JP3396904B2 - Polypropylene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polypropylene resin.
A method for improving the crystallinity and rigidity of a composition.

[0002]

2. Description of the Related Art Polypropylene-based polymers have excellent moldability, mechanical properties, electrical properties, etc., and are therefore applied to various fields as materials for film molding, sheet molding, blow molding, injection molding and the like. There is.

However, although the resin generally has excellent physical properties, there is a problem that the resin has low crystallinity and rigidity, and depending on a certain use, the resin has excellent original performance. The current situation is that its application is limited because it cannot be fully withdrawn.

Various attempts have been made so far for the purpose of improving the crystallinity and rigidity of polypropylene-based polymers.
For example, a method of adding a resin modifier such as a metal salt of a carboxylic acid, a metal salt of an aromatic carboxylic acid, a metal salt of an aromatic phosphoric acid, an amine salt or a metal salt of an aliphatic dicarboxylic acid, or a sorbitol derivative is known. ing.

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

[0006]

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

[0007]

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

That is, the method for improving the crystallinity and rigidity of the crystalline polypropylene-based resin molded product according to the present invention is to use a polypropylene-based resin in which the dicarboxylic acid amide compound represented by the general formula (1) and the general formula ( It is characterized by containing one or more amide compounds selected from the group consisting of amino acid amide compounds represented by 2).

[0009]

Embedded image R ² —NHCO—R ¹ —CONH—R ³
(1) [In the formula, R ¹ represents a saturated or unsaturated aliphatic, alicyclic or aromatic dicarboxylic acid residue having 1 to 24 carbon atoms. R
² , R ³ are the same or different, and are a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms, a naphthyl group, an anthryl group,

[Chemical 2]

[Chemical 3]

[Chemical 4] Or

[Chemical 5] Represents a group represented by. R ⁴ and R ⁵ are the same or different,
It represents a linear or branched alkyl group having 1 to 4 carbon atoms. X and Y are the same or different and each represents a nitro group or a carbon number of 1 to
4 alkoxy groups or

Embedded image represents a group represented by —COOR ⁶ . R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms. m and n each represent an integer of 2 to 4. o and p each represent an integer of 1 to 3. ]

[0010]

[0011]

Embedded image R ⁸ CONH-R ⁷ -CONH-R
⁹ (2) [In formula, R < ⁷ > represents a C1-C15 alicyclic or aromatic amino acid residue. R ⁸ and R ⁹ have the same meaning as R ² in formula (1) and may be the same or different. ]

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

[Chemical 17] [In the formula, R ¹ has the same meaning as described above. ] The aliphatic, alicyclic or aromatic dicarboxylic acid represented by or its anhydride, and general formula (1b)

[Chemical 18] Or general formula (1c)

[Chemical 19] [In the formula, R ² and R ³ have the same meanings as described above. ] One or two or more kinds of aliphatic, alicyclic or aromatic monoamines represented by the above formula can be easily prepared by amidation according to a conventionally known method.

As the aliphatic dicarboxylic acid, more specifically, malonic acid, diphenylmalonic acid, succinic acid, methylsuccinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Examples are 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid and 1,18-octadecanedioic acid.

Specific examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid and 1,3-adamantanedicarboxylic acid. To be done.

Specific examples of the aromatic dicarboxylic acid include p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid and terephthalic acid. 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 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,
Examples include 4'-isophthaloyldibenzoic acid and 4,4'-terephthaloyldibenzoic acid.

Specific examples of the aliphatic monoamine include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine. Examples include decylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, oleylamine and the like.

As the alicyclic monoamine, more specifically, dimethylcyclohexylamine, diethylcyclohexylamine, dipropylcyclohexylamine, diisopropylcyclohexylamine, dibutylcyclohexylamine, di-tert-butylcyclohexylamine,
Methylisopropylcyclohexylamine, trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, methoxycyclohexylamine, ethoxycyclohexylamine, butoxycyclohexylamine, dimethoxycyclohexylamine, diethoxycyclohexylamine, trimethoxycyclohexylamine, chlorocyclohexylamine, dichlorocyclohexylamine Amine, trichlorocyclohexylamine, bromocyclohexylamine, dibromocyclohexylamine, tribromocyclohexylamine, nitrocyclohexylamine, dinitrocyclohexylamine, methoxycarbonylcyclohexylamine, ethoxycarbonylcyclohexylamine, butoxycarbonylcyclo Hexylamine, amino decalin and the like.

