JP2521053B2 - Antistatic agent master-batch granular composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antistatic masterbatch granular composition having excellent processability and providing a diluted resin with a fast-acting and long-lasting antistatic effect. is there.

[Prior art]

Generally, synthetic resins, for example, olefin polymers such as polyethylene and polypropylene have a large electric insulation and easily accumulate static electricity.

Since this charging phenomenon impairs the appearance of the synthetic resin product and further hinders secondary processing such as printing and coating, many antistatic methods for synthetic resin products have been proposed.

This antistatic method is roughly classified into two types, a method of applying an antistatic surfactant on the surface and a method of kneading the surfactant into the inside, and the latter internal kneading method is Since the internal kneading type antistatic agent bleeds out on the surface of the resin after the resin is molded to exert its effect, the antistatic effect is required to be fast and durable.

As a method of adding the internal kneading type antistatic agent,
A method of dry blending a raw material resin and an antistatic agent at the time of molding and a method of using a masterbatch in which an antistatic agent is preliminarily kneaded in a resin at a high concentration at the time of forming are known, and particularly a method of using a masterbatch is easy. Since an antistatic agent can be mixed, it is widely used by those skilled in the art.

For example, JP-B-47-48889 and JP-B-48-24016 disclose masterbatches for polypropylene resin in which an amorphous polypropylene is kneaded with an antistatic agent or an antifogging agent.

Since these masterbatches use an amorphous resin having a low melt viscosity, the antistatic agent and the antifogging agent are well dispersed in the molded article, and they have the advantage of being excellent in the dispersing effect. In addition, since the antistatic agent bleeds out, the surface of the molded article becomes sticky, the mold becomes cloudy, and the durability of the effect is lost. Further, since the masterbatch itself has high tackiness and is apt to cause blocking, workability is poor and lack of uniform mixing with the raw material resin,
Further, it has a drawback that the physical properties of the molded product are significantly affected.

〔Purpose〕

It is an object of the present invention to provide an antistatic agent masterbatch granular composition which is excellent in processability and gives a diluted resin a fast-acting and long-lasting antistatic effect.

〔Constitution〕

According to the present invention, an antistatic agent masterbatch granular composition characterized by containing 30 to 65% by weight of non-crystalline polypropylene, 10 to 65% by weight of crystalline polypropylene and 5 to 25% by weight of antistatic agent. Things are offered.

The antistatic agent masterbatch granular composition of the present invention uses, as the base resin, two types of polypropylene resins having different crystallinities and contains these resins and the antistatic agent in a specific ratio, so that the antistatic agent Since the bleed-out of the agent can be appropriately controlled, the antistatic effect excellent in durability and quick effect is exhibited, and the masterbatch composition itself is excellent in processability without causing blocking.

A base resin having a low crystallinity and a non-crystalline polypropylene having a low melt viscosity alone is inferior in processability because the masterbatch granular composition itself is easily blocked. In addition, the physical properties of the molded product obtained by blending this masterbatch deteriorate, and the antistatic agent excessively bleeds out on the surface of the molded product, so that the molded product becomes sticky and a persistent antistatic effect cannot be obtained. However, the object of the present invention cannot be achieved.

In addition, as the base resin, the one using the crystalline polypropylene alone does not exhibit the antistatic effect at an early stage,
Further, it is difficult to uniformly disperse the antistatic agent in the molded product, and when it is used together with the pigment, there arises a problem that the dispersibility of the pigment is adversely affected. Therefore, the effect of the present invention can be expected. Can not.

Further, in the case where non-crystalline polypropylene is used as a binder and additives such as an antistatic agent are attached to the surface of crystalline polypropylene (Japanese Patent Publication No. 59-51570), the surface is coated with non-crystalline polypropylene. Therefore, it has high tackiness, the compositions cause blocking, and also lacks in uniform mixing with the raw material resin, so that workability and processability are poor, and it is possible to exert the excellent effect of the present invention. Can not.

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

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

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

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

When the amount of the amorphous polypropylene used in the composition is less than 30% by weight, the amount of the amorphous polypropylene in the molded product becomes small when the composition is compounded and molded, so that the antistatic effect Quick effect is lost, or antistatic effect is not uniform. Further, when a pigment is used in a molded article, there is a problem that the dispersibility of the pigment is adversely affected.

