JPS6330546A - Antistatic particulate master batch composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has excellent processability and imparts an instantaneous and persistent antistatic effect to diluted resins, consisting of non-crystalline PP, crystalline PP and an antistatic agent. CONSTITUTION:30-65 wt% non-crystalline PP is blended with 10-65 wt% crystalline PP, 5-25 wt% antistatic agent (e.g., a polyoxyethlene alkylamine) and optionally, an antioxidant, an ultraviolet absorber, a lubricant, a nucleating agent, a pigment, an inorg. filler, etc. The mixture is kneaded, cooled and crushed to obtain an antistatic particulate master batch compsn. The compsn. is blended with a polyolefin resin such as low-density PE, high-density PE, PP etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an antistatic agent masterbatch granular composition that has excellent processability and provides fast-acting and long-lasting antistatic effects to diluted resins. be.

[Prior art]

Generally, synthetic resins such as gaolefin polymers such as polyethylene and polypropylene have high electrical insulation properties and tend to accumulate static electricity.

Since this charging phenomenon impairs the appearance of synthetic resin products and also hinders secondary processing such as printing and painting, many methods for preventing static electricity on synthetic resin products have been proposed.

This antistatic method can be roughly divided into two types: a method of applying an antistatic surfactant to the surface and a method of kneading the surfactant into the interior. After resin molding, the internally kneaded antistatic agent bleeds out onto the resin surface to exhibit its effect, and the antistatic effect is required to be fast-acting and long-lasting.

As methods for adding this internally kneaded antistatic agent, there are two known methods: tri-blending the raw resin and antistatic agent during molding, and using a masterbatch in which the antistatic agent is kneaded into the resin in advance at a high concentration during molding. In particular, the method of using a masterbatch is widely put into practical use by those skilled in the art because the antistatic agent can be easily mixed therein.

For example, Special Publication No. 47-48889, Special Publication No. 48-2
No. 4016 discloses a masterbatch for polypropylene resin in which an antistatic agent and an antifogging agent are kneaded into amorphous polypropylene.

These masterbatches use an amorphous resin with a low melt viscosity, so they have the advantage that antistatic agents and antifogging agents are well dispersed in the molded product and have excellent dispersion effects. Since the antistatic agent bleeds out, the molded product surface becomes sticky, the mold becomes cloudy, and the durability of the effect is lost. Furthermore, since the masterbatch itself has high stickiness and is prone to blocking, it has disadvantages such as poor workability, lack of homogeneous mixing with the raw material resin, and significant influence on the physical properties of the molded product.

〔the purpose〕

An object of the present invention is to provide an antistatic agent masterbatch granular composition that has excellent processability and provides fast-acting and long-lasting antistatic effects to diluted resins.

〔composition〕

According to the present invention, amorphous polypropylene of 30 to 65
An antistatic agent masterbatch granular composition is provided, characterized in that it contains 10-65% by weight of crystalline polypropylene and 5-25% by weight of an antistatic agent.

The antistatic agent masterbatch granular composition of the present invention uses two types of polypropylene resins with two different crystallinities as base resins, and contains these resins and an antistatic agent in a specific ratio, so that it has antistatic properties. Since the bleed-out of the agent can be appropriately controlled, a long-lasting and fast-acting antistatic effect is exhibited, and the masterbatch composition itself has excellent processability without causing blocking.

When non-crystalline polypropylene with low crystallinity and low melt viscosity is used alone as the base resin, the masterbatch granular composition itself tends to block, resulting in poor processability. In addition, the physical properties of molded products obtained by blending this masterbatch may deteriorate, and the antistatic agent may bleed out excessively on the surface of the molded product, making the molded product sticky and unable to provide a lasting antistatic effect. , the purpose of the present invention cannot be achieved.

In addition, when crystalline polypropylene is used alone as the base resin, the antistatic effect does not develop quickly, and the antistatic agent is difficult to disperse uniformly into the molded product.
When used in combination with pigments, there arises the problem that the dispersibility of the pigments is adversely affected, and therefore the effects of the present invention cannot be expected.

