorphous fraction depends on the kind and grade of the polybutene-1 resin used and the molding conditions, but is generally about 20 to 80% by weight, particularly 30 to 70% by weight, based on the final molded article.

The polybutene-1 resin composition of the present invention is prepared by mixing the above-described components in a conventionally known mixer (Henschel mixer, ribbon blender, Banbury mixer or the like) and melting and kneading the mixture with a single or twin-screw extruder or the like. The obtained resin composition can be advantageously used as a resin material for, for example, pipes, thick and thin films, cups, bottles, consumer articles, automobile parts, containers, parts for electric appliances and nonwoven fabric, and is molded by a method suitable for the intended product, such as injection molding, extrusion molding, blow molding or press molding.

The molding can be carried out under usual conditions. For example, injection molding can be carried out at a resin temperature of about 140 to 300°C, preferably about 180 to 250°C, and at a mold temperature of about 10 to 80°C, preferably about 20 to 60°C. Extrusion molding is, for example, carried out at a resin temperature of about 140 to 300°C, preferably about 170 to 230°C, with molding for producing thin and thick films being carried out at a cooling roll temperature of about 10 to 80°C, preferably about 20 to 60°C. For the manufacture of pipes, cooling for solidification after size formation may be carried out by air cooling or water cooling and it is recommended that the melt be cooled to a temperature of about 10 to 80ºC, preferably about 20 to 60ºC.

After molding, the resulting molded product comprising F-II is left at a temperature of about 0 to 50°C, preferably about 10 to 40°C, to cause the conversion of F-II to F-I.

In the case of the composition of the invention comprising sulfonyldibenzoic acid dianilides such as 4,4'-sulfonyldibenzoic acid dianilide, the conditions under which the composition is molded and left are substantially the same as mentioned above.

Effect of the invention

As indicated above, the addition of at least one of the amide compounds of the present invention produces a polybutene-1 resin composition which undergoes the F-II to F-I crystal conversion at an increased rate, produces a large amount of F-I immediately after molding, and has remarkably improved molding processability.

Thus, a molded product obtained by molding the polybutene-1 resin composition of the present invention substantially completes the necessary conversion of F-II to F-I only by being left for a short period of time immediately after molding, and the period of time for being left is much shorter than that for polybutene-1 resin containing no amide compound. In particular, the period of time required to complete about 80% of the conversion of F-II to F-I (at which point the molded product is substantially a finished molded article and can therefore be transported satisfactorily without damaging the properties thereof) is greatly shortened, as will be apparent from the examples below.

Among a series of steps in a molding cycle, the step of leaving the molded product shortly after molding takes the longest time. Reducing the time required for this step results in a significant Improvement in productivity when the time reduction is on the order of at least several hours or even on the order of 1 to 2 hours and also the space in a warehouse where the molded product is left shortly after molding is saved. Thus, the present invention contributes to productivity and cost reduction to a great extent.

Furthermore, when a certain amide compound, particularly a sulfonyldibenzoic acid dianilide such as 4,4'-sulfonyldibenzoic acid dianilide is added as an amide compound to the polybutene-1 resin, a sufficient amount of F-III as well as F-II is formed from the melt of the polybutene-1 resin composition. In addition, the F-II converts to F-I in a short period of time to obtain a molded product containing F-I and a sufficient amount of F-III. Thus, a polybutene-1 resin composition which forms F-III by a melt molding process and is useful for imparting low-temperature heat-sealing properties can be obtained, as will be clear from the examples below.

Examples

The following examples and comparative examples illustrate the present invention in more detail.

In the following examples and comparative examples, the identification of F-I and F-II was carried out by the X-ray diffraction method described by T. Oda et al. in Kobunshi Ronbunshu, 31, 2, 129-134 (1974), and F-III was identified by the melting point and infrared spectra as described by Bert H. et al., J. Polym. Sci., Part C, 6, 43-51 (1964).

Examples 1-39

To 100 parts by weight of a commercially available isotactic polybutene-1 resin (MFR: 0.2 g/10 min.) was added each amount of amide compounds shown in Table 1. The mixture was ground and melted in a Henschel mixer and kneaded in a single-screw extruder with a diameter of 20 mm at 230 °C to obtain pellets.

