JP3275355B2 - Crystalline polypropylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for molding a crystalline polypropylene resin composition capable of producing a large amount of .beta. Crystal structure .
By this, in the crystalline polypropylene resin molded body
The present invention relates to a method for increasing the β crystal content .

[0002]

2. Description of the Related Art Crystalline polypropylene includes α, β,
There are each transformation of γ and δ and a smectic transformation that occurs when the molten polypropylene is rapidly cooled. Among these, the β transformation (hereinafter referred to as “β crystal”) has a lower melting point and lower density than the α transformation (hereinafter referred to as “α crystal”) found in conventional general-purpose natural pellets. It is known to have interesting properties in application, such as different crystalline state and fracture state (Polymer Chemistry, 30 , 694-698, (1)
978)).

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 a β crystal nucleating agent, γ-quinacridone is known so far (POLYMERLETTERS, 6 , 539-546,
(1968)). However, when the nucleating agent is applied, there are drawbacks in that the obtained product is colored red, and special equipment and operation are required for mixing with the polymer.

[0005] The present invention is a practical polypropylene-based resin obtained by applying a novel and useful β-crystal nucleating agent capable of solving the disadvantages of quinacridone-based compounds and efficiently obtaining a β-crystal polypropylene product having excellent hue. Β crystal content in the compact
The purpose is to propose a method of increasing

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to propose a β crystal nucleating agent which can achieve the above object,
The inventors have found that adipic acid dianilide and suberic acid dianilide function as β-crystal nucleating agents, and have completed the present invention based on such findings. Adipic acid dianilide and suberic acid dianilide are known compounds, but they are not yet known to be effective as β crystal nucleating agents. This property is unique, and even with the dianilide of the same aliphatic dibasic acid, dianilide of succinic acid, glutaric acid, and pimelic acid does not function as a practical β crystal nucleating agent.

That is, the method for increasing the content of β crystals in the crystalline polypropylene resin molded article according to the present invention comprises the steps of:
Polypropylene resin and dianilide adipate
And at least one selected from suberic acid dianilide
Crystalline Polypropylene Resin Set Containing Three Kinds of β Nucleating Agent
It is characterized by molding a product.

As a method of blending the β crystal nucleating agent with the polypropylene resin, either a method of blending at the time of polymerization or 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 is obtained, but is usually about 0.0001 to 5 parts by weight, preferably about 0.001 part by weight, per 100 parts by weight of polypropylene. About 1 part by weight, more preferably 0.005 to less than 0.05 part by weight. 0.0
If the amount is less than 001 parts by weight, it is difficult to form β crystals, and if the amount exceeds 5 parts by weight, no significant difference in effect is observed, which is economically disadvantageous, and both are not preferred.

As described above, the β crystal nucleating agent according to the present invention is capable of converting a crystalline polypropylene resin into β crystal in a very small amount, and is 20 to 93% by weight under ordinary molding conditions.
Can be obtained.

The polypropylene resin according to the present invention is:
A polymer containing propylene as a main component, specifically, a polypropylene homopolymer, propylene mainly composed of propylene and ethylene and / or 1-
Alkene random copolymer, the same block copolymer and the polypropylene resin and a small amount of thermoplastic resin,
For example, high density polyethylene, polybutene-1, poly-
Examples thereof include a blend polymer with 4-methylpentene-1.

In particular, a catalyst comprising a transition metal compound (for example, a titanium halide such as titanium trichloride or titanium tetrachloride) supported on a carrier mainly composed of magnesium halide such as magnesium chloride is used as the resin. When a polypropylene-based resin prepared using a catalyst system comprising a combination of an aluminum compound (triethylaluminum, diethylaluminum chloride, etc.) is applied, the desired effect of the present invention can be obtained by adding a smaller amount of a β crystal nucleating agent. It can be obtained stably.

The melt flow rate of the crystalline polypropylene resin component (hereinafter abbreviated as “MFR”; JIS K 6758)
-1981) is appropriately selected depending on the molding method to be applied, and is usually about 0.1 to 100 g / 10 min, preferably about 0.5 to 50 g / 10 min.

The resin composition according to the present invention may contain a stabilizer (epoxy compound, etc.), an antioxidant (phenol compound, phosphite compound, etc.), an ultraviolet absorber (benzophenone compound, Benzotriazole compounds), neutralizing agents, nucleating agents, antistatic agents, antiblocking agents, lubricants (aliphatic hydrocarbons, higher fatty acids and their alkali metal or alkaline earth metal salts, fatty acid esters, higher fatty acid amides, Rosin derivatives, etc.), coloring agents,
Various additives such as elastomers and inorganic minerals (such as talc and hydrotalcite) can be used in combination as long as the effects of the present invention are not impaired.