Furthermore, in the case of a product in which amorphous polypropylene is used as a binder and additives such as antistatic agents are attached to the surface of crystalline polypropylene (Japanese Patent Publication No. 59-51570), the surface is coated with amorphous polypropylene. Therefore, it has high tackiness, causes blocking among the compositions, and lacks uniform mixability with the raw material resin, resulting in poor workability and processability, and cannot achieve the excellent effects of the present invention. .

Next, the present invention will be explained in more detail.

In the present invention, 30 to 65 wt% of amorphous polypropylene and 10 to 65 wt% of crystalline polypropylene are used as the base resin.

Amorphous polypropylene is generally obtained as a by-product during the production of crystalline polypropylene, and block copolymers, random copolymers, and homopolymers are known. Any of the above polymers can be used, or two or more of these polymers can be used in combination.

In the present invention, the amorphous polypropylene is contained in an amount of 30 to 65% by weight, preferably 35 to 65% by weight based on the total weight of the composition.
It is necessary to use 50% by weight.

If the amount of amorphous polypropylene used in the composition is less than 30% by weight, the amount of amorphous polypropylene in the molded product will decrease when the composition is blended and molded, resulting in a decrease in the antistatic effect. Fast-acting properties are lost, and the antistatic effect is not uniform. Furthermore, when pigments are used in molded articles, there is a problem in that the dispersibility of the pigments is adversely affected.

Furthermore, when the amount of amorphous polypropylene used exceeds 65% by weight, the antistatic agent bleeds out excessively, causing cloudiness in the mold of the molded article and loss of sustainability of the effect. Furthermore, the surface of the molded product becomes sticky and the physical properties of the molded product are impaired. In addition, in such a composition, the granular composition itself has a high blocking property, and is unsuitable for use as a masterbatch due to poor processability.

In addition, in the present invention, crystalline polypropylene is used as the base resin in addition to the above-mentioned amorphous polypropylene.
Use 65 weight 2. In this case, any crystalline polyolefin that is generally commercially available as crystalline polypropylene can be used.

In the present invention, this crystalline polypropylene is added in an amount of 10 to 65% by weight, preferably 20 to 5% by weight, based on the total weight of the composition.
It is necessary to use 0% by weight.

If the amount of crystalline polypropylene used in the composition is less than 10 years old, blocking of the composition cannot be prevented and the sustainability of the antistatic effect cannot be maintained. Furthermore, if the amount used exceeds 65% by weight, a fast-acting antistatic effect will not be exhibited.

The antistatic agent used in the present invention is not particularly limited, as long as it is generally known as a kneading type antistatic agent.
Any one can be used. Examples of such antistatic agents include the following compounds, which may be used alone or in combination of two or more.

Polyoxyethylene alkylamine, N, N(bis)2
-Hydroxyethylalkylamine, N, N(bis)2
- fatty acid ester of hydroxyethylalkylamine,
Higher alcohol, fatty acid ester of polyhydric alcohol, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol fatty acid ester, alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate, alkyl phosphate,
Tetraalkylammonium salts, trialkylbenzylammonium salts, alkylbetaine type amphoteric salts, imidazolinium type amphoteric salts, alanine type amphoteric salts, etc.

Further, in the present invention, it is necessary to use the antistatic agent in an amount of 5 to 25% by weight, preferably 5 to 20% by weight, based on the total weight of the composition.

If the concentration is less than 5% by weight, the proportion of amorphous polypropylene in the molded product increases, which affects the physical properties of the molded product. It is possible to knead more than 25% by weight, but in that case, the amount of masterbatch granular composition added to the molded product will be small, and the dilution ratio of the masterbatch will be large, making it difficult to prevent static electricity in the molded product. Effects are not uniformly exerted.

The method for producing the granular composition of the present invention is not particularly limited and may be carried out by known means. For example, a granular composition is obtained after cross-mixing, cooling, and pulverization using a conventional plastic molding machine, such as a Banbury mixer, a Herschel mixer, a vented screw extruder, or a kneader.