The pellets were pressure molded at 200ºC and 100 kg/cm2 for 5 minutes and then the molded product was crystallized in a pressure molding machine for crystallization at 50ºC for 5 minutes to obtain a 0.2 mm thick film.

Then, about 5 mg of the polybutene-1 resin pressed into a film was melted by a DSC (differential scanning calorimeter) at 200 °C for 10 minutes and cooled at a rate of 20 °C/min. The crystallization temperature (TC) was measured and is shown in Table 1.

Comparison example 1

The crystallization temperature of the polybutene-1 resin as such as used in Example 1 was measured in the same manner as in Example 1. The results are shown in Table 1.

As is apparent from Table 1, the polybutene-1 resin composition of the invention comprising a polybutene-1 resin and the amide compound has a remarkably higher crystallization temperature than the polybutene-1 resin containing no amide compound. Therefore, the composition of the invention is advantageous in that it crystallizes more quickly from the melt and therefore the molding process is carried out more quickly.

The chemical structures of the amide compounds used in Examples 1 to 39 and other examples are shown in Table 2 below. Table 1

Table 2[EMI-TB] Table 2 (continued)[EMI-TB] Table 2 (continued)[EMI-TB] Examples 40-57

Pressed films, each comprising one of the amide compounds shown in Table 3, were prepared in the same manner as in Example 1 and left at room temperature.

Samples (about 5 mg each) were prepared by punching the pressed polybutene-1 resin film immediately after molding and after each 10 hours of keeping at room temperature. Each sample was placed in the sample holder of a DSC and heated in a nitrogen atmosphere at a rate of 10°C/min to perform differential scanning calorimetry.

The peak area of F-II (melting peak temperature: 111 to 116ºC) (hereinafter referred to as "S2") and the peak area of F-I (melting peak temperature: 122 to 128ºC) (hereinafter referred to as "S1") on the obtained DSC thermogram were determined, and then a curve showing the time course of the percentage of the F-I peak area based on the total peak area, that is, [S1/(S1 + S2)] × 100 (%) (hereinafter referred to as "Z") was obtained.

When the value of Z, which represents a part of F-I and the degree of transition from F-II to F-I, becomes about 80%, the crystal phase of the sample (molded product) is mostly composed of F-I and therefore the sample is practically a finished article and can be transported or handled. Therefore, the time (in hours) required for the sample to reach the Z value of 80% (hereinafter referred to as "80% conversion time") was determined from the obtained curve.

Table 3 shows the Z-value of each of the samples immediately after molding and 80% transformation time of each of the samples.

Comparison example 2

The Z value and 80% conversion time of the polybutene-1 resin used as such in Example 40 were determined in the same manner as in Example 40.

Table 3 shows the results. Table 3

It is clear from Table 3 that, compared with the polybutene-1 resin as such not containing the amide compound of the invention, the molded products prepared from the polybutene-1 resins of the invention had a larger proportion of F-I immediately after molding and more rapidly achieved the conversion of F-II to FI, as shown by a great reduction in the 80% conversion time. Therefore, the polybutene-1 resin compositions of the present invention are very advantageous in that they achieve a considerable improvement in productivity.

It is apparent from Table 3 that the use of the amide compounds of formula (1) in which R¹ is a trimesic acid residue achieves shorter 80% conversion time compared to the use of the same amount (0.5 parts by weight) of the compounds of formula (1) in which R¹ is a residue of tetracarboxylic acid or dicarboxylic acid.

Examples 58-67

0.25 parts by weight of each of the amide compounds shown in Table 4 was added to 100 parts by weight of a commercially available isotactic polybutene-1 resin (MFR: 0.05 g/10 min.). The mixture was ground and melted in a Henschel mixer and kneaded in a single-screw extruder with a diameter of 20 mm at 230 °C to obtain pellets.

The pellets were compression molded at 200ºC and 100 kg/cm2 for 5 minutes and then the molded product was crystallized in a cold press machine for 5 minutes to obtain a 0.2 mm thick film.

Then, about 5 mg of the molded polybutene-1 resin film was melted by a DSC at 200°C for 10 minutes and cooled at a rate of 20°C/min. The crystallization temperature (Tc) was measured.

The results are shown in Table 4.

Comparison example 3

The crystallization temperature of polybutene-1 resin as such used in Example 58 was measured in the same manner as in Example 58. The result is shown in Table 4. Table 4

Examples 68-74

A pressed film comprising each of the amide compounds shown in Table 5 was prepared in the same manner as in Example 58.

