JP2003128806A - Excellent antistatic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent antistatic film having excellent antistatic ability for the packaging of electronic circuit boards and electronic parts; the packaging and covering of electronic, medical or precision instruments; the dustproof packaging of medicinal drugs, cosmetics and food; the packaging of dangerous materials; and so on. SOLUTION: The film is composed of at least a monolayer film of 10 μm or larger in thickness comprising a polyolefin composition containing 0.01% to 5% of polymer charge-transfer bonded body comprising an organic boron polymer compound represented by structural formula (1). By this, the antistatic ability is improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to packaging and packaging in the field of semiconductors, packaging of electronic circuit boards, packaging of electronic parts, packaging and covers of electronic equipment, medical equipment, precision equipment and the like, as well as pharmaceuticals, cosmetics and food products. Dustproof packaging,
The present invention relates to a film having an excellent antistatic ability for the purpose of packaging dangerous goods such as explosives.

[0002]

2. Description of the Related Art Plastic films are used in a wide range of fields because they have excellent properties such as transparency, durability and light weight. However, since the plastic film is an electrically insulating base material, various problems due to static electricity may occur depending on the method of use or application. Especially in the electronics field,
The destruction and damage of ICs and LSIs due to static electricity is becoming a problem, and countermeasures against static electricity are an important and urgent theme. Therefore, it is necessary to improve the electrical characteristics of the insulating material itself, which is apt to generate an electrostatic charge in the surroundings.
BACKGROUND ART Plastics in which metal-plated fibers and the like are kneaded, and films and sheets in which carbon black, graphite, tin oxide, zinc oxide, indium oxide and the like are mixed have been used for packing and packaging.

However, these inorganic conductive agents cannot be converted into a material that is not charged as a whole unless they are mixed in a matrix resin constituting a film or sheet so much that they are in contact with each other, and the cost is increased. In addition, the physical properties of the base material are significantly changed. Further, there is also a drawback that a transparent antistatic molded article cannot be produced from a film or sheet containing these inorganic conductive agents.

On the other hand, an internal kneading type antistatic agent to which a surfactant is applied may be added in a small amount, does not extremely change the physical properties of the substrate material, and can form a transparent film. Since it can be processed at a low cost, it has been widely used as a measure against static electricity mainly for the purpose of preventing dust adhesion. However, the antistatic agent exhibits its effect only when the molecules migrate to the surface of the substrate material, and what appears on the surface is unstable, and it depends on external conditions such as temperature, humidity or contact, friction, and factors. It is disturbed or removed, and most of the molecules inside move to the surface and escape from the surface after a certain period of time. I couldn't. Furthermore, since the antistatic mechanism itself depends on the carrier effect (ion conduction mechanism) brought about by the hydrophilic group part of the molecule of the antistatic agent existing on the surface, the orientation adsorption state of the molecule of the antistatic agent on the surface may be a little. However, if the disturbance occurs, it becomes impossible to attenuate the charged charges by 100%. Therefore, it cannot be said in a strict sense that the addition of the antistatic agent is a means capable of eliminating the influence of the static electricity in the surroundings at the time of transporting, using, or the like of the IC or LSI-related functional product.

Therefore, as a solution to these problems, a polymer charge transfer type conjugate produced by reacting an organic boron polymer compound in which boron atoms are regularly incorporated in the molecule with a hydroxyalkylamine. Is used as an antistatic agent, the chargeability is removed, and the technology that allows the instantaneous charge generated by contact, friction, external voltage application, etc. to be quickly and completely leaked is described above. Different from the antistatic agent, it has been proposed as a material capable of producing a permanent and stable non-charged product. However, molded articles and films obtained from a resin composition containing a polymer charge transfer type binder composed of this organoboron polymer compound are treated with a corona treatment or the like on the surface where the antistatic ability is desired to be exhibited. There was a problem that the effect would not be exhibited unless the molecular charge transfer type binder was transferred to the surface of the substrate material, or a stable antistatic effect could not be obtained depending on use conditions.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and has a resin composition mainly composed of a polyolefin resin containing a polymer charge transfer type binder comprising an organic boron polymer compound. It is intended to provide a film excellent in antistatic ability, which is characterized by comprising a material.

[0007]

The present invention has been made to achieve the above object. The invention according to claim 1 is a polymer charge transfer type compound comprising an organic boron polymer compound represented by the structural formula (1). It is a film having excellent antistatic ability, which is composed of at least a monolayer film having a thickness of 10 μm or more, which is made of a polyolefin resin composition containing 0.01% to 5% of a binder.

