KR20090058007A - Antistatic composition and molding thereof - Google Patents

Abstract

An antistatic composition comprising a polyolefin of below 2.5 g/10min melt flow rate and a polymer antistatic agent.

Description

Antistatic composition and its moldings {ANTISTATIC COMPOSITION AND MOLDING THEREOF}

The present invention relates to an antistatic composition. More specifically, the present invention relates to an antistatic composition comprising a polymer antistatic agent added to a polyolefin, and a molded article thereof.

Polypropylene and polyethylene are general-purpose resins and are used in all industries, such as automobiles, machine parts, containers, packaging, building materials, and household goods. Since these resins are nonconductive materials, when used for applications requiring antistatic properties, antistatic agents such as surfactants are added to these resins to impart antistatic properties.

As a resin composition which added the antistatic agent to resin, For example, patent document 1 has the ionic salt (A) which consists of nitrogen-onium cation which has one or more allyl groups, and weakly coordinated anion, and at least An antistatic polymer composition containing one kind of polymer and / or elastomer (B) is described.

Patent Literature 2 also describes an antistatic composition in which a salt having an anion having a fluoro group and a sulfonyl group is dispersed in a composition containing a resin and / or an elastomer.

However, these methods could not necessarily give sufficient antistatic performance with respect to polypropylene and polyethylene.

Patent Document 1: Japanese Unexamined Patent Publication No. 2005-350579

Patent Document 2: Japanese Unexamined Patent Publication No. 2006-137790

This invention is made | formed in view of the above-mentioned problem, and an object of this invention is to provide the antistatic composition which has sufficient antistatic performance, and the molded article obtained from it.

Disclosure of Invention

According to this invention, the following antistatic composition etc. are provided.

1. An antistatic composition containing a polyolefin having a melt flow rate of less than 2.5 (g / 10 min) and a polymer type antistatic agent.

2. The antistatic composition according to 1, wherein the amount of the polyolefin, which accounts for the total amount of the polyolefin and the polymer type antistatic agent, is 95 to 60 wt%, and the amount of the polymer type antistatic agent is 5 to 40 wt%.

3. Sheet or film which consists of said antistatic composition of 1 or 2.

4. Sheet or film of 3 whose thickness is 10 micrometers or more.

5. Laminated body containing the sheet | seat or film of said 3 or 4.

6. The molded article which consists of a sheet | seat, a film, or a laminated body in any one of said 3-5.

According to this invention, the antistatic composition which has high antistatic performance and the molded article obtained from it can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the relationship between MFR and surface specific resistance of polypropylene of a surface layer.

2 is a diagram illustrating a relationship between the surface layer thickness of a sheet and the surface specific resistance value.

3 is a diagram showing the relationship between the compounding amount of the antistatic agent and the surface specific resistance value.

It is a schematic diagram of the cross section of the sheet | seat manufactured in Example 20.

4B is a schematic view of the cross section of the sheet prepared in Example 21. FIG.

4C is a schematic view of the cross section of the sheet prepared in Comparative Example 4. FIG.

5 is a view showing a micrograph of a sheet cross section prepared in Example 20. FIG.

FIG. 6 is a view showing a micrograph of a sheet cross section prepared in Example 21. FIG.

It is a figure which shows the micrograph of the sheet cross section manufactured in the comparative example 4. FIG.

Best Mode for Carrying Out the Invention

Hereinafter, the antistatic composition of this invention is demonstrated concretely.

The antistatic composition of the present invention is characterized by containing a polyolefin having a melt flow rate (MFR) of less than 2.5 (g / 10 min) and a polymer type antistatic agent. The polyolefin used in the present invention has a lower MFR than that used conventionally. This invention finds out that the antistatic performance of a composition can be improved significantly by using the polyolefin with a low MFR, and a polymeric antistatic agent.

In addition, in this invention, MFR means the measured value (g / 10min) in 230 degreeC and a load of 2.16 kg.

The polyolefin used in the present invention is not particularly limited as long as the MFR is less than 2.5, and those commercially available commercially can be used without any problem. Preferably the polyolefin is polypropylene, polyethylene. It is preferable that MFR of polyolefin is 0.3-1.6.

Polypropylene includes homopolymer polypropylene, copolymer polypropylene (block, random, graft) and the like. For example, E110G (MFR = 0.3) or E105GM (MFR = 0.5) manufactured by Prime Polymer Co., Ltd. can be used. Polyethylene includes homopolymer polyethylene, copolymer polyethylene (block, random, graft), low density polyethylene, high density polyethylene and the like. For example, HE30 (MFR = 0.3) by Prime Polymer Co., Ltd. can be used.

