JP3374419B2 - Crystalline polypropylene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a crystalline polypropylene resin composition containing a nucleating agent capable of forming a large amount of β type crystal structure , and a crystalline polypropylene resin molded article.
To increase the β crystal content of the.

[0002]

2. Description of the Related Art For crystalline polypropylene, α, β,
The γ and δ transformations and the smectic transformation that occurs when the molten polypropylene is rapidly cooled are known. Of these, the β-modification (hereinafter referred to as “β-crystal”) has a lower melting point and a lower density than the α-modification (hereinafter referred to as “α-crystal”) found in conventional general-purpose natural pellets. It has interesting properties for application, such as different crystal states and fracture states (Polymer Chemistry, 30 , 694-698, (1978)).

As a method for producing β crystals, there are a method of crystallizing molten polypropylene under a temperature gradient and a method of adding and mixing a small amount of a nucleating agent (hereinafter referred to as “β crystal nucleating agent”). The latter method is more practical because it takes time and only a small amount of sample can be obtained.

As such β crystal nucleating agent, γ-quinacridone has been known so far (POLYMERLETTERS, 6 , 539-546,
(1968)). However, when the nucleating agent is applied, the resulting product has a drawback that it is colored red and special equipment and operation are required for mixing with the polymer.

The present invention eliminates the disadvantages of quinacridone compounds, is excellent in hue, and is a practical compound prepared by blending a novel β crystal nucleating agent capable of efficiently obtaining a product containing a large amount of β crystal polypropylene. An object of the present invention is to propose a novel crystalline polypropylene resin composition.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies as a result of proposing a β crystal nucleating agent capable of achieving such a problem.
It was found that an amide compound having a specific structure can exert a predetermined effect, and the present invention has been completed based on such findings.

That is, the crystalline polypropylene resin composition according to the present invention is characterized by containing the amide compound represented by the general formula (1).

Embedded image R ² —CONH—R ¹ —NHCO—R ³ (1) [wherein, R ¹ is an aliphatic diamine residue having 1 to 24 carbon atoms,
Represents an alicyclic diamine residue or an aromatic diamine residue (excluding a xylylenediamine residue), and R ² and R ³ are the same or different and are a cycloalkyl group having 3 to 14 carbon atoms,
A cycloalkenyl group,

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5] (Wherein R ¹ is an aliphatic divalent group having 1 to 24 carbon atoms)
In the case of amine residue, cycloalkyl having 3 to 14 carbon atoms
Groups, cycloalkenyl groups and

[Chemical 3] Excludes groups represented by. ) Represents. R ⁴ and R ⁵ represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ⁶ and R ⁷ each represent a linear or branched chain having 1 to 3 carbon atoms. Represents an alkylene group. ] Also,
The crystalline polypropylene-based resin molding of the present invention contains β crystal.
The method of increasing the abundance is represented by the general formula (1).
Crystalline polypropylene resin composition containing a compound
It is characterized by molding an article.

The amide compound represented by the general formula (1) is easily prepared by amidating a predetermined aliphatic diamine, alicyclic diamine or aromatic diamine with a predetermined monocarboxylic acid according to a conventional method. be able to.

Examples of the aliphatic diamine according to the present invention include saturated or unsaturated aliphatic diamines represented by the following general formula (2), and more specifically, 1,2-diaminopropane, 1 , 3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane,
Examples are 1,6-diaminohexane and the like.

[Chemical 11] [In the formula, R ⁸ represents a saturated or unsaturated alkylene group having 1 to 24 carbon atoms. ]

As the alicyclic diamine, an alicyclic diamine represented by the following general formula (3), for example, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane,
4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like, Examples thereof include alicyclic diamines such as isophorone diamine and menthen diamine.

[Chemical 12] [Wherein R ⁹ is

[Chemical 13] Or

[Chemical 14] Represents R ¹⁰ and R ¹¹ are the same or different and represent a hydrogen atom or an alkylene group having 1 to 3 carbon atoms, and R ¹² and R ¹³ are the same or different and represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms. ]

Examples of the aromatic diamine include aromatic diamines represented by the following general formula (4), and more specifically, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1, Examples thereof include 5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl sulfone. Xylylenediamine cannot obtain a predetermined effect even if it is an aromatic diamine.

[Chemical 15] [Where X is

[Chemical 16] ,

[Chemical 17] Or

[Chemical 18] Represents Y is _{-CH 2 -, - O -,} - SO 2 -, - S-,
-CO- or -C (CH _{3) 2} - represents a. ]

Examples of the above monocarboxylic acid include phenylacetic acid, cyclohexylacetic acid, cyclopropanecarboxylic acid,
Cyclobutanecarboxylic acid, cyclopentanecarboxylic acid,
Cyclohexanecarboxylic acid, 2-methyl-cyclohexanecarboxylic acid, 3-methyl-cyclohexanecarboxylic acid, 4-methyl-cyclohexanecarboxylic acid, 4-tert-
Butyl-cyclohexanecarboxylic acid, benzoic acid, o-methyl-benzoic acid, m-methyl-benzoic acid, p-methyl-benzoic acid, p-ethyl-benzoic acid, p-butylbenzoic acid, p
Examples include -tert-butylbenzoic acid and the like.