The invention described in claim 2 is the same as claim 1.
In the film having excellent antistatic ability described in (3), the single layer film is laminated with another film or a metal foil without surface treatment.

Furthermore, the invention described in claim 3 is the film excellent in antistatic ability according to claim 2,
It is characterized in that the single-layer film and the other film or the metal foil are laminated by a sand laminating method using a polyolefin resin as a sand resin.

Furthermore, the invention according to claim 4 provides the film excellent in antistatic ability according to claim 3,
The sand resin used when laminating the single-layer film and the other film or metal foil by the sandrami method has a density of 0.88 to 0.91, and as a comonomer component,
It is a linear rhoden polyethylene resin that uses butene, hexene, and octene.

Furthermore, the invention described in claim 5 is the film excellent in antistatic ability according to any one of claims 1 to 4, wherein the polyolefin resin constituting the monolayer film is a polyethylene resin. It is characterized by

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic explanatory view of one embodiment of a film having excellent antistatic ability according to the present invention. The film 1 has a single-layer structure, and specifically, a polyolefin resin composition containing 0.01% to 5% of a polymer charge transfer type binder composed of an organic boron polymer compound represented by the general formula (1). And a monolayer film having a thickness of 10 μm or more.

General formula (1) applicable in the present invention
The polymer charge transfer type binder comprising the organoboron polymer compound shown in 1) has characteristics such as electrochemical polarization, and when it is contained in 0.01% to 5% polyolefin resin, the polyolefin resin The film made of the composition exhibits an effect of absorbing the electric charge charged on the surface.

If the proportion of the polymer charge transfer type binder comprising the organoboron polymer compound is less than 0.01%, the antistatic ability is not exhibited, and if it is more than 5%, the film-forming machine is used during film processing. If the resin composition slips in the screw (3) and a film cannot be formed (cannot be extruded), the desired antistatic effect cannot be obtained.

Further, in the polyolefin resin composition containing 0.01% to 5% of the polymer charge transfer type binder comprising the organic boron polymer compound, an inorganic filler, an organic filler, another polyolefin resin, It is also possible to blend a polymer material such as an elastomer within a range that does not impair the effects of the present invention to improve workability, rigidity, flexibility and the like. The above-mentioned polymer material is 50% of the composition of the present invention.
It is preferable to mix them in an amount up to.

In addition to the above components, other compounding agents, such as stabilizers, antioxidants, processing aids such as lubricants and antiblocking agents, flame retardants, various pigments,
Dyes, ultraviolet absorbers and the like can be appropriately added.

The resin composition constituting the film 1 is produced by kneading a polyolefin resin and a polymer charge transfer type binder composed of the organic boron polymer compound represented by the structural formula (1) by any conventionally known compounding method. can do. For example, the kneading may be performed with an open roll, an intensive mixer, a cokneader, a single screw or twin screw extruder, or the like. Specifically, a powdery or pelletized polyolefin resin is blended with a polymer charge transfer type binder composed of a predetermined organic boron polymer compound represented by the general formula (1) and desired additional components, and a Henschel mixer or the like is used. After kneading, the mixture may be melt-mixed with a single-screw or twin-screw extruder to obtain a pellet resin composition. The compounding ingredients may be added to the resin during kneading, or may be added by a masterbatch method. Then, the film 1 having excellent antistatic ability of the present invention is obtained by forming a film using the resin composition having the above composition by a general-purpose film forming method. The film 1 excellent in antistatic ability thus obtained has a thickness of 10 μm.
The above single-layer film, not a multi-layer film obtained by coextrusion provided with a layer of a resin composition containing a polymer charge transfer type binder composed of an organoboron polymer compound, rather than an organic layer to another layer It is possible to maintain a stable antistatic effect without worrying about the migration of the polymer charge transfer type binder composed of the boron polymer compound.

Further, in the case of extrusion molding of a film or sheet, hollow molding, etc., it is possible to form a multi-layer with another resin. Depending on the purpose, one side or both sides of the organic compound represented by the structural formula (1) can be used. Although a single layer film made of a resin composition containing a polymer charge transfer type binder made of a boron polymer compound can be laminated, as described above, from the viewpoint of stability of the antistatic ability, it is less preferable to make a multilayer. Absent.