Samples (about 5 mg each) were obtained by punching the pressed polybutene-1 resin film immediately after molding and after each 10 hours of keeping at room temperature. Each sample was placed in the sample holder of a DSC and heated in a nitrogen gas atmosphere at 10°C/min to perform differential scanning calorimetry.

The Z value immediately after molding and the 80% conversion time were determined in the same manner as in Example 40. Table 5 shows the results.

Comparison example 4

The Z value immediately after molding and the 80% conversion time of the polybutene-1 resin used as such in Example 68 were determined in the same manner as in Example 68. The results are shown in Table 5. Table 5

Example 75

A polybutene-1 resin molded film was prepared in the same manner as in Example 1, except for using 0.5 parts by weight of 4,4'-sulfonyldibenzoic acid dianilide as an amide compound per 100 parts by weight of the polybutene-1 resin.

Five test pieces (about 5 mg each) were cut from the obtained film, and each of the samples was placed in the sample holder of a DSC, melted at 200°C for 10 minutes, and crystallized by cooling at a rate of 20°C/min to 25°C to prepare a crystallized product. The obtained crystallized products (samples) were left at a temperature of 25°C.

Using these samples, the melting peak was measured immediately after the sample was prepared (0 hours) and 24, 48, 72 and 96 hours thereafter by heating each of the samples at a rate of 10°C/min. using DSC to determine the proportions of F-I, F-II and F-III with respect to the melting peak area.

The melting temperature and peak area percentage of each of the crystals F-I, F-II and F-III were shown in Table 6.

Comparison example 5

The melting temperature and peak area percentage of each of the crystals of the polybutene-1 resin as such were determined in the same manner as in Example 75. The results were shown in Table 6. Table 6

As is clear from Table 6, the polybutene-1 resin composition comprising polybutene-1 resin and 4,4'-sulfonyldibenzoic acid dianilide can give a molded product containing F-III having a low melting point of 97°C in a high proportion, whereas the polybutene-1 resin as such not containing the amide compound does not produce a molded product containing such F-III.

The content of F-III does not substantially vary at room temperature. Therefore, the resulting finished molded article will have excellent low-temperature heat-sealing properties.

As also shown in Table 6, the molded product immediately after molding contained F-III and F-II, and then the F-II was converted to F-I quite rapidly to obtain a molded product containing F-III and F-I and free from F-II after about 60 hours by leaving at 25°C. Thus, the conversion of F-II to F-I is also accelerated compared with the polybutene-1 resin as such.

Example 76

A sample was prepared in the same manner as in Example 75, except for using a commercially available copolymer of butene-1 (as a main comonomer) and ethylene (MFR: 1.0 g/10 min), and the melting peak temperature and area percentage of each of the crystals were determined in the same manner as in Example 75.

Table 7 shows the results.

Comparison example 6

The melting peak temperature and area percentage of each of the crystals in the polybutene-1 resin as such used in Example 76 were determined in the same manner as in Example 75.

Table 7 shows the results. Table 7

As is clear from Table 7, when the butene-1-ethylene copolymer is used, the obtained resin composition containing 4,4'-sulfonyldibenzoic acid dianilide can give a molded product comprising F-III having a low melting point of 88°C.

Thus, the composition of Example 76 exhibits excellent low-temperature heat-sealing properties.

Claims (28)