Among the diamide compounds obtained from the above diamine and monocarboxylic acid, more preferable compounds are N, N'-dicyclohexanecarbonyl-p-phenylenediamine and N, N'-dibenzoyl-1,5-diaminonaphthalene. , N, N'-dibenzoyl-1,4-diaminocyclohexane, N, N'-dicyclohexanecarbonyl-1,4-diaminocyclohexane and the like are exemplified.

As a method of blending the β-crystal nucleating agent with the polypropylene resin, both a method of blending at the time of polymerization and a method of adding and mixing to a separately prepared polymer can be applied.

The application amount of the β crystal nucleating agent can be appropriately selected as long as a predetermined effect can be obtained, but usually, it is about 0.0001 to 5 parts by weight, more preferably 0. It is about 001 to 1 part by weight.
If it is less than 0.0001 parts by weight, β crystals are difficult to form, and if it is contained in excess of 5 parts by weight, no significant difference in effect is observed.
It is economically disadvantageous and neither is preferable.

As described above, the β crystal nucleating agent according to the present invention can convert a crystalline polypropylene resin into β crystal in an extremely small amount, and it is 20 to 92% by weight under normal molding conditions.
It is possible to obtain a molded product containing the β crystal.

The polypropylene resin according to the present invention is
It is a polymer having propylene as a main constituent and includes not only a propylene homopolymer but also a copolymer with another α-olefin (having 2 to 12 carbon atoms). Specifically, polypropylene homopolymer, propylene-ethylene random copolymer containing propylene as a main component, propylene-ethylene block copolymer, and the polypropylene resin and a small amount of thermoplastic resin, for example, high-density polyethylene, polybutene-1, poly-4. Examples include blend polymers with methylpentene-1.

Such a polymer can be obtained by polymerizing a predetermined monomer in the presence of a catalyst. As the catalyst, not to mention the commonly used Ziegler-Natta type catalyst,
A catalyst in which a transition metal compound (for example, titanium halide such as titanium trichloride or titanium tetrachloride) is supported on a carrier whose main component is magnesium halide such as magnesium chloride, and an alkylaluminum compound (triethylaluminum, diethyl A catalyst system in combination with aluminum chloride) can also be used.

Melt flow rate of crystalline polypropylene resin component (hereinafter abbreviated as "MFR". JIS K 6758
-1981) is appropriately selected according to the molding method to be applied, and is usually about 0.1 to 100 g / 10 minutes, preferably about 0.5 to 50 g / 10 minutes.

In the resin composition according to the present invention, if necessary, stabilizers (epoxy compounds etc.), antioxidants (phenolic compounds, phosphite ester compounds etc.), ultraviolet absorbers (benzophenone compounds, Benzotriazole compounds), neutralizing agents, nucleating agents, antistatic agents, antiblocking agents, lubricants (aliphatic hydrocarbons, higher fatty acids and their alkali metal salts or alkaline earth metal salts, fatty acid esters, higher fatty acid amides, Rosin derivative, etc.), colorant,
Various additives such as elastomers and inorganic minerals (talc, hydrotalcite, etc.) can be used together within a range that does not impair the effects of the present invention.

As applicable molding methods, injection molding,
Examples include extrusion molding and compression molding.

The resin composition according to the present application is characterized in that it has a lower melting point than that of α-crystal polypropylene and a small force required for deformation under heating, and is very useful for improving secondary workability. Therefore, by molding under the desired mixing method and molding processing conditions, the β crystal can be easily contained at a high level (currently, the content ratio of 92% by weight has been confirmed) with a good hue. A molded product can be obtained. This polypropylene molded product can be applied to a wide range of fields such as containers, sheets and films.

In the resin composition according to the present invention, the content ratio of the α-type crystal structure and the β-type crystal structure can be controlled by selecting molding conditions such as cooling conditions. It is particularly effective for roughening the surface of the biaxially stretched film. The obtained surface-roughened film is excellent in blocking resistance, printability, adhesiveness, etc., and is very useful in the fields of packaging films, printing paper, tracing paper, oil-immersed plastic capacitors and the like.

[0024]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The β crystal content was determined by the following measuring method.

[Measurement of β Crystal Content] D: 5-10 mg of sample
Set it in the SC sample holder and run it in a nitrogen atmosphere at 230
After melting at 0 ° C for 5 minutes, the temperature is lowered to near room temperature at 20 ° C / minute. Next, the temperature is raised at 20 ° C./min, and the β crystal content (area%) is determined from the peak areas of α crystal and β crystal of the DSC thermogram obtained at this time. The formation of β crystal was confirmed by X-ray diffraction.