When producing the granular composition of the present invention, crystalline polypropylene and amorphous polypropylene may be blended individually, or crystalline polypropylene and amorphous polypropylene may be mixed in advance and granulated. It is also possible.

In the granular composition of the present invention, commonly used additives such as antioxidants, stabilizers such as ultraviolet absorbers, lubricants, nucleating agents, pigments, and inorganic fillers can be mixed as necessary. .

The amount used is determined depending on the purpose of the additive.

Examples of antioxidants include butylated hydroxytoluene, n-octadecyl-β-(hydroxy-3').

5'-di-t-butylphenyl)propionate, 4°4'-butylidenebis(3-t-butyl-m-cresol), 1.1.3-tris(2-methyl-4-hydroxy-5-t- butylphenyl)butane and the like.

Examples of UV absorbers include pt-butylphenyl salicylate, 2-hydroxy-4-n-octoxybenzophenone, 2-2' dihydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-5'- Examples include methylphenyl)benzotriazole and the like.

Examples of the lubricant include synthetic paraffin, polyethylene wax, higher fatty acid amide, and ethylenebis fatty acid amide.

In addition, nucleating agents include silica, aluminum hydroxide,
Examples include talc, metal fatty acid salts, calcium carbonate, and the like.

Examples of target resins that can be blended with the granular composition of the present invention include so-called low-density polyethylene (LDPE),
Examples include high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and copolymers thereof.

The polyolefin resin blended with the masterbatch granular composition according to the present invention can be molded by any processing method such as injection molding, blow molding, or extrusion molding.

〔effect〕

The antistatic agent masterbatch granular composition of the present invention uses polypropylene of different crystallinity as the base resin, thereby making it possible to control the bleed-out of the antistatic agent, and giving the diluted resin fast-acting and long-lasting properties. Provides antistatic effect. A molded article obtained by blending the composition into a polyolefin raw material resin exhibits an antistatic effect at an early stage, and the effect is long-lasting. Also,
The antistatic effect of the molded product is uniform, does not adversely affect the physical properties of the molded product, and has excellent pigment dispersibility.

Furthermore, the masterbatch granular composition itself has excellent processability without causing blocking, and can be suitably used.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 4.5 kg of crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd.; J-700G) was placed in a Banbury mixer and kneaded at 60 revolutions per minute and 160° C. for 10 minutes.

Next, amorphous polypropylene (manufactured by Tokuyama Soda ■; Tokuyama APP-D, block copolymer, melt viscosity 50,000 to 50
4.0 kg of 10,000 CP) was added and kneaded for 5 minutes.

Next, antistatic agent A for polyolefin [compound product of glycerin monostearate and N,N(bis)2-hydroxyethyl hardened beef tallow amine (80/20)] 1.5k
g was added and mixed for another 5 minutes, and then the mixture was taken out and mixed using a mixing roll at a resin temperature of 170° C. for 15 minutes to obtain a sheet with a thickness of about 3 mm+. This sheet was shredded with a pelletizer to obtain a masterbatch composition.

A portion of this was used as a sample for the blocking test.

After mixing 3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka ■; Noblen MA4) in a blender for 90 seconds, the molding temperature was 220°C.
Injection molding pressure 100kg/ant, total cycle 6
Injection molding was performed under conditions of 0 seconds to obtain a plate with a thickness of 2 mm. This plate was used as a sample for antistatic effect measurement.

Example 2 Amorphous polypropylene (manufactured by Yasan Soda ■; Tokuyama APP-E, homocopolymer, melt viscosity 120) was placed in a melt mixing stirring pot.
~150 cp) 4.0 kg, crystalline polypropylene (manufactured by Idemitsu Petrochemical ■; J-3050H 4.5 kg), antistatic agent B for polyolefin [blended product of glycerin monostearate and stearyl alcohol (50150))1.
5 kg was added and melted by heating at 230° C. for 1 hour. The resulting molten mixture was linearly dropped onto a steel belt, cooled and solidified, and cut with a cutter to obtain a granular masterbatch composition.