On the other hand, when the amount of the non-crystalline polypropylene used exceeds 65% by weight, the antistatic agent excessively bleeds out, and the mold of the molded article becomes cloudy or loses its sustainability. In addition, the surface of the molded product becomes sticky and the physical properties of the molded product are impaired. Further, with such a composition, the granular composition itself has a high blocking property and is not suitable for use as a masterbatch because of poor processability.

Further, in the present invention, a crystalline polypropylene with the above-mentioned non-crystalline polypropylene as a base resin 10 ~
Use 65% by weight. In this case, as the crystalline polyolefin, any commercially available crystalline polypropylene can be used.

In the present invention, it is necessary to use the crystalline polypropylene in an amount of 10 to 65% by weight, preferably 20 to 50% by weight, based on the total weight of the composition.

10% by weight of crystalline polypropylene in the composition
If the amount is smaller, blocking of the composition cannot be prevented and the antistatic effect cannot be maintained.
Further, when the amount used exceeds 65% by weight, the antistatic effect having a rapid effect is not exhibited.

The antistatic agent used in the present invention is not particularly limited, and any of those generally known as a kneading type antistatic agent can be used. Examples of such an antistatic agent include the compounds shown below, which are used alone or as a mixture of two or more kinds.

Polyoxyethylene alkylamine, N, N (bis) 2
-Hydroxyethylalkylamine, N, N (bis) 2-
Hydroxyethyl alkylamine fatty acid ester, higher alcohol, polyhydric alcohol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol, polyoxyethylene alkylphenyl ether, polyoxyethylene glycol fatty acid ester, alkyl sulfonate, alkylbenzene Sulfonate, alkyl sulfate, alkyl phosphate,
Tetraalkylammonium salt, trialkylbenzylammonium salt, alkylbetaine type amphoteric salt, imidazolinium type amphoteric salt, alanine type amphoteric salt and the like.

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.

When the concentration is less than 5% by weight, the proportion of the 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 is small, so the dilution ratio of the masterbatch is large and the antistatic property of the molded product is prevented. The effect is not evenly exhibited.

The method for producing the granular composition of the present invention is not particularly limited and may be carried out by a known means. For example, a usual plastic molding machine, that is, a Banbury mixer, a Herschel mixer, a screw-extrusion molding machine with a vent, a kneader, and a granular composition are obtained after kneading, cooling and pulverizing.

During the production of the granular composition of the present invention, the crystalline polypropylene and the amorphous polypropylene may be individually blended during the blending, or the crystalline polypropylene and the amorphous polypropylene may be blended in advance and granulated. It is also possible.

If necessary, the granular composition of the present invention may be mixed with stabilizers such as antioxidants and ultraviolet absorbers, lubricants, nucleating agents, pigments, and commonly used additives such as inorganic fillers.
The usage fee is determined according to the purpose of the additive.

Examples of antioxidants include butylated hydroxytoluene, n-octadecyl-β- (hydroxy-3 ', 5'-
Di-t-butylphenyl) propionate, 4,4'-butylidene bis (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'-. Methylphenyl) benzotriazole and the like can be mentioned.

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

Examples of the nucleating agent include silica, aluminum hydroxide, talc, metal fatty acid salt, calcium carbonate and the like.

The target resin to which the granular composition in the present invention can be added is, for example, so-called low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), or a combination thereof. Examples thereof include polymers.

The polyolefin resin containing the masterbatch granular composition according to the present invention may be, for example, injection molded, blow molded,
It can be molded by any processing method such as extrusion molding.

〔effect〕

The antistatic agent masterbatch granular composition of the present invention enables control of the antifreeze fried-out by using polypropylene having different crystallinity as a base resin, and the diluted resin has fast-acting and long-acting properties. Gives an antistatic effect. A molded article obtained by blending the composition with a polyolefin raw material resin exhibits an antistatic effect at an early stage, and the effect is persistent. Further, the antistatic effect of the molded product is uniform, the physical properties of the molded product are not adversely affected, and the pigment dispersibility is excellent. Further, the masterbatch granular composition itself has excellent processability without causing blocking and can be suitably used.

〔Example〕

 Next, the present invention will be described in more detail by way of examples.