1. A polybutene-1 resin composition comprising a polybutene-1 resin and an amide compound, wherein the amide compound is at least one member selected from: (1) Polycarboxylic acid type amide compounds represented by the formula (1) R¹-(CONH-R²)k (1), in which k is an integer from 2 to 6; R¹ 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 having 6 to 30 carbon atoms or a residue of an aromatic polycarboxylic acid having 8 to 36 carbon atoms; and R² is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, a group represented by the formula (a), (b), (c) or (d) (wherein R³, R⁵, R⁶ and R⁻ are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group or a halogen atom, R⁴ and R⁻ are the same or different and each represents a straight or branched chain alkylene group having 1 to 4 carbon atoms, i and n each represent an integer from 1 to 5, and m and j each represent an integer from 0 to 5); (2) Polyamine type amide compounds represented by the formula R9 -(NHCO-R10 )p (2), in which R⁹ is a residue of a saturated or unsaturated alicyclic polyamine having 3 to 25 carbon atoms or a residue of an aromatic polyamine having 6 to 25 carbon atoms, R¹⁰ has the same meaning as R² in formula (1), and p is an integer from 2 to 6, and (3) Amide compounds of the amino acid type represented by the formula (R¹²NHCO)q-R¹¹-(NHCO-R¹³)r (3), in which R¹¹ is a residue of a saturated aliphatic amino acid having 2 to 25 carbon atoms, a residue of an unsaturated aliphatic amino acid having 3 to 25 carbon atoms, a residue of a saturated or unsaturated alicyclic amino acid having 7 to 15 carbon atoms or a residue of an aromatic amino acid having 7 to 25 carbon atoms, R¹² and R¹³ each have the same meaning as R² in formula (1) and are the same or different, and q and r each represent an integer from 1 to 5 and the sum of q plus r is 2 to 6. 2. The polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound represented by the formula (1) in which R¹ is a residue of a saturated aliphatic polycarboxylic acid having 4 to 10 carbon atoms, a residue of a saturated alicyclic polycarboxylic acid having 8 to 16 carbon atoms, or a residue of an aromatic polycarboxylic acid having 8 to 17 carbon atoms. 3. The polybutene-1 resin composition according to claim 1, wherein R¹ is a residue formed by removing all carboxylic acid groups from a polycarboxylic acid selected from p-phenylenediacetic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimesic acid, tricarballylic acid, DSTC (diphenylsulfonetetracarboxylic acid), TDA (3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid), BTC (1,2,3,4-butanetetracarboxylic acid) and 4,4'-sulfonyldibenzoic acid. 4. The polybutene-1 resin composition according to claim 1, wherein R¹ is a residue formed by removing all carboxylic acid groups from trimesic acid. 5. Polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound of the formula (1) in which k 3 is, R¹ is a residue of a saturated aliphatic tricarboxylic acid having 6 to 10 carbon atoms, a residue of a saturated alicyclic tricarboxylic acid having 8 to 12 carbon atoms or a residue of an aromatic tricarboxylic acid having 9 to 12 carbon atoms, and R² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 8 carbon atoms or a halogen atom, and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is an alkylene group having 1 to 3 carbon atoms, R⁶ is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and j is an integer from 0 to 3. 6. Polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound of the formula (1) in which k 3 is, R¹ is a radical formed by removing all carboxylic acid groups from a tricarboxylic acid selected from the group consisting of trimesic acid, tricarballylic acid and 1,3,5-pentanetricarboxylic acid, and R² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 4 carbon atoms and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 4 carbon atoms and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is a methylene group, R⁶ is an alkyl group having 1 to 4 carbon atoms and j is an integer from 0 to 3. 7. Polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound of the formula (1) in which k 2 is, R¹ is a residue of a saturated aliphatic dicarboxylic acid having 4 to 10 carbon atoms, a residue of a saturated alicyclic dicarboxylic acid having 7 to 10 carbon atoms or a residue of an aromatic dicarboxylic acid having 8 to 17 carbon atoms, and R² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 8 carbon atoms or a halogen atom and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is an alkylene group having 1 to 3 carbon atoms, R⁶ is an alkyl group having 1 to 4 carbon atoms or a halogen atom and j is an integer from 0 to 3. 8. Polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound of the formula (1) in which k 2 is, R¹ is a radical formed by removing all carboxylic acid groups from a dicarboxylic acid selected from p-phenylenediacetic acid, adipic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and 4,4'-sulfonyldibenzoic acid, and R² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 4 carbon atoms and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 4 carbon atoms and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is a methylene group, R⁶ is an alkyl group having 1 to 4 carbon atoms and j is an integer from 0 to 3. 9. The polybutene-1 resin composition according to claim 1, wherein the amide compound is sulfonyldibenzoic acid dianilide. 10. The polybutene-1 resin composition according to claim 9, wherein the amide compound is 4,4'-sulfonyldibenzoic acid dianilide. 11. The polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound represented by formula (2) in which R⁹ represents a residue of a saturated alicyclic polyamine having 6 to 15 carbon atoms or a residue of an aromatic polyamine having 6 to 17 carbon atoms. 12. The polybutene-1 resin composition according to claim 1, wherein the amide compound is at least one amide compound represented by formula (2) in which R⁹ is a radical resulting from removal of all amino groups from p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, tris(4-aminophenyl)methane, 3,3'-diaminobenzidine or melamine. 13. The polybutene-1 resin composition according to claim 1, wherein the amide compound comprises at least one amide compound represented by formula (2) in which p is 2 or 3, R⁹ is a residue of a saturated alicyclic di- or triamine having 6 to 13 carbon atoms or a residue of an aromatic di- or triamine having 6 to 13 carbon atoms, and R¹⁰ is an alkyl group having 2 to 9 carbon atoms, a cycloalkyl group having 6 or 7 carbon atoms, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is an alkylene group having 1 to 3 carbon atoms, R⁸ is an alkyl group having 1 to 4 carbon atoms or a halogen atom and j is an integer from 0 to 3. 14. The polybutene-1 resin composition according to claim 1, wherein the amide compound comprises at least one amide compound represented by formula (2) in which p 2 is, R⁹ is a residue formed by removing all amino groups from a diamine selected from p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 1,4-diaminocyclohexane and 4,4'-diaminodicyclohexylmethane, and R¹⁰ is an alkyl group having 2 to 5 carbon atoms, a cyclohexyl group, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 4 carbon atoms and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 4 carbon atoms and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is a methylene group, R⁸ is an alkyl group having 1 to 4 carbon atoms and j is an integer from 0 to 3. 15. The polybutene-1 resin composition according to claim 1, wherein the amide compound is an amide compound represented by formula (3) in which R¹¹ is a residue of a saturated aliphatic amino acid having 2 to 12 carbon atoms, a residue of a alicyclic amino acid having 7 to 9 carbon atoms or a residue of an aromatic amino acid having 7 to 15 carbon atoms. 16. The polybutene-1 resin composition according to claim 1, wherein the amide compound is an amide compound represented by formula (3) in which R¹¹ is a residue of a saturated aliphatic amino acid having 2 to 5 carbon atoms, a residue of an alicyclic amino acid having 7 to 9 carbon atoms, or a residue of an aromatic amino acid having 7 to 11 carbon atoms, q is 1 or 2, r is 1 or 2, and the sum of q and r is 2 or 3. 17. The polybutene-1 resin composition according to claim 1, wherein the amide compound is an amide compound represented by formula (3) in which R¹¹ represents a residue formed by removing all amino groups and all carboxylic acid groups from β-aminopropionic acid, 8-aminocaprylic acid, aspartic acid, glutamic acid, p-aminomethylcyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, 3,5-diaminocyclohexanecarboxylic acid, p-aminobenzoic acid, 5-amino-1-naphthoic acid, p-aminophenylacetic acid, 3,5-diaminobenzoic acid or 4,4'-diamino-3,3'-dicarboxydiphenylmethane. 18. The polybutene-1 resin composition according to claim 1, wherein the amide compound is an amide compound represented by formula (3) in which R¹¹ represents a residue formed by removing all amino groups and all carboxylic acid groups from β-aminopropionic acid, aspartic acid, glutamic acid, 4-aminocyclohexanecarboxylic acid or p-aminobenzoic acid. 19. A polybutene-1 resin composition according to claim 1, wherein the amide compound is an amide compound represented by formula (3) in which R¹² is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 8 carbon atoms or a halogen atom and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 6 carbon atoms or a halogen atom and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is an alkylene group having 1 to 3 carbon atoms, R⁶ is an alkyl group having 1 to 4 carbon atoms or a halogen atom and j is an integer from 0 to 3, R¹³ is an alkyl radical having 2 to 9 carbon atoms, a cycloalkyl radical having 6 or 7 carbon atoms, a phenyl group, a group of formula (a) in which R³ is an alkyl radical having 1 to 6 carbon atoms or a halogen atom and i is an integer from 1 to 3, a group of formula (c) in which R6 is an alkyl radical having 1 to 6 carbon atoms or a halogen atom and n is an integer from 1 to 3, or a group of formula (d) in which R7 is an alkylene radical having 1 to 3 carbon atoms, R8 is an alkyl radical having 1 to 4 carbon atoms or a halogen atom and j is an integer from 0 to 3, q is 1 or 2, r is 1 or 2 and the sum of q and r is 2 or 3. 