Specific examples of the aromatic monoamine include dimethylaniline, diethylaniline, dipropylaniline, diisopropylaniline, dibutylaniline, di-tert-butylaniline, methylisopropylaniline, trimethylaniline, triethylaniline and tripropyl. Aniline, anisidine, ethoxyaniline,
Butoxyaniline, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, chloroaniline, dichloroaniline, trichloroaniline, bromoaniline,
Dibromoaniline, tribromoaniline, nitroaniline, dinitroaniline, aminobenzoic acid methyl ester, aminobenzoic acid ethyl ester, aminobenzoic acid propyl ester, aminobenzoic acid isopropyl ester, aminobenzoic acid butyl ester, aminobenzoic acid isobutyl ester, 1 Examples include -naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like.

Among the amide compounds represented by the general formula (1), more effective compounds include glutaric acid bis (2,4,6-trimethylanilide) and adipic acid bis (2,5-dimethylanilide). , Bis adipate (2,
6-dimethylanilide), adipic acid bis (2,6-diethylanilide), adipic acid bis (2,4,6-trimethylanilide), adipic acid bis (1-naphthylamide), p-phenylenediacetate bis (2 , 6-diethylanilide), 1,4-cyclohexanedicarboxylic acid bis (2,6-dimethylanilide), and the like.

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

The amino acid-based amide compound represented by the general formula (2) is represented by the following general formula _{^{(2 a) H 2 N-}} R 7 -COOH (2a) [ wherein, ^{R 7} is as defined above. Aliphatic represented by, alicyclic or aromatic amino acids and formula ^{(2 b) R 8 -COOH (} 2b) [ wherein, ^{R 8} is as defined above. One or more aliphatic represented _{by], 9 -NH 2 (2c)} [ in the formula alicyclic or aromatic monoamines and general formula (2 ^{c) R,} R ⁹ is a as defined above . ] One or two or more kinds of aliphatic, alicyclic or aromatic monocarboxylic acids represented by the above formula can be easily prepared by amidation according to a conventionally known method.

As the aliphatic amino acid, more specifically,
Aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutyric acid, β
-Aminobutyric acid, γ-aminobutyric acid, α-amino-α-methylbutyric acid, γ-amino-α-methylenebutyric acid, α-aminoisobutyric acid, β-aminoisobutyric acid, α-amino-n-valeric acid, δ-amino- n-valeric acid, β-aminocrotonic acid,
α-amino-β-methylvaleric acid, α-aminoisovaleric acid, 2-amino-4-pentenoic acid, α-amino-
n-caproic acid, 6-aminocaproic acid, α-aminoisocaproic acid, 7-aminoheptanoic acid, α-amino-n
-Caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like are exemplified.

As the alicyclic amino acid, more specifically,
1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2
-Norbornanecarboxylic acid and the like are exemplified.

As the aromatic amino acid, more specifically,
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-
Amino hippuric 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,
Examples thereof include 7-amino-2-naphthoic acid and 8-amino-2-naphthoic acid.

The starting material is monoamines of the general formula (2) amide compounds represented by the Ru raw material monoamine same der an amide compound represented by the general formula (1). Also,
Nocarboxylic acids are more suitable as aliphatic monocarboxylic acids.
Physically, acetic acid, propionic acid, butyric acid, valeric acid, capro
Acid, enanthate, caprylic acid, pelargonic acid, capri
Acid, undecyl acid, lauric acid, tridecyl acid, milli
Stearic acid, pentadecyl acid, palmitic acid, heptadecyl
Acid, stearic acid, nonadecanoic acid, acrylic acid, black
Tonic acid, oleic acid, elaidic acid, sorbic acid, lino
Examples thereof include phosphoric acid, linoleic acid and pivalic acid. Fat
As the cyclic monocarboxylic acid, more specifically, dimethyl
Cyclohexane carboxylic acid, diethyl cyclohexane
Rubonic acid, di-tert-butylcyclohexanecarboxylic
Acid, trimethylcyclohexanecarboxylic acid, methoxy
Chlorohexanecarboxylic acid, ethoxycyclohexanecal
Boric acid, dimethoxycyclohexanecarboxylic acid, diet
Xycyclohexanecarboxylic acid, trimethoxycyclohexyl
Xancarboxylic acid, triethoxycyclohexanecarbo
Acid, chlorocyclohexanecarboxylic acid, dichlorosic
Rohexanecarboxylic acid, bromocyclohexanecarboxylic acid
Acid, dibromocyclohexanecarboxylic acid, tribromosilane
Chlorohexanecarboxylic acid, nitrocyclohexanecarbo
Acid, dinitrocyclohexanecarboxylic acid, decalinka
Rubonic acid and the like are exemplified. As an aromatic monocarboxylic acid
And more specifically, dimethyl benzoic acid, diethyl benzoate
Aromatic acid, di-tert-butylbenzoic acid, trimethylbenzoic acid
Acid, methoxybenzoic acid, ethoxybenzoic acid, dimethoxy
Benzoic acid, diethoxybenzoic acid, trimethoxybenzoic acid
Acid, triethoxybenzoic acid, chlorobenzoic acid, dichloro
Benzoic acid, bromobenzoic acid, dibromobenzoic acid, trib
Lomobenzoic acid, Nitrobenzoic acid, Dinitrobenzoic acid, Te
Lephthalic acid monomethyl ester, 1-naphthoic acid, 2-
Examples include naphthoic acid and 9-carboxyanthracene.
It