The present invention has been described above by taking the film 1 having a single layer structure and excellent in antistatic ability as an example. However, the present invention is not limited to this, and the physical strength such as tearability, puncture strength and the like. Alternatively, in order to improve chemical properties such as oxygen barrier properties and moisture resistance, other films and metal foils may be laminated and laminated on the single layer film. At the time of bonding, the bonding is performed without surface treatment such as corona treatment, ozone treatment, and frame treatment for increasing the activity of the bonded surface. When the monolayer film constituting the film having excellent antistatic ability according to the present invention is subjected to a surface treatment, a polymer charge transfer type binder composed of an organoboron polymer compound is attracted to the treated surface, and the organoboron is formed in the film. A concentration gradient of the polymer charge transfer type binder composed of the polymer compound occurs, and the antistatic effect on the untreated surface, that is, the surface of the laminated film becomes unstable.

Further, when high laminating strength (laminating strength) is required at the time of laminating, it is preferable to perform laminating by a sand laminating method. In addition, the sand resin used when laminating by the sand laminating method has a density of 0.88 to 0.9.
Further, by using a linear rhoden polyethylene resin using butene, hexene, and octene as the comonomer component, further laminating strength can be obtained. That is, if the resin used when laminating by the sand lam method is a linear rhoden polyethylene resin using butene, hexene, and octene as comonomer components having a density of 0.88 to 0.91, the AC agent (anchor coating agent) ), Sufficient bonding strength can be obtained without using
Since it can be used without the use of an agent, the effect of reducing the antistatic ability of the AC agent and eliminating elution of the AC agent to the inner surface can be obtained.

Further, when a packaging bag is made of the film having excellent antistatic ability of the present invention, when the films are adhered to each other by heat sealing with the surface of the monolayer film having excellent antistatic property constituting the bag as an inner surface, The polymer charge transfer type binder composed of the boron polymer compound acts as an inhibition of the heat-sealing property. At this time, by applying a polyethylene resin having a low melting point among the polyolefin resins as the resin constituting the film having excellent chargeability of the present invention, it is possible to reduce the deterioration of the heat sealability as described above. . Further, additives such as antioxidants, slip agents, and anti-blocking agents can be eliminated from this polyethylene resin, which is considered as a method of using the film of the present invention, and is a packaging material for packaging bags for electronic materials. Will be suitable as.

Although the film having excellent antistatic ability of the present invention has been described above, this film is used in many fields for the purpose of preventing static electricity and removing static electricity. For example, by taking advantage of its excellent antistatic function, packaging materials for transporting and storing ICs (carriers, trays, bags, racks, containers, etc.), electronic parts boxes, magnetic tapes, audio tape cases, slip sheets, explosives, etc. It is applied to packaging materials for goods. Further, by making use of the static electricity removing function, it can be applied to a charge eliminating roll, a sheet or the like, or as a semiconductor material to information recording paper, various resistors and the like. Incidentally, in the resin composition constituting the film having excellent antistatic ability of the present invention, silver, copper, brass, iron or the like powdered or fibrous, or carbon black or tin-coated titanium oxide, tin. By coexisting with a conductive filler such as coated silica, it is possible to provide a more accurate electromagnetic wave shield material.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following examples. <Example 1> polyethylene resin (manufactured by Mitsui Chemicals; Mirason M-16P, density = 0.923 g / cm ^3, melt flow rate = 3.7 g / 10 min) with respect to an organic represented by the structural formula (2) 2% by weight of a polymer charge transfer type binder composed of a boron polymer compound was added, and the addition was performed with an extruder.
Melt kneading at 0 ° C. gave pellets.

[0024]

[Chemical 2]

Next, using this pellet, a film having a thickness of 40 μm was obtained by an inflation method at 160 ° C. This film was stored in an environment of 25 ° C. and 65% for 12 hours, and the surface resistivity was measured to be 2 × 10 ⁹ Ω / □,
It was confirmed that the film had a sufficient antistatic effect. Furthermore, the film was stored at 25 ° C. and 65% for 3 months, and the surface resistivity was measured to be 1.5 × 10 ⁹
It was Ω / □ and maintained a sufficient antistatic effect.

Example 2 The single-layer film obtained in Example 1 and the PET / Al multi-layer film were laminated with a polyethylene resin (Mitsui Chemicals; Mirason M) so that the Al surface was on the inside.
-14P, density = 0.919 g / cm ³ , melt flow rate = 5.1 g / 10 min), and the lamination was performed by the sand lam method. At the time of bonding, the single layer film obtained in Example 1 was not subjected to surface treatment such as corona treatment and frame treatment, and the Al surface of the multilayer film was subjected to corona treatment, and an adhesive was applied on the Al surface. Was applied as an anchor agent. After such processing, the Mirason M-
14P was attached by a sand lamella method at an extrusion temperature of 320 ° C. and a thickness of 30 μm. Next, this film was subjected to an aging treatment at 50 ° C. for 2 days and then stored in an environment of 25 ° C. and 65% for 12 hours, and the surface resistivity was measured to be 3 × 10 ⁹ Ω / □. It was confirmed that the film had a sufficient antistatic effect without any change from that before bonding. In addition, the film at 25 ℃ 65
% For 3 months and the surface resistivity was measured to be 3 × 10 ⁹ Ω / □, indicating that a sufficient antistatic effect was maintained.