When using a mixture of polypropylene and polyethylene, for example, polypropylene: polyethylene = 20 to 80: 80 to 20.

The polymer type antistatic agent used in the present invention includes, in addition to the polymer type antistatic agent, an ion conductive polymer type antistatic agent in which an ionic compound is added to the polymer type antistatic agent.

A polymeric antistatic agent is a high molecular compound which makes a PEO (polyethylene oxide) chain | strand an electroconductive unit in a molecule | numerator, for example, A polyethyleneglycol methacrylate copolymer, polyetheresteramide (PEEA), polyether ester Amideimide (PEAI), polyethylene oxide-polypropylene oxide (PEO-PPO) copolymer, and the like.

Moreover, a polyether block polyolefin type copolymer, a polyoxyalkylene type copolymer, or an ethylene oxide propylene oxide allyl glycidyl type copolymer is mentioned.

It is preferable to use the polymer type antistatic agent of the ion conductivity which mix | blended the ionic compound with the polymer type antistatic agent in the polymeric antistatic agent used by this invention.

An ion conductive polymer type antistatic agent exhibits antistatic properties by moving Li ions or the like along the polymer ion conducting path. The ion conductive polymer antistatic agent contains an ionic salt and a polymer antistatic agent.

As the ionic salt, for example, an ionic salt composed of nitrogen onium cation having one or more allyl groups and weakly coordinated anions is preferable. This ionic salt has high ion density and high ion mobility, and therefore has high ion conductivity.

Examples of the nitrogen onium cation include aliphatic nitrogen onium cation, unsaturated cyclic nitrogen onium cation, and aromatic nitrogen onium cation.

In aliphatic nitrogen-onium cation, quaternary amines are preferable, and quaternary alkylamines having 1 to 18 carbon atoms of alkyl groups other than the allyl group are particularly preferable.

Examples of the unsaturated cyclic nitrogen onium cation and aromatic nitrogen onium cation include pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium and triazium. Can be. It is more preferable if it is the quaternary amine of these unsaturated cyclic nitrogen onium cation and aromatic nitrogen onium cation.

With no yakbae satellite used in the ionic salts of the present invention it is on, at least one highly fluorinated alkyl alcohol not containing an organic fluorine yakbae satellite on-sulfonyl, BF ₄ ^- is is ^- or PF _6. The high fluorinated alkylsulfonyl group refers to a perfluoroalkanesulfonyl group or a partially fluorinated alkanesulfonyl group in which all of the non-fluorinated carbide bond substituents are bonded to a carbon other than a carbon atom bonded directly to the sulfonyl group.

In addition, an ionic salt can be manufactured using a well-known method (for example, Watanabe Masayoshi et al. "Function creation and application of an ionic liquid" N.T.S. (2004)).

Moreover, as another ionic salt, the salt provided with the anion which has a fluoro group and a sulfonyl group is mentioned. This salt is used in the state dissolved in water.

The salt having an anion having a fluoro group and a sulfonyl group is at least 1 in the group consisting of bis (fluoroalkylsulfonyl) imide ions, tris (fluoroalkylsulfonyl) methed ions, and fluoroalkylsulfonate ions. And an anion selected from the dog and a cation selected from at least one of the group consisting of an alkali metal, a Group 2A element, a transition metal, and an amphoteric metal.

It is preferable that bis (fluoroalkylsulfonyl) consists of a mid ion, a tris (fluoroalkylsulfonyl) metide ion, and a fluoroalkyl sulfonic acid ion among the salt comprised by the said anion and cation. Specifically, bis (trifluoromethanesulfonyl) imide lithium Li (CF ₃ SO ₂ ) ₂ N, bis (trifluoromethanesulfonyl) imide potassium K (CF ₃ SO ₂ ) ₂ N, bis ( Trifluoromethanesulfonyl) imide sodium Na (CF ₃ SO ₂ ) ₂ N, tris (trifluoromethanesulfonyl) methedritium Li (CF ₃ SO ₂ ) ₃ C, tris (trifluoromethanesulfonyl ) Meta Potassium K (CF ₃ SO ₂ ) ₃ C, Tris (trifluoromethanesulfonyl) method sodium Na (CF ₃ SO ₂ ) ₃ C, trifluoromethanesulfonate Li (CF ₃ SO ₃ ), Preferred are potassium trifluoromethanesulfonate K (CF ₃ SO ₃ ) and sodium trifluoromethanesulfonate Na (CF ₃ SO ₃ ).