Example 1 4.5 kg of crystalline polypropylene (J-700G, manufactured by Idemitsu Petrochemical Co., Ltd.) was charged into a Banbury mixer, and the rotation speed was 60 per minute.
The mixture was rotated and kneaded at 160 ° C. for 10 minutes. Then, amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama APP-D,
4.0 kg of the block copolymer and melt viscosity of 50,000 to 500,000 CP) were added and kneading was performed for 5 minutes. Then, an antistatic agent A for polyolefin [a blend of glycerin monostearate and N, N (bis) 2-hydroxyethyl cured tallow amine (80
/ 20)] 1.5 kg was added and kneading was continued for another 5 minutes, then the mixture was taken out, and the resin temperature was 170 ° C with a mixing roll.
The mixture was kneaded for 15 minutes to obtain a sheet having a thickness of about 3 mm. This sheet was chopped with a pelletizer to obtain a masterbatch composition. A part of this was used as a sample for the blocking property test.

After mixing 3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Petrochemical Co., Ltd .; Noblene MA4) for 90 seconds with a blender, molding temperature 220 ° C., injection molding pressure 100 kg / cm ² , Injection molding was performed under the condition of a total cycle of 60 seconds to obtain a plate having a thickness of 2 mm. This plate was used as a sample for measuring the antistatic effect.

Example 2 Amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama APP-E, homopolymer, melt viscosity 120-
150cp) 4.0 kg, crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-3050H 4.5 kg), antistatic agent for polyolefin B [blend of glycerin monostearate and stearyl alcohol (50/50)] 1.5 kg It was charged and heated and melted at 230 ° C for 1 hour. The molten mixture obtained by melting was linearly dropped on a steel belt, cooled and solidified, and cut with a cutter to obtain a granular masterbatch composition.

3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (Mitsubishi Oil Chemical Co., Ltd .; Noblen MA4) were mixed for 90 seconds with a blender, and then kneaded with an extruder equipped with a T-die at a resin temperature of 220 ° C. After that, extrusion molding was performed to create a sheet with a thickness of 0.7 mm (width 30 mm).

Example 3 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-30
50H) 4.5 kg, non-crystalline polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama APP-C, random copolymer, melt viscosity 1
50-600cp) 4.0kg with a Henschel mixer for 30 seconds,
Mixed. Then antistatic agent C [N, N for polyolefin
(Bis) 2-hydroxyethyl hardened beef tallow amine and stearyl alcohol blended product (50/50)] 1.5 kg was added and further mixed for 30 seconds. This mixture was put into a screw extruder with a vent, kneaded at a resin temperature of 220 ° C., and cooled to obtain strand pellets.

An injection-molded article was obtained by the same forming method as in Example 1 using 3 parts by weight of the above masterbatch composition and 100 parts by weight of crystalline polypropylene (Noblene MA4 manufactured by Mitsubishi Petrochemical Co., Ltd.).

Example 4 Amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama AP)
P-D, block copolymer, melt viscosity 50,000-500,000 cp) and crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-3050
Resin (non-crystalline polypropylene / crystalline polypropylene = 75/25) 6.0 kg obtained by kneading H) with an extruder, 2.5 kg of antistatic agent B, powdery crystalline polypropylene (Sumitomo Chemical Co., Ltd .; Noblene HW100) (1.5 kg) was mixed with a blender for 90 seconds, and a masterbatch composition was obtained in the same manner as in Example 3.

An injection-molded article was obtained by 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 (Noblene MA4 manufactured by Mitsubishi Yuka Co., Ltd.).

Example 5 Amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama AP)
PE, homopolymer, melt viscosity 120-150 cp) 3.0 kg, crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-3050H)
A masterbatch composition was obtained according to the method of Example 3 with 6.5 kg and 0.5 kg of the antistatic agent for polyolefin B.
An injection-molded article was obtained according to the molding method of Example 1 from 9 parts by weight of the obtained masterbatch composition and 100 parts by weight of crystalline polypropylene (Noblene MA4 manufactured by Mitsubishi Oil Chemical Co., Ltd.).

Example 6 Amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama AP)
P-D, block copolymer, dissolution viscosity 50,000-500,000 cp) 6.3
kg, crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-
3050H) 1.2 kg and antistatic agent A 2.5 kg for polyolefin were used to obtain a masterbatch composition according to the method of Example 3. 1.5 parts by weight of the obtained masterbatch composition and crystalline polypropylene (manufactured by Mitsubishi Yuka Co., Ltd .; Nobren MA)
4) 100 parts by weight was used to obtain an injection molded product according to the molding method of Example 1.