Among the amide compounds represented by the general formula (2) , more effective compounds include p- (N-butylcarbonylamino) benzoic acid butylamide and 4- [N-
(2,4,6-Trimethylbenzoyl) aminomethyl]
Phenylacetic acid (2,4,6-trimethylanilide), 4
-[N- (2,4,6-trimethylbenzoylamino]]
Examples include cyclohexanecarboxylic acid (2,4,6-trimethylanilide) and the like.

The polypropylene resin used in the present invention is a polymer containing propylene as a constituent component, and is a propylene homopolymer, propylene and other α-olefins such as ethylene, butene-1, pentene-.
Random or block copolymers of 1,4-methylpentene-1, hexene-1, etc., vinyl acetate, etc. or the above polypropylene resin system and a small amount of thermoplastic resin such as high density polyethylene, polybutene, poly-4-methyl. A blend polymer with pentene or the like is exemplified, and particularly, the effect thereof is great for a propylene homopolymer and a propylene-ethylene block copolymer system resin.

As the catalyst applied for producing such a polymer, not only the generally used Ziegler-Natta type catalyst but also transition metal compounds (for example, titanium halides such as titanium trichloride and titanium tetrachloride) are used. It is also possible to use a catalyst system in which a catalyst in which (1) is held on a carrier containing magnesium halide as a main component such as magnesium chloride is combined with an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.).

Melt flow rate of polypropylene resin component (hereinafter abbreviated as "MFR". JIS K 67
58-1981) is appropriately selected according to the molding method used, and is usually about 0.1 to 200 g / 10 minutes, preferably about 0.5 to 100 g / 10 minutes.

The compounding amount of the amide compound according to the present invention is
It is not particularly limited as long as a predetermined effect can be obtained and can be appropriately selected, but is usually about 0.001 to 5 parts by weight, more preferably about 0.01 to 2 parts by weight, based on 100 parts by weight of the polypropylene resin. is there. When the amount is less than 0.001 part by weight, it is difficult to obtain a predetermined modifying effect, and when the amount is more than 5 parts by weight, a modifying effect commensurate with the blending amount cannot be expected, which is not practical. However, it is uneconomical and is not preferable in any case.

In the resin composition according to the present invention, if necessary, stabilizers (epoxy compounds etc.), antioxidants (phenolic compounds, phosphite ester compounds etc.), antibacterial agents,
UV absorbers (benzophenone compounds, benzotriazole compounds, etc.), heat stabilizers, light stabilizers (hindered amine compounds, etc.), neutralizing agents, antistatic agents, antiblocking agents, flame retardants, heavy metal deactivators, lubricants (Fatty acid metal salt), dispersant, peroxide (organic peroxide), organic / inorganic pigment, filler (talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), A foaming agent, an elastomer, a processing aid, a nucleating agent and the like can be added within a range that does not impair the effects of the present invention.

The polypropylene resin composition thus obtained has excellent moldability, toughness, and excellent transparency.

The polypropylene resin composition of the present invention comprises
The resin composition obtained by mixing the predetermined components using a conventionally known mixing device (Henschel mixer, ribbon blender, Banbury mixer, etc.) and melt-kneading with a single-screw or twin-screw extruder, etc. , Film, sheet,
Suitable as a resin material for small containers, syringes, daily necessities, automobile parts, containers, home appliances parts, non-woven fabrics, etc.
It is molded by various methods such as injection molding, extrusion molding, blow molding, etc. depending on the intended product.

[0040]

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

Preparation of Resin Composition : 100 parts by weight of a predetermined polypropylene resin is mixed with a predetermined amount of an amide compound, mixed with a Henschel mixer, and pelletized with a 20 mmφ uniaxial extruder.