Among them, bis (trifluoromethanesulfonyl) imide lithium, tris (trifluoromethanesulfonyl) methide and lithium trifluoromethanesulfonate are mentioned. In particular, bis (trifluoromethanesulfonyl) imide lithium and lithium trifluoromethanesulfonate are preferable.

Moreover, as for the compounding quantity of an ionic salt, about 0.01-30 mass parts is preferable with respect to 100 mass parts of polyolefins.

As a commercial item of the ion conductive polymer antistatic agent used by this invention, Sanko Chemical TBX-25, copper TBX-310, etc. by Sanko Chemical Industry Co., Ltd. are mentioned. These are antistatic agents which consist of a combination of a polyether / polyolefin block copolymer and a lithium ion chloride compound.

In this invention, although it is preferable to use the above-mentioned polymer type antistatic agent of ion conductivity, you may use another polymer type antistatic agent (for example, Pelletate 203, the product made from acidic chemicals), etc. together.

Moreover, in this invention, antistatic agents other than a polymeric antistatic agent, for example, a low molecular-type surfactant (for example, Elecon PP720A, Dainichi Purification make), etc. can also be used together.

In the antistatic composition of the present invention, the amount of the polyolefin in the total amount of the polyolefin and the polymer antistatic agent is preferably 95 wt% or less, particularly preferably 60 to 95 wt%, and the amount of the polymer antistatic agent is 40 to 5 wt%. It is preferable. When the amount of the resin exceeds 95 wt%, the surface resistance value may increase, and when the amount of the resin is less than 60 wt%, the characteristics of the resin inherent may not be obtained.

You may mix | blend resin, various additives, etc. other than polyolefin with the antistatic composition of this invention in the range which does not impair the objective of this invention.

As resin, ABS resin etc. are mentioned, for example.

In addition, well-known additives, such as a crystalline nucleating agent, antioxidant, a heat stabilizer, a ultraviolet absorber, a flame retardant, a flame retardant adjuvant, a coloring agent, a pigment, an antibacterial and antifungal agent, a light resistant agent, a plasticizer, and a filler, are mentioned.

The antistatic composition of this invention may consist essentially of a polyolefin and a polymeric antistatic agent, and may consist only of these components. The term "substantially consists of" means that the composition consists only of a polyolefin and a polymer antistatic agent, and may contain the above known additives in addition to these components.

The antistatic composition of the present invention can be used as a raw material for various molded products by mixing the above components by dry blending or the like, or pelletizing by melt kneading with an extruder such as a biaxial kneader.

For example, the mixture or pellets may be introduced into an extrusion molding machine, an injection molding machine, or the like, and processed into a sheet, a film, or various antistatic components. Moreover, a laminated body can be obtained by co-extrusion method etc. In general, in a molded article, only its surface portion may have an antistatic property in many cases. Therefore, it is preferable to set it as a laminated structure and to form the layer which consists of the antistatic composition of this invention only in a surface layer from a viewpoint of the reduction of the usage-amount of an antistatic agent.

Moreover, containers, such as trays for electronic components, can be manufactured by shape | molding a sheet | seat, a film, and a laminated body by well-known methods, such as vacuum molding.

Moreover, it is preferable that the thickness (thickness of the surface layer which consists of an antistatic composition in the case of a laminated sheet) of the sheet which consists of an antistatic composition of this invention is 10 micrometers or more. If it is less than 10 micrometers, control of multilayer extrusion may become difficult.

In addition, there are no adverse effects such as antistatic performance by increasing the thickness of the sheet. However, if the thickness is too thick, it may be undesirable in terms of cost. It is especially preferable that the thickness of a sheet is 10 micrometers-2 mm.

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, each raw material used in the Example is as follows.

In addition, MFR is the value (g / 10min) measured by 230 degreeC and 2.16 kg of loads.