Mix 3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka ■: Noblen MA4) in a blender for 90 seconds, and heat the mixture at a resin temperature of 220°C.
After kneading with an extruder equipped with a die, extrusion molding was performed to produce a sheet with a thickness of 0.7 mm (width: 30 mm).

Example 3 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd.; J-305
0H) and 4.0 kg of amorphous polypropylene (manufactured by Tokuyama Soda ■; Tokuyama APP-C, random copolymer, melt viscosity 150-600 cp) were crushed and mixed for 30 seconds in a Henschel mixer. After that, antistatic agent C for polyolefins (N, N (bis) 2-hydroxyethyl combination product of hardened tallow amine and stearyl alcohol (5015)
0)) 1.5 kg was added and further mixed for 30 seconds. This mixture was put into a vented screw extruder and kneaded at a resin temperature of 220°C, and after cooling, strand pellets were obtained.

An injection molded product was obtained using the same molding method as in Example 1 using 3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka@; Noblen MA4).

Example 4 Amorphous polypropylene (manufactured by Tokuyama Soda ■; Tokuyama APP-
D, block copolymer, melt viscosity 50,000 to 500,000 cp) and crystalline polypropylene (manufactured by Idemitsu Petrochemical ■; J-305
Resin obtained by kneading 08) with an extruder (amorphous polypropylene/crystalline polypropylene = 75725) 6
．． 0 kg, 2.5 kg of antistatic agent B, powdered crystalline polypropylene (Jumin Chemical ■; Noblen HW100
) After mixing 1.5 kg in a blender for 90 seconds, a masterbatch composition was obtained in the same manner as in Example 3.

An injection molded product was obtained using the same molding method as in Example 1 using 3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka ■: Noblen MA4).

Example 5 Amorphous polypropylene (manufactured by Tokuyama Soda ■: Tokuyama APP-
E, homocopolymer, melt viscosity 120-150 cp) 3
．． 0kg, crystalline polypropylene (Idemitsu Petrochemical Support;
According to the method of Example 3, using 6.5 kg of J-3050t () and 0.5 kg of antistatic agent B for polyolefin,
A masterbatch composition was obtained. Example 1 was prepared using 9 parts by weight of the obtained masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka ■; Noblen MA4).
An injection molded product was obtained according to the molding method.

Example 6 Amorphous polypropylene (manufactured by Tokuyama Soda ■; Tokuyama APP-
D, block copolymer, solution viscosity 50,000 to 500,000 cp)6
．． 3 kg, crystalline polypropylene (manufactured by Idemitsu Petrochemical ■;
J-3050) 1) A masterbatch composition was obtained according to the method of Example 3 using 1.2 kg of antistatic agent A for polyolefins and 2.5 kg. An injection molded article was obtained according to the molding method of Example 1 using 1.5 parts by weight of the obtained masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka ■; Noblen A4).

Comparative Example 1 Amorphous polypropylene (manufactured by Tokuyama Soda ■; Tokuyama APP-
E, homocopolymer, melt viscosity 120-150 cp)8.
A masterbatch composition was obtained according to the method of Example 1 using 5 kg of the antistatic agent C1 and 5 kg of the antistatic agent for polyolefin C1. 3 parts by weight of the obtained masterbatch composition and crystalline polypropylene (manufactured by Mitsubishi Yuka ■; Noblen MA4)
An injection molded product was obtained according to the molding method of Example 1 using 100 parts by weight.

Comparative Example 2 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd.; J-305
0H) 8.5kg and antistatic agent for polyolefin 81.
A masterbatch composition was obtained using 5 kg according to the method of Example 3. 3 parts by weight of the obtained masterbatch composition and crystalline polypropylene (manufactured by Mitsubishi Yuka ■; Noblen M)
A4) An injection molded product was obtained according to the molding method of Example 3 using 100 parts by weight.

