JPH01223162A - Electrically conductive resin composition and prevention of static electrification using same - Google Patents

Abstract

PURPOSE:To obtain the title inexpensive composition outstanding in antistatic capability, transparency etc., capable of preventing static electrification when applied on the surface of synthetic resin forms, by incorporating a resin having ether-type oxygen linkage with a specific beta-diketone-based metal complex. CONSTITUTION:The objective composition can be obtained by incorporating (A) a resin having ether-type oxygen linkage in the main or side chain, pref., vinyl chloride-(meth)acrylic polyalkylene oxide ester copolymer resin or vinyl chloride-polyoxyalkylene monoalkyl ether copolymer resin with (B) 0.5-20wt.% (pref., 1-15wt.%) of a beta-diketone-based metal complex of the formula [M is metal (pref., Li); n is 1-4; R1 and R2 are each H, 1-30C (cyclic) aliphatic hydrocarbon group, aromatic hydrocarbon group or oxy group therefrom] (e.g., acetylacetone metal complex). The layer of said composition is formed on the surface of a synthetic resin form to accomplish the objective prevention of static electrification.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a conductive resin composition with excellent antistatic properties and an antistatic method using the same.

(Prior art) Synthetic resins such as vinyl chloride resins are inexpensive, have good moldability, and have excellent properties, so they can be used for various molded products,
Widely used as sheets and films. However, synthetic resin molded bodies such as vinyl chloride resins are easily charged with electricity, which causes various problems.

Various vinyl chloride-based conductive resin compositions that prevent such charging have been proposed.

For example, in JP-A No. 62-260847, a metal salt such as lithium perchlorate is added to a vinyl chloride copolymer having vinyl chloride units and specific (meth)acrylic acid polyalkylene oxide ester units. A vinyl chloride-based conductive resin composition is disclosed.

(Problems to be Solved by the Invention) Since such a conductive resin composition has excellent conductivity,
It has excellent antistatic properties, good transparency and bleedability, and low surface stickiness.

However, although the transparency and bleedability were good, and the surface was less sticky, it was still not satisfactory and there were problems that needed to be solved.

The present invention solves the above problems, and its purpose is to provide a conductive resin composition and an antistatic method that are inexpensive and have improved antistatic properties, transparency, bleedability, and surface stickiness. Our goal is to provide the following.

(Means for Solving the Problems) The conductive resin composition of the present invention comprises a resin having an ether type oxygen bond containing a β-diketone metal complex represented by the following formula (I).

(In the formula, M is a metal, n is 1 to 4, R+, R1 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cycloaliphatic hydrocarbon group, an aromatic hydrocarbon group, or ) Furthermore, the antistatic method of the present invention achieves the above object by forming a layer of the conductive resin composition described above on the surface of the synthetic resin molded article. be done.

In the present invention, examples of resins having an ether type oxygen bond include polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacecool resins, polyetherimide resins, maleic acid resins, acrylic ester resins, and vinyl chloride-acrylic acid. Ester copolymer resin, or vinyl chloride-(meth)acrylic acid polyalkylene oxide ester copolymer resin, vinyl chloride-
There are polyoxyalkylene monoalkyl ether copolymer resins, etc., and refers to resins having an ether type oxygen bond -〇- in the main chain or side chain.

In particular, in the present invention, when a vinyl chloride-(meth)acrylic acid polyalkylene oxide ester copolymer resin or a vinyl chloride-polyoxyalkylene monoalkyl ether copolymer resin is used as the resin having an ether type oxygen bond, a small amount of The use of a β-diketone metal complex is preferable because it exhibits antistatic properties.

In the present invention, the β-diketone metal complex represented by the above formula (I) is contained in the above resin to form a resin composition. By introducing this β-diketone metal complex, conductivity is developed and the antistatic properties of the resin are improved.

The β-diketone metal complex is generally contained in an amount of 0.5 to 20% by weight, preferably 1.0 to 15% by weight. If it is less than 0.5% by weight, it is difficult to obtain the desired chargeability, and if it is more than 20% by weight, it may bleed from the resin composition, which is undesirable.

Examples of the β-diketone metal complexes include acetylacetone metal complexes, dibenzoylmethane metal complexes, acetoacetate metal complexes, malonic acid diester metal complexes, and these lithium complexes are most preferably used.

In order to obtain a conductive resin composition by incorporating a β-diketone metal complex into the above resin, the resin composition may be obtained by directly adding and mixing or kneading the above complex compound to the above resin under appropriate conditions. In addition, the resin composition may be obtained by dissolving the above resin and metal salt in a suitable organic solvent to obtain a solution of the resin composition, or by removing the organic solvent from the solution of the resin composition. The forms of objects include powder, granules, plates,
It may be in any form such as a tube, sheet, film, various containers, or paint solution.

As described above, the conductive resin composition of the present invention can be molded into various shapes, and in particular, when a layer of the conductive resin composition described above is formed on the surface of various synthetic resin molded articles of various shapes. , antistatic can be achieved effectively and inexpensively with a small amount of the composition.

The synthetic resins constituting the above-mentioned synthetic resin moldings include resins having ether-type oxygen bonds constituting the conductive resin compositions mentioned above, vinyl chloride resins, acrylic resins, styrene resins, polyamide resins, and polyimide resins. Resins and the like are suitable because they have good adhesion to the resin composition.

In the case of olefin resins such as polyethylene and polypropylene, those whose surfaces are subjected to, for example, corona discharge treatment to increase wetting tension are used.