(1) polypropylene

E110G (Homopolypropylene): Prime Polymer Preparation, MFR = 0.3

E105GM (Homopolypropylene): Prime Polymer Preparation, MFR = 0.5

E200GV (Homopolypropylene): Prime Polymer Manufacture, MFR = 1.6

E330GV (Homopolypropylene): Prime Polymer Manufacture, MFR = 2.4

E304GP (Homopolypropylene): Prime Polymer Preparation, MFR = 2.8

F704NT (Homopolypropylene): Prime Polymer Manufacture, MFR = 8.3

E2000GV (Homopolypropylene): Prime Polymer Manufacture, MFR = 18

F704NT (Homopolypropylene): Prime Polymer Preparation, MFR = 8.1

(2) polyethylene

HE30 (Low Density Polyethylene): Prime Polymer Preparation, MFR = 0.3

(3) ion conductive polymer type antistatic agent

TBX-25: Sanko Chemical Industry Co., Ltd.

Example 1

Using a single screw extruder, a two-layer sheet was produced by coextrusion.

The raw material of the surface layer used what dry-blended E110G (85 wt%) which is polypropylene, and TBX-25 (15 wt%) which is an antistatic agent. In addition, E105GM (100 wt%) which is polypropylene was used as a raw material of a base material layer. The conditions at the time of sheet shaping were as follows.

Heater set temperature; 200 to 240 ℃

Sheet cooling temperature; 60 ℃

Sheet take-up speed; 2 m / min

Sheet thickness (total thickness); 0.4 mm

The kind of polypropylene used, the compounding ratio of polypropylene and an antistatic agent, the thickness of the sheet surface layer, and its surface specific resistance value are shown in Table 1.

In addition, the surface specific resistance value was measured about the sample stored for 12 hours or more at 23 degreeC and 50% RH after manufacture based on JISK6911, making sample shape into 11 cm x 11 cm.

Examples 2-4 Comparative Examples 1-3

Except using the polypropylene shown in Table 1, it carried out similarly to Example 1, and manufactured and evaluated the two-layer sheet. The results are shown in Table 1.

From the results of Examples 1-4 and Comparative Examples 1-3, the relationship between the MFR of polypropylene of a surface layer and the surface specific resistance value of the surface layer was calculated | required. The results are shown in FIG. Further, in the value (vertical axis) of the surface resistivity, 1.0E + X is the mean of 1 × 10 ^X. For example, 1.0E + 08 means 1 × 10 ⁸ . The same applies to FIGS. 2 and 3.

From this figure, it was confirmed that the surface specific resistance value of the sheet largely depends on the MFR of the polypropylene, and changes critically in the region where the MFR is less than 2.5.

Examples 5-8

As shown in Table 1, except having changed the compounding ratio of polypropylene (E110G) and antistatic agent (TBX-25), it carried out similarly to Example 1, and manufactured and evaluated the two-layer sheet. The results are shown in Table 1.

Examples 9 and 10

As shown in Table 1, except having changed the thickness of the sheet surface layer, it carried out similarly to Example 1, and manufactured and evaluated the two layer sheet. The results are shown in Table 1.

Examples 11 and 12

As shown in Table 1, except having changed the compounding ratio of polypropylene (E110G) and antistatic agent (TBX-25), and the thickness of the sheet surface layer, it carried out similarly to Example 1, and manufactured and evaluated the two-layer sheet. The results are shown in Table 1.

Examples 13-17

As shown in Table 2, except having used polypropylene, polyethylene, or polyethylene instead of polypropylene as resin, it carried out similarly to Example 1, and manufactured and evaluated the two-layer sheet. The results are shown in Table 2.

Example 18

The relationship between the surface layer thickness and surface specific resistance of the two-layer sheet was evaluated.

Specifically, a two-layer sheet was produced in the same manner as in Example 1 except that the thickness of the sheet surface layer was changed to 10 µm, 130 µm, and 160 µm.

Similarly, except having changed the polypropylene into E105GM and changing the thickness of the sheet surface layer into 10 micrometers, 120 micrometers, and 150 micrometers, it carried out similarly to Example 1, and manufactured the 2-layer sheet.

In addition, control of the surface layer thickness was performed by making sheet taking speed constant and adjusting the rotation speed of an extruder.

About the obtained sheet | seat, the relationship between the surface layer thickness of a sheet | seat and surface specific resistance value was investigated. The results are shown in Table 3 and FIG. 2.

Example 19

About the relationship between the compounding quantity of an antistatic agent and the surface specific resistance value, it evaluated by changing the film thickness of a surface layer (50 micrometers, 130 micrometers, and 160 micrometers).

Specifically, a two-layer sheet was produced in the same manner as in Example 1 except that the compounding amount of the antistatic agent (TBX25) was set to 15 wt%, 20 wt%, 30 wt%, and 40 wt% for each film thickness.