Example 1 Propylene homopolymer powder (MFR = 14 g / 10
Min) 0.05 parts by weight of N, N'-dicyclohexanecarbonyl-p-phenylenediamine was added to 100 parts by weight, mixed with a Henschel mixer, and pelletized with a 20 mmφ uniaxial extruder. Next, the obtained pellets are 230 ° C x 1
It was compression molded under the condition of 0 minutes to obtain a sheet having a thickness of 0.5 mm. The β crystal content of the obtained sample was 84%, and coloring of the sheet was not observed.

Example 2 A sheet was prepared in the same manner as in Example 1 except that N, N'-dibenzoyl-1,5-diaminonaphthalene was used as the β crystal nucleating agent. The β crystal content of the obtained sample was 44%,
No coloring of the sheet was observed.

Example 3 A sheet was prepared in the same manner as in Example 1 except that N, N'-dibenzoyl-1,4-diaminocyclohexane was used as the β crystal nucleating agent. The β crystal content of the obtained sample was 92%, and coloring of the sheet was not observed.

Example 4 N, N'-dicyclohexanecarbonyl-1, as a β crystal nucleating agent,
A sheet was prepared in the same manner as in Example 1 except that 4-diaminocyclohexane was applied. The β crystal content of the obtained sample was 85%, and coloring of the sheet was not observed.

Comparative Example 1 A sheet was prepared in the same manner as in Example 1 except that N, N'-dicyclohexanecarbonyl-p-phenylenediamine was not added, and its β crystal content was determined. The β crystal content of the obtained sample was a trace amount. No coloring of the sheet was observed.

Comparative Example 2 A sheet was prepared in the same manner as in Example 1 except that γ-quinacridone was used as the β crystal nucleating agent. However, β crystals in the obtained sample were trace amounts under the conditions.
The sheet was colored red.

[0032]

EFFECTS OF THE INVENTION By applying the crystalline polypropylene resin composition according to the present invention, a molded article containing a large amount of β crystal can be efficiently produced under industrial conditions.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Naoki Ikeda               13 Fukumi-ku, Kyoto City, Fukumi-ku, Kyoto Prefecture               Inside Shin Nippon Rika Co., Ltd. (72) Inventor Hiroshi Kitagawa               13 Fukumi-ku, Kyoto City, Fukumi-ku, Kyoto Prefecture               Inside Shin Nippon Rika Co., Ltd.                (56) Reference JP-A-4-261447 (JP, A)

Claims (4)

(57) [Claims] 1. The amide compound represented by the general formula (1) is added in an amount of 0.0001 to 100 parts by weight of polypropylene.
A crystalline polypropylene resin composition containing 5 parts by weight . Embedded image R ² —CONH—R ¹ —NHCO—R ³ (1) [wherein, R ¹ is an aliphatic diamine residue having 1 to 24 carbon atoms,
Represents an alicyclic diamine residue or an aromatic diamine residue (excluding a xylylenediamine residue), and R ² and R ³ are the same or different and are a cycloalkyl group having 3 to 14 carbon atoms,
A cycloalkenyl group, [Chemical 3] [Chemical 4] Or [Chemical 5] (Wherein R ¹ is an aliphatic divalent group having 1 to 24 carbon atoms)
In the case of amine residue, cycloalkyl having 3 to 14 carbon atoms
Group, cycloalkenyl group and embedded image Excludes groups represented by. ) Represents. R ⁴ and R ⁵ represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ⁶ and R ⁷ each represent a linear or branched chain having 1 to 3 carbon atoms. Represents an alkylene group. ] 2. An amide compound represented by the general formula (1)
A crystalline polypropylene resin composition containing
The crystalline polypropylene resin molded body
A method of increasing the β crystal content. ^{R 2 -CONH-R 1 -NHCO-} R 3 (1) [ wherein, ^{R 1} represents an aliphatic diamine residue having 1 to 24 carbon atoms,
Alicyclic diamine residue or aromatic diamine residue (however,
Excludes silylenediamine residues. ), And R ² and R ³ are
The same or different, a cycloalkyl group having 3 to 14 carbon atoms,
A cycloalkenyl group, Or Represents a group represented by. R ⁴ and R ⁵ are hydrogen atoms or carbon
Number 1 to 4 linear or branched alkyl group, alkene
Represents a nyl group, and R ⁶ and R ⁷ are straight-chain or
Represents a branched alkylene group. ] 3. The compounding amount of the amide compound is a crystalline poly
0.0001 to 5 per 100 parts by weight of propylene resin
The crystalline polypropylene according to claim 2, which is parts by weight.
A method of increasing the β crystal content in a resin-based molded article. 4. A crystalline polypropylene resin composition
Characterized by making the β crystal content 20 to 92% by weight
The crystalline polypropylene-based resin molding according to claim 2,
A method of increasing the β crystal content in the body.