The applicable molding methods include injection molding,
Extrusion molding, compression molding and the like are exemplified.

The resin composition according to the present invention has characteristics such as a lower melting point than α-crystal polypropylene and a small force required for deformation under heating, and is very useful for improving secondary workability and the like. Yes, by molding under the desired mixing method and molding processing conditions, β-crystals can be easily formed at an unprecedented level (currently, a content ratio of 94% by weight has been confirmed) and a good hue is obtained. A molded article can be obtained. This polypropylene molded article can be applied to a wide range of fields such as containers, sheets, films and the like.

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

[0018]

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 measurement method. [Measurement of β Crystal Content] A sample (5-10 mg) is set in a DSC sample holder, melted at 230 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled to near room temperature at 20 ° C./min. 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 in the DSC thermogram obtained at this time.

Example 1 Polypropylene homopolymer powder (MFR = 14 g / 1)
0 minutes) 0.03 parts by weight of adipic dianilide in 100 parts by weight
Parts by weight and mixed with a Henschel mixer.
And pelletized with a single screw extruder. Next, the obtained pellet was compression-molded under the conditions of 230 ° C. × 10 minutes, and the thickness of the pellet was adjusted to 0.
A sheet of 5 mm was used. The β crystal content of the obtained sample was 89.
%Met.

Example 2 A sheet was prepared in the same manner as in Example 1 except that 0.04 parts by weight of suberic acid dianilide was used as the β crystal nucleating agent.
The β crystal content of the obtained sample was 82%.

Example 3 A polypropylene homopolymer (M
A sheet was prepared in the same manner as in Example 1 except that FR = 4.3 g / 10 minutes) was applied. The β crystal content of the obtained sample was 81%.

Example 4 A sheet was prepared in the same manner as in Example 1 except that an ethylene-propylene random copolymer (MFR = 23 g / 10 min) was used as the polypropylene. The β crystal content of the obtained sample was 63%.

Comparative Example 1 The content of β crystals was determined in the same manner as in Example 1 except that no adipic anilide was added. The β crystal content of the obtained sample was a trace amount.

Comparative Example 2 A sheet was prepared in the same manner as in Example 2 except that dianilide succinate was used as a β crystal nucleating agent. Β of the obtained sample
The crystal content was 9%.

Comparative Example 3 A sheet was prepared in the same manner as in Example 2 except that dianilide glutarate was used as a β crystal nucleating agent. The β crystal content of the obtained sample was 3%.

Comparative Example 4 A sheet was prepared in the same manner as in Example 2 except that 3,3-dimethylglutaric acid dianilide was used as the β crystal nucleating agent. The β crystal content of the obtained sample was a trace amount.

Comparative Example 5 A sheet was prepared in the same manner as in Example 2 except that pimelic dianilide was used as the β crystal nucleating agent. The β crystal content of the obtained sample was 5%.

Comparative Example 6 A sheet was prepared in the same manner as in Example 2 except that azelaic acid dianilide was used as the β crystal nucleating agent. The β crystal content of the obtained sample was a trace amount.

Comparative Example 7 A sheet was prepared in the same manner as in Example 2 except that dianilide sebacate was used as a β crystal nucleating agent. The β crystal content of the obtained sample was a trace amount.

[0030]

According to the present invention, by applying the method for increasing the content of β crystals in the crystalline polypropylene resin molded article according to the present invention, a large amount of β crystals can be efficiently contained under industrially advantageous conditions. In addition, a molded article without coloring can be manufactured.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor, Uji Kawashima, 13 Yoshimura Yakuracho, Fushimi-ku, Kyoto-shi, Kyoto, Japan Nippon Rika Co., Ltd. A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/10-23/16 C08K 5/20 C08J 3/00 CES C08F 6/00 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A crystalline polypropylene resin, and
Select from dianilide adipic acid and dianilide suberic acid
Crystalline poly-containing at least one β crystal nucleating agent
By molding a propylene-based resin composition,
Increasing β crystal content in polypropylene resin moldings
Way. 2. The amount of the β crystal nucleating agent in the crystalline polypropylene
0.0001 to 5 parts by weight based on 100 parts by weight of the lene resin
The crystalline polypropylene resin according to claim 1, which is
A method for increasing the content of β crystals in a compact. 3. The crystalline polypropylene resin molded article
characterized in that the content of β crystals is 20 to 94% by weight.
The crystalline polypropylene-based resin molding according to claim 1,
A method for increasing the β crystal content in the body.