Comparative Example 1 Amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama AP)
According to the method of Example 1, a masterbatch composition was obtained by using P-D, a homopolymer, a melt viscosity of 120 to 150 cp) 8.5 kg, and an antistatic agent for polyolefin C 1.5 kg. An injection-molded article was obtained according to the molding method of Example 1 by using 3 parts by weight of the obtained masterbatch composition and 100 parts by weight of crystalline polypropylene (manufactured by Mitsubishi Petrochemical Co., Ltd .; Nobrene MA4).

Comparative Example 2 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-30
A masterbatch composition was obtained according to the method of Example 3 with 8.5 kg of 50H) and 1.5 kg of the antistatic agent for polyolefin B. 3 parts by weight of the obtained masterbatch composition and crystalline polypropylene (manufactured by Mitsubishi Yuka Co., Ltd .; Nobren MA4) 100
An injection-molded article was obtained according to the molding method of Example 3 in parts by weight.

Comparative Example 3 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-30
50H) 1.65 kg and amorphous polypropylene (manufactured by Tokuyama Soda Co., Ltd .; Tokuyama APP-D, block copolymer, melt viscosity 50,000-500,000 cp) 7.5 kg, polyolefin antistatic agent A0.
With 85 kg, a masterbatch composition was obtained according to the method of Example 3. An injection-molded article was obtained in accordance with the molding method of Example 3 by using 4.5 parts by weight of the obtained masterbatch composition and 100 parts by weight of crystalline polypropylene (Noblene MA4 manufactured by Mitsubishi Petrochemical Co., Ltd.).

Comparative Example 4 Crystalline polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd .; J-30
50H) 3.5 kg and amorphous polypropylene (Tokuyama Soda Co., Ltd.)
Made; Tokuyama APP-C, random copolymer, melt viscosity 150-60
A masterbatch composition was obtained from 3.5 kg of 0 cp) and 3.0 kg of antistatic agent A for polyolefin according to the method of Example 3. 1.5 parts by weight of the obtained masterbatch composition and crystalline polypropylene (manufactured by Mitsubishi Yuka Co., Ltd .; Nobren MA)
4) 100 parts by weight was used to obtain an injection molded product according to the molding method of Example 3.

Next, the masterbatch obtained in each of Examples 1 to 6 and Comparative Examples 1 to 4 was examined for the antistatic effect on the blocking property and the occurrence of mold fog. Table 1 shows the results. In addition,
The evaluation method was as follows.

Evaluation method 1. Blocking test 10 kg of the masterbatch composition was packed in a 1 kg plastic bag.
Then, leave it in a constant temperature chamber at 50 ° C for 1 month. After one month, the presence or absence of blocking was visually determined.

○: No blocking was observed, Δ: Some blocking was observed, ×: Blocking was severe.

2. Antistatic effect Surface resistivity after 30 minutes of molding and one month after molding
It was measured at 20 ° C and a relative humidity of 65% relative humidity (using an ultra-ultra-insulator).

3. Occurrence of mold fog The occurrence of mold fog in the molding machine was visually evaluated after molding.

○: No cloudiness of the mold is observed.

Δ: Some clouding of the mold is observed.

X: The cloudiness of the mold is remarkably observed.

As is clear from Table 1, the masterbatch granular composition of the present invention provides an excellent antistatic effect with fast-acting and long-lasting properties, and does not cause mold haze, and also the masterbatch composition itself. It can be seen that since no blocking occurs, its handleability and workability are good.

Examples 7 to 12 As shown in Table 2, crystalline polypropylene, amorphous polypropylene, and an antistatic agent were further added with optional components,
The masterbatch particulate composition was prepared in a conventional manner.

Even when the granular composition shown in Table 2 was uniformly kneaded into the resin, excellent fast-acting and long-lasting antistatic effects were obtained as in Examples 1 to 6, and the mold fogging and blocking were prevented. There was no problem.

Claims (1)

(57) [Claims] 1. A non-crystalline polypropylene of 30 to 65% by weight,
An antistatic masterbatch particulate composition comprising 10 to 65% by weight of crystalline polypropylene and 5 to 25% by weight of an antistatic agent.