A method for forming a layer of the above-mentioned conductive resin composition on the surface of a synthetic resin molded article is to dissolve the resin composition in a suitable organic solvent to form a solution, and apply it, spray it, dip it, etc. The method used is to apply it to the surface of a synthetic resin molded body and then dry it. Alternatively, a method of coating by melt extrusion under appropriate conditions without using an organic solvent may also be adopted.

(Function) In the present invention, the β-diketone metal complex has excellent compatibility with the resin having an ether type oxygen bond.

Therefore, the resin composition of the present invention does not cause bleeding, surface stickiness, or decrease in transparency. In addition, β
- When a diketone-based metal complex is contained, a path through which ions of the metal complex can move well is formed continuously in this resin composition, which results in good conductivity and excellent antistatic properties. shows.

(Example) Examples and comparative examples of the present invention are shown below.

A copolymer resin of 72% by weight of vinyl chloride and 28% by weight of polyethylene glycol polybutylene glycol methacrylate (Blemmer 55 pH!T-800, manufactured by NOF Corporation) was mixed with a toluene/methyl ethyl ketone/cyclohexanone mixed solvent (weight ratio 1). /1/4) to form a solution with a concentration of 12% by weight. To this solution, 3% by weight of acetylacetone lithium complex was added as a methanol solution to obtain a solution of a conductive resin composition.

This solution was poured onto a glass plate, dried at a temperature of 50°C for 30 minutes, and then further dried at a temperature of 110°C for 60 minutes to a thickness of 30 μm.
A thick casting film was produced. The surface resistivity, transparency, bleedability, and surface stickiness of this film were measured as follows. The results are shown in Table 1.

(I) Surface specific resistance value The above casting film was heated at 20°C, 565%RH.
After leaving it for 24 hours, the surface high resistance needle (HirestaMC
The surface specific resistance value was measured using P-TBSTER (manufactured by Mitsubishi Yuka Co., Ltd.).

(2) The transparent casting film was visually observed and rated very good as O1, good as 0, and poor as ×.

(3) Bleeding The casting film was left at room temperature and visually observed, and evaluated as × when a lot of cloudiness or precipitates were observed on the film surface, ○ when there was little, and O when there was very little.

(4) Leave the casting film with a sticky surface at room temperature and use finger pressure to determine whether the surface is highly sticky or O1 if it is small.
A very small one was evaluated as O.

1 team 1 polyester resin (Erythyl, manufactured by Unitika) in toluene/methyl ethyl ketone/mixed solvent (weight ratio 1/3)
to obtain a 12% by weight solution. The same procedure as in Example 1 was carried out except that 10% by weight of dibenzoylmethane lithium complex was added to this solution. The results are shown in Table 1.

One piece of polyether resin (Noryl, manufactured by General Electric Co., USA) was mixed with an ethylene chloride/carbon tetrachloride mixed solvent (
(weight ratio: 1/1) to obtain a solution with a concentration of 12% by weight. The same procedure as in Example 1 was carried out except that 15% by weight of the acetylacetone lithium complex was added to this solution.

The results are shown in Table 1.

Group 11 The same procedure as in Example 1 was carried out except that 5% by weight of acetylacetone iron complex was added instead of 3% by weight of acetylacetone lithium complex in Example 1. The results are shown in Table 1.

1 Application 1 The solution of the conductive resin composition obtained in Example 1 was applied to a transparent hard vinyl chloride resin plate with a thickness of 2 mm using a doctor blade to a thickness of 20μ. A layer of composition was formed.

The adhesion of this layer was good. Regarding this coated plate,
The surface resistivity, transparency, bleedability, and surface stickiness were measured in the same manner as in Example 1.

The results are shown in Table 1.

Hokuai Sarako vinyl chloride resin was dissolved in a tetrahydrofuran/cyclohexanone mixed solvent (weight ratio 3/1) to form a 12% by weight solution. The same procedure as in Example 1 was carried out except that 10% by weight of the acetylacetone lithium complex was added to this solution. The results are shown in Table 1.

Five comparison group 1 The same procedure as in Example 1 was carried out except that the acetylacetone lithium complex of Example 1 was not added. The results are shown in Table 1.

Comparison (1) The same procedure as in Example 1 was carried out except that 4% by weight of lithium perchlorate was added in place of 3% by weight of the lithium acetylacetone complex in Main Example 1.

The results are shown in Table 1.

(Margin below) Table 1 (Effects of the Invention) The conductive resin composition of the present invention contains a specific β-diketone metal complex in a resin that fosters ether-type oxygen bonds. The composition has excellent conductivity, is inexpensive, has excellent antistatic properties, and maintains its antistatic properties over a long period of time. It also has good transparency and bleedability, and has almost no surface stickiness.

Furthermore, in the antistatic method of the present invention, a layer of the conductive resin composition described above is formed on the surface of the synthetic resin molded article, so that antistatic properties of the synthetic resin molded article can be effectively and inexpensively prevented using a small amount of the composition. done to.

Claims (1)

[Claims] 1. The following formula (
A conductive resin composition containing a β-diketone metal complex represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...Formula (I) (In the formula, M is a metal, n is 1 to 4, R_1 and R_2 are hydrogen atoms, and aliphatic hydrocarbons having 1 to 30 carbon atoms. group, cycloaliphatic hydrocarbon group, aromatic hydrocarbon group, or these oxy groups.) 2. The following formula (I) is applied to the resin having an ether-type oxygen bond on the surface of the synthetic resin molded article. An antistatic method comprising forming a layer of a conductive resin composition containing the β-diketone metal complex shown below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...Formula (I) (In the formula, M is a metal, n is 1 to 4, R_1 and R_2 are hydrogen atoms, and aliphatic hydrocarbons having 1 to 30 carbon atoms. group, a cycloaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an oxy group thereof.)