20. The polybutene-1 resin composition according to claim 1, wherein the amide compound is an amide compound represented by formula (3) in which R¹² is an alkyl group having 3 or 4 carbon atoms, a cyclohexyl group, a phenyl group, a group of formula (a) in which R³ is an alkyl group having 1 to 4 carbon atoms and i is an integer from 1 to 3, a group of formula (c) in which R⁶ is an alkyl group having 1 to 4 carbon atoms and n is an integer from 1 to 3, or a group of formula (d) in which R⁷ is a methylene group, R⁶ is an alkyl group having 1 to 4 carbon atoms and j is an integer from 0 to 3, R¹³ is an alkyl group having 2 to 5 carbon atoms, a cyclohexyl group, a phenyl group, a group of the formula (a) in which R³ is an alkyl group having 1 to 4 carbon atoms and i is an integer from 1 to 3, a group of the formula (c) in which R⁶ is an alkyl group having 1 to 4 carbon atoms and n is an integer from 1 to 3, or a group of the formula (d) in which R⁷ is a methylene group, R⁶ is an alkyl group having 1 to 4 carbon atoms and j is an integer from 0 to 3, q is 1 or 2, r is 1 or 2 and the sum of q and r is 2 or 3. 21. The polybutene-1 resin composition according to claim 1, wherein the amide compound comprises at least one compound selected from p-phenylenediacetic acid dianilide, p-phenylenediacetic acid dicyclohexylamide, tricarballylic acid tris(2-methylcyclohexylamide), adipic acid bis(2,6-dimethylanilide), butanetetracarboxylic acid tetracyclohexylamide, butanetetracarboxylic acid tetrabenzylamide, trimesic acid tris(t-butylamide), trimesic acid tricyclohexylamide, trimesic acid tris(2-methylcyclohexylamide), trimesic acid tribenzylamide, 1,4-cyclohexanedicarboxylic acid dianilide, N,N'-dibenzoyl-1,4-diaminocyclohexane, N,N'-dicyclohexanecarbonyl-p-phenylenediamine, N,N'-dibenzoyl-1,5-diaminonaphthalene, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, terephthalic acid dianilide, terephthalic acid dibenzylamide and p-(N-butylcarbonylamino)benzoic acid butylamide. 22. A polybutene-1 resin composition according to any one of claims 1 to 21, which comprises 0.001 to 10 parts by weight of the amide compound based on 100 parts by weight of the polybutene-1 resin. 23. The polybutene-1 resin composition according to any one of claims 1 to 22, wherein the polybutene-1 resin is a butene-1 homopolymer, a copolymer of butene-1 and another -olefin containing at least 60% by weight of butene-1, or a polymer mixture comprising (a) at least one member selected from the butene-1 homopolymer and the copolymer as a major component and (b) at least one member selected from thermoplastic resins and elastomers as a minor component. 24. A process for accelerating the crystal phase transformation of a polybutene-1 resin from Form-II (tetragonal crystal modification) to Form-I (hexagonal crystal modification), the process comprising the steps of: a) molding the polybutene-1 resin composition containing the polybutene-1 resin and at least one amide compound of the formulas (1), (2) or (3) according to any one of claims 1 to 21 to obtain a molded product comprising Form-II and b) Maintaining the molded product at a temperature of about 0 to 50ºC to convert Form II to Form I. 25. The method of claim 24, wherein the composition comprises 0.001 to 10 parts by weight of the amide compound based on 100 parts by weight of the polybutene-1 resin. 26. The process of claim 24 or 25, wherein the polybutene-1 resin is a butene-1 homopolymer, a copolymer of butene-1 and another α-olefin containing at least 60% by weight of butene-1, or a polymer blend comprising (i) at least one member selected from the butene-1 homopolymer and the copolymer as a major component and (ii) at least one member selected from the group consisting of thermoplastic resins and elastomers as a minor component. 27. A process for producing a shaped article comprising Form I and Form III crystal modifications, the process comprising the steps of: a) molding a polybutene-1 resin composition containing a polybutene-1 resin and sulfonyldibenzoic acid dianilide to obtain a molded product comprising Form-II and Form-III, and b) Maintaining the molded product at a temperature of about 0 to 50ºC to convert Form II to Form I. 28. The method of claim 27, wherein the sulfonyldibenzoic acid dianilide is 4,4'-sulfonyldibenzoic acid dianilide.