Example 3 Polyethylene resin (Mitsui Chemicals; Millason M-14P, density = 0.919 g / cm)
³ , melt flow rate = 5.1 g / 10 min), 8% by weight of a polymer charge transfer type binder composed of the organic boron polymer compound represented by the general formula (2) was added to the extruder. Melted and kneaded at 190 ° C. to obtain pellets. next,
The pellets and the polyethylene resin were mixed at a ratio of 1:10 to obtain a resin composition in which the kneading ratio of the polymer charge transfer type binder composed of the organic boron polymer compound was 0.8% by weight. Then, using this resin composition, a film having a thickness of 20 μm was obtained by a casting method at 240 ° C. Subsequently, the film was stored in an environment of 25 ° C. and 65% for 12 hours, and the surface resistivity was measured and found to be 1.5 × 10 ¹⁰ Ω / □, which had a sufficient antistatic effect. Furthermore,
The film was stored at 25 ° C. and 65% for 3 months, and the surface resistivity was measured to be 2.5 × 10 ¹⁰ Ω / □,
The antistatic effect was sufficient.

Example 4 The single-layer film obtained in Example 1 and the PET / Al multi-layer film were made of a polyethylene resin (Mitsui Chemicals; Mirason M, with the Al surface facing inside).
-14P, density = 0.919 g / cm @ 3, melt flow rate = 5.1 g / 10 min), and the lamination was carried out by the sandrami method. At the time of bonding, the film obtained in Example 1 was not subjected to surface treatment such as corona treatment and frame treatment, and the Al surface of the multilayer film was subjected to corona treatment. Then, after such treatment, an adhesive agent is applied thereon as an anchor agent, and then Mirason M-1
4P was attached by a sand lamella method at an extrusion temperature of 320 ° C. and a thickness of 50 μm. Next, this film is aged at 50 ° C. for 2 days, and then,
It was stored in an environment of 25 ° C and 65% for 12 hours, and the surface resistivity was measured to be 2 x 10 ¹⁰ Ω / □, which is the same as before bonding and has a sufficient antistatic effect. confirmed. Further, the film was stored at 25 ° C. and 65% for 3 months, and the surface specific resistance value was measured to be 1
It was × 10 ¹⁰ Ω / □, and the sufficient antistatic effect was maintained.

Example 5 The single-layer film obtained in Example 1 and the PET / Al multi-layer film were linear rhoden polyethylene resin (manufactured by Japan Polychem; LLDPE, density = 0.890 g / c
m ³ and melt flow rate = 3.7 g / 10 minutes), and the lamination was performed by the sand lamella method. At this time, Example 1
No surface treatment such as corona treatment or frame treatment was performed on the single-layer film obtained in, and only the corona treatment was performed on the Al surface of the multilayer film, without applying an anchoring agent on it. , LLDPE were laminated at a thickness of 50 μm under the conditions of an extrusion temperature of 290 ° C. Next, this film was stored in an environment of 25 ° C. and 65% for 12 hours, and the surface resistivity was measured to be 4.5 × 10 ¹⁰ Ω / □,
It was confirmed to have a sufficient antistatic effect without any change from that before the bonding. In addition, the film at 25 ℃
It was stored at 65% for 3 months and the surface resistivity was measured to be 4.2 × 10 ¹⁰ Ω / □, indicating that a sufficient antistatic effect was maintained.

<Example 6> Polypropylene resin (Nippon Polychem; FA3DA, melt flow rate = 7 g / 10)
4% by weight of the organic boron polymer compound represented by the general formula (2), and melt-kneaded at 190 ° C. in an extruder to obtain pellets. It was Next, a film having a thickness of 40 μm was obtained from the pellets by an inflation method at 180 ° C. This film was stored in an environment of 25 ° C. and 65% for 12 hours, and the surface resistivity was measured to be 1.2 × 10 ⁹ Ω / □, which was confirmed to have a sufficient antistatic effect. It was
Further, the film was stored at 25 ° C. and 65% for 3 months, and the surface resistivity was measured and found to be 1.4 × 10 ⁹ Ω / □, indicating that a sufficient antistatic effect was maintained.