Comparative Example 3 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd.; J-305
0H) 1.65 kg, amorphous polypropylene (manufactured by Tokuyama Soda i11; Tokuyama APP-D, block copolymer, melt viscosity 50,000 to 500,000 cp) 7.5 kg, and antistatic agent A for polyolefins 0.85 kg. A masterbatch composition was obtained according to the method of Example 3. 4.5 parts by weight of the obtained masterbatch composition and crystalline polypropylene (
An injection molded product was obtained according to the molding method of Example 3 using 100 parts by weight of Noblen MA4 (manufactured by Mitsubishi Yuka ■).

Comparative Example 4 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd.; J-305
0H) 3.5 kg and amorphous polypropylene (manufactured by Tokuyama Soda ■; Tokuyama APP-C, random polymer, melt viscosity 15
0~600cp) 3.5kg and #E for polyolefin
From antistatic agent A3, Okg, according to the method of Example 3,
A masterbatch composition was obtained. An injection molded article was obtained according to the molding method of Example 3 using 1.5 parts by weight of the obtained masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Yuka ■; Noblen MA4).

Next, the above-mentioned Examples 1 to 6. The blocking antistatic effect of the masterbatches obtained in Comparative Examples 1 to 4 and the occurrence of mold fogging were investigated. The results are shown in Table 1. The evaluation method was as follows.

Evaluation method 1: Blocking property test The masterbatch composition was packed in a 1 kg plastic bag, and
A load of 1.5 kg was applied and the sample was left in a constant temperature room at 50°C for one month. - After one month, the presence or absence of blocking was visually determined.

O...Blocking not recognized, Δ...There is some blocking, ×...Blocking is severe.

2. Antistatic effect The surface resistivity after 30 minutes of molding and after 3 months of molding was measured at a constant humidity of 20° C. and 65% relative humidity (using a super insulation meter).

3. Occurrence of mold fogging The occurrence of mold fogging in the molding machine was visually determined after molding.

○: No mold fogging was observed.

Δ: Slight occurrence of mold clouding is observed.

×: Significant occurrence of mold fogging is observed.

As is clear from Table 1, the masterbatch granular composition of the present invention provides a fast-acting and long-lasting antistatic effect and does not cause mold fogging, and the masterbatch composition itself also It can be seen that the handleability and processability are good because no blocking occurs.

Examples 7 to 12 As shown in Table 2, optional components were further added to crystalline polypropylene, amorphous polypropylene, and an antistatic agent, and masterbatch granular compositions were prepared by a conventional method.

Similar to Examples 1 to 6, when the granular composition shown in Table 2 is uniformly kneaded into the resin, an excellent fast-acting and long-lasting antistatic effect can be obtained, and mold fogging and blocking can be prevented. There were no problems.

Procedures Amendment Written by the Commissioner of the Patent Office on April 1, 1988 Black 1) Akira Kishi 1, Indication of the case 1986 Patent Application No. 174900 3, Person making the amendment Relationship with the case Patent applicant address Tokyo Honjo-chome 3-7, Sumida-ku, Tokyo Name
(676) Lion Corporation Representative Kobayashi
Atsushi 4, Agent 151 Address 1-58-10-8 Yoyogi, Shibuya-ku, Tokyo
Contents of amendment The following amendments will be made to the specification of this application.

(1) Page 13, lines 8 to 9 [A plate with a thickness of 2 mm was obtained.

Using this plate, a plate with a thickness of 2 mm was obtained.

Correct this plate to ``.

(2) "Homo copolymer j" on page 13, line 13, page 15, bottom line, and page 16, bottom line will be corrected to "homopolymer."

(3) On page 14, line 4, replace “mixed liquid,” with “after mixing,”
I will correct it.

(4) "Random polymer" in line 8 of page 18 will be corrected to "random copolymer."

(5) Table 2 on page 22 will be corrected as shown in the attached sheet.

Claims (1)

[Claims] 30 to 65% by weight of amorphous polypropylene, 10 to 65% by weight of crystalline polypropylene, and 5 to 65% of antistatic agent.
An antistatic agent masterbatch granular composition containing 25% by weight.