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

Measurement of flexural modulus : The pellets obtained above are put into an injection molding machine to obtain a test piece having a thickness of 4 mm. The flexural modulus of this test piece is measured according to JIS K7203. The bending speed is 10 mm / min.

Examples 1 to 71 Propylene homopolymer powder (MFR = 14 g / 10
Min, hereinafter referred to as "resin 1". The crystallization temperature and flexural modulus of a resin composition prepared by adding 0.2 part by weight of a predetermined amide compound to 100 parts by weight were measured. The results obtained are shown in Table 1.

Comparative Example 1 The crystallization temperature and flexural modulus of the resin 1 itself were measured. The results obtained are shown in Table 1.

[Table 1]

[Table 2]

[Table 3]

Examples 72-78 Propylene-ethylene block copolymer powder (MFR
= 2 g / 10 minutes, hereinafter referred to as "resin 2". ) The crystallization temperature and the flexural modulus of a resin composition prepared by adding 0.2 part by weight of the amide compound shown in Table 2 to 100 parts by weight were measured. The results obtained are shown in Table 2.

Comparative Example 2 The crystallization temperature and the flexural modulus of the resin 2 itself were measured. The results obtained are shown in Table 2.

[Table 4]

Examples 79-85 Propylene-ethylene random copolymer powder (MFR
= 14 g / 10 minutes, hereinafter referred to as "resin 3". ) The crystallization temperature and flexural modulus of a resin composition prepared by adding 0.2 part by weight of the amide compound shown in Table 3 to 100 parts by weight were measured. The results obtained are shown in Table 2.

Comparative Example 3 The crystallization temperature and flexural modulus of the resin 3 itself were measured. The results obtained are shown in Table 3.

[Table 5]

[0050]

EFFECT OF THE INVENTION By blending the amide compound according to the present invention, a polypropylene resin composition having a high crystallization temperature and a greatly improved flexural modulus can be obtained.

Front page continuation (72) Inventor Masafumi Yoshimura, 13 Narajima Yakura-cho, Fushimi-ku, Kyoto-shi, Kyoto, Japan Shin-Nippon Rika Co., Ltd. (72) Inventor Hiroshi Kitagawa 13 Yaha-cho Yasima-jima, Fushimi-ku, Kyoto-shi, Kyoto Shin-Nihon Rika Co., Ltd. (72) Inventor, Yoshitaka Ryojima Yakura-cho, Fushimi-ku, Kyoto City, Kyoto Prefecture, Shin-Nippon Rika Co., Ltd. (56) References JP-A-60-192765 (JP, A) JP-A-51-114482 (JP, A) JP-A-50-12134 (JP, A) JP-A-6-128424 (JP, A) JP-A-5-287117 (JP, A) JP-A-5-262936 (JP, A) JP-A-6-107875 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/02-23/16 C08K 5/20 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A polypropylene-based resin having the general formula (1)
A dicarboxylic acid amide compound represented by
Contain one or more amide compounds selected from the group consisting of amino acid amide compounds represented by (2)
By allowing the crystalline polypropylene resin composition to
To improve the crystallinity and rigidity of the. Embedded image R ² —NHCO—R ¹ —CONH—R ³
(1) [In the formula, R ¹ represents a saturated or unsaturated aliphatic, alicyclic or aromatic dicarboxylic acid residue having 1 to 24 carbon atoms. R
² , R ³ are the same or different, and are linear or branched alkyl or alkenyl groups having 1 to 18 carbon atoms, naphthyl groups, anthryl groups, and [Chemical 3] [Chemical 4] Or [Chemical 5] Represents a group represented by. R ⁴ and R ⁵ are the same or different,
It represents a linear or branched alkyl group having 1 to 4 carbon atoms. X and Y are the same or different and each represents a nitro group or a carbon number of 1 to 1.
4 represents an alkoxyl group or a group represented by —COOR ⁶ . R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms. m and n each represent an integer of 2 to 4. o and p each represent an integer of 1 to 3. ] R ⁸ CONH-R ⁷ -CONH-R
⁹ (2) [In formula, R < ⁷ > represents a C1-C15 alicyclic or aromatic amino acid residue. R ⁸ and R ⁹ have the same meaning as R ² in formula (1) and may be the same or different. ] 2. The amount of amide compound compounded is polypropylene.
0.001 to 5 parts by weight per 100 parts by weight of resin
The crystalline polypropylene resin composition according to claim 1.
A method for improving the crystallinity and rigidity of a product.