The relationship between the compounding quantity of an antistatic agent and the surface specific resistance value obtained from the evaluation result of a sheet | seat is shown in FIG.

Example 20

Except having made thickness of the surface layer into 60 micrometers, it carried out similarly to Example 1, and manufactured and evaluated the two-layer sheet. The surface resistivity was 4.3 x 10 ⁸ (Ω / sq).

Moreover, 11 cm x 11 cm of sample was taken out from the sheet | seat, and after manufacture, it stored at 23 degreeC and 50% RH for 12 hours or more. The flakes were taken out from almost the center of this sample, stained and fixed with ruthenium tetraoxide, and then sliced with cryomicrotome. The cross section of the TD direction and MD direction of the flaky sample was observed with the transmission electron microscope (H-7650, Hitachi Corporation make), and it photographed. As shown in the cross-sectional schematic diagram of FIG. 4A, it was found that the antistatic agent was distributed throughout the thickness of the surface layer and was concentrated in the central portion. In other words, there was a rough distribution in the layer. The photograph (* 5000) of FIG. 5 photographed the center part in which the antistatic agent is concentrated.

Example 21

A two-layer sheet was produced and evaluated in the same manner as in Example 1 except that the compounding ratio of polypropylene (E110G) and antistatic agent (TBX-25) was set to 60:40 and the thickness of the surface layer was set to 70 µm. The surface resistivity was 6.6 × 10 ⁷ (Ω / sq).

In the same manner as in Example 20, the cross section of the sheet was observed and photographed. As shown in the cross-sectional schematic diagram of FIG. 4B, it was found that the antistatic agent was distributed throughout the thickness of the surface layer and was concentrated in the central portion. In the same manner as in Example 20, there was a roughness distribution in the layer, but the degree of compaction of the antistatic agent in the central portion was higher than in Example 20. The photograph (* 5000) of FIG. 6 photographed the center part in which the antistatic agent is concentrated.

Comparative Example 4

A homogeneous polypropylene (F704NT) having a high MFR was used as the polypropylene, and a two-layer sheet was produced and evaluated in the same manner as in Example 1 except that the thickness of the surface layer was 70 μm. The surface resistivity was 2.9 x 10 ¹¹ (Ω / sq).

In the same manner as in Example 20, the cross section of the sheet was observed and photographed. As shown in the cross-sectional schematic diagram of FIG. 4C, the antistatic agent was distributed only over the entire surface portion having a thickness of about 20 μm of the surface layer, and there was no dense distribution as in Examples 20 and 21. The photograph (* 5000) of FIG. 7 has taken the part containing the surface part of a surface layer.

4-7, it turned out that the sheet cross section of Example 20, 21 has a specific structure by which antistatic agent is concentrated in the center part compared with the comparative example 4. As shown to FIG.

Example 22

A 9 cm x 9 cm sample was taken out from the two-layered sheet prepared in Example 1, using a stretching apparatus (manufactured by BRUCKNER) under stretching conditions of a temperature of 158 ° C, a preheating time of 60 seconds, and a speed of 6 m / min. It extended | stretched with the draw ratio 2x2, 3x2, 3x3, 4x3, respectively. The cooling time was 10 seconds. For each sample, the surface specific resistance value was measured before and after stretching. The results are shown in Table 4.

The antistatic composition of the present invention may be, for example, an antistatic container such as a tray, an automotive part requiring an antistatic property, a home appliance device part, an electronic device part, an electronic material manufacturing device, a battery member, an information office device part, or a communication device. , Housing parts, optical mechanical members, household goods, industrial members, building materials, flooring materials, packaging distribution members, and the like. It is especially preferable as a material for containers and packaging materials, such as a carrier tray of electronic components, such as an IC, a capacitor | condenser, a transistor, and LSI.

Claims (6)

An antistatic composition containing a polyolefin having a melt flow rate of less than 2.5 (g / 10 min) and a polymer type antistatic agent. The method of claim 1, The antistatic composition whose amount of the said polyolefin occupies for the total amount of the said polyolefin and a polymeric antistatic agent is 95 to 60 wt%, and the quantity of the said polymeric antistatic agent is 5 to 40 wt%. The sheet or film which consists of an antistatic composition of Claim 1 or 2. The method of claim 3, wherein A sheet or film having a thickness of 10 μm or more. The laminated body containing the sheet | seat or film of Claim 3 or 4. The molded article which consists of a sheet | seat, a film, or a laminated body in any one of Claims 3-5.

Images