Comparative Example 1 Polyethylene resin (Mitsui Chemicals; Millason M-16P, density = 0.923 g / cm)
³ , melt flow rate = 3.7 g / 10 minutes),
A 40 μm thick film was obtained by the inflation method. This film was stored in an environment of 25 ° C. and 65% for 12 hours, and the surface resistivity was measured to be 9 × 10 ¹⁶ Ω / □,
There was no antistatic effect.

<Comparative Example 2> Polyethylene resin (Mitsui Chemicals; Mirason M-16P, density = 0.923 g / cm)
3, melt flow rate = 3.7 g / 10 min), 2% by weight of a polymer charge transfer type binder composed of the organic boron polymer compound represented by the general formula (2) was added to the extruder. Melted and kneaded at 190 ° C. to obtain pellets. Using the pellet and the polyethylene resin, a multilayer film having a thickness of 40 μm / 40 μm was obtained by a multilayer inflation method. Store this multilayer film for 12 hours in an environment of 25 ° C and 65%,
When the surface resistivity was measured, it was 5 × 10 ¹⁴ Ω / □, and there was no antistatic effect.

<Comparative Example 3> The film obtained in Example 1 and the PET / Al multilayer film were made of a polyethylene resin (Mitsui Chemicals; Mirason M-14) with the Al surface facing inward.
P, density = 0.919 g / cm ³ , melt flow rate = 5.1 g / 10 min), and the lamination was carried out by the sandrami method. At the time of bonding, a corona treatment was performed to bond the single-layer film obtained in Example 1 so as to increase the activity of the bonded surface, and the films were bonded. Other conditions are the same as in Example 2,
Corona treatment is applied to the Al surface of the multilayer film, and an epoxy adhesive is applied as an anchoring agent on the Al surface.
The pieces were laminated by the sand lamella method with a thickness of μm. Next, this film was subjected to an aging treatment under the conditions of 50 ° C. for 2 days, and then stored in an environment of 25 ° C. and 65% for 12 hours,
When the surface resistivity was measured, it was 7 × 10 ¹⁵ Ω / □, and the surface resistivity value was larger than that before bonding, and the antistatic effect was not recognized.

[0034]

INDUSTRIAL APPLICABILITY The present invention is excellent in chargeability, at least composed of a single layer film made of a polyolefin resin composition containing a polymer charge transfer type binder made of an organic boron polymer compound represented by the structural formula (1). Since it is a film, it has excellent stability and durability of the antistatic effect, and it does not transfer the low molecular weight component as an antistatic agent to the surface of the substrate to develop the antistatic ability. The film can be used as a film for use in a film, a film for a packaging material for electronic materials, and the like, and has a great practical effect.

[Brief description of drawings]

FIG. 1 is a schematic constitutional explanatory view of a film having excellent antistatic ability of the present invention.

[Explanation of symbols]

1. A film with excellent antistatic ability

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05F 1/00 H05F 1/00 K // (C08L 23/00 C08L 67:02 67:02) (72) Inventor Isao Morimoto 1-5-1 Taito, Taito-ku, Tokyo F-terms in Toppan Printing Co., Ltd. (reference) 4F071 AA15 AA44 AE16 AF38 AH04 BA01 BB06 BB09 BC01 4F100 AB01B AB33B AK01A AK01B AK03A AK03C AK63B10BA03A02 BA02 BA02 BA02 BA02 BA02 GB16 JA13C JG03 JG03A YY00A YY00C 4J002 BB021 CF112 FD10 GG02 5G067 BA02 CA03 DA13

Claims (5)

[Claims] 1. A polymer charge transfer type binder comprising an organic boron polymer compound represented by structural formula (1) is 0.01% to 5%.
Made of a polyolefin resin composition containing 10 μm in thickness
A film excellent in antistatic ability, characterized by comprising at least the above monolayer film. [Chemical 1] 2. The film having excellent antistatic ability according to claim 1, wherein another film or a metal foil is laminated on the monolayer film without surface treatment. 3. A film having excellent antistatic ability, characterized in that the monolayer film and the other film or metal foil are laminated by a sand laminating method using a polyolefin resin as a sand resin. 4. A sand resin used when laminating a monolayer film to another film or a metal foil by a sand laminating method has a density of 0.88 to 0.91 and uses butene, hexene and octene as comonomer components. A film having excellent antistatic ability according to claim 3, which is a linear rhoden polyethylene resin. 5. The polyolefin resin constituting the monolayer film is a polyethylene resin.
A film having excellent antistatic ability according to claim 4.