JPH10278160A - Electrically conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep an enough antistatic power and no-lost transparency even under lowly humid state by a method wherein an electrically conductive composition including the suspended particles or colloidal particles of an electrically conductive polymer and a thermoplastic resin is applied on at least one side of a base material. SOLUTION: This electrically conductive laminate is obtained by applying an electrically conductive composition including the suspended particles or colloidal particles of an electrically conductive polymer and a thermoplastic resin is applied on at least one side of an inorganic or organic base material. At the preferable electrically conductive polymer, a water-soluble sulfonated polyaniline, an organic solvent-soluble polypyrrole or a long chain alkyl group substituent combined polypyrrole, a polythiophene, its derivative and the like are exampled. The electrically conductive composition includes the colloidal particles or suspended particles of the thermoplastic resin excluding the electrically conductive polymer. For the thermoplastic resin as mentioned above, an ester-based one is preferable from the view point of its film formability and the strength of a film coated surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive laminate, and more particularly to a film, a sheet, a fiber, a woven fabric, a plastic, and the like having excellent antistatic properties and conductivity even under low humidity. Specifically, antistatic fiber, conductive fiber, thermal paper, photographic support film, magnetic tape,
Examples include products that impart antistatic or conductivity properties to industrial films such as OHPs, shielding materials, and LCDs, and products that impart antistatic properties or conductivity to packaging films such as carrier tapes, trays, magazines, and IC / LSI packages. Can be

[0002]

2. Description of the Related Art Conventionally, thermoplastic films such as polyester and nylon have been used in large quantities and in a wide range as packaging films and industrial films because of their excellent heat resistance, dimensional stability and mechanical strength. . Polyethylene, polypropylene, polyvinyl chloride, etc., are inferior in heat resistance, but are widely used as packaging materials because of their good moldability and low cost. Since the synthetic resin is generally hydrophobic, static electricity is easily generated on the surface of the structure formed of the synthetic resin, and dust and the like adhere to the surface, causing various troubles.

[0003] Generally, a surfactant is used as an antistatic agent for a film, a packaging material, or the like, but the surfactant has a surface resistance (1) sufficient to suppress adhesion of dust, dust and the like.
0 ¹⁰ Ω / □ or less), and the antistatic ability tends to change under the influence of ambient moisture and moisture. In particular, there is a disadvantage that the surface resistance of the film, which has been reduced by the surfactant, is significantly increased under low humidity, and the desired antistatic ability cannot be obtained. As a result, dust adheres to the film and the surface of the packaging material, causing various troubles.

[0004] In today's high-tech environment, there is a demand for a film free from static electricity in a low humidity environment. For this purpose, an antistatic agent giving a surface resistance value of 10 ¹⁰ Ω / □ or less under a low humidity environment has been developed. Is desired. Conductive polymers such as polyaniline and polypyrrole are known as materials giving such a low surface resistance value. All of them are soluble in a specific organic solvent, but water or a water / alcohol mixed solvent system is used. Is insoluble or non-dispersible, so a method has been adopted in which a sulfonic acid group or a long-chain alkyl group is bonded to an aromatic ring to improve the solubility in an organic solvent and apply the solution. However, not only a sufficient film strength cannot be obtained by using the conductive polymer alone, but also when a resin having good compatibility with the conductive polymer is used in combination, a predetermined surface resistance value cannot be obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and its object is to make use of the excellent features of the original structure-forming body even under low humidity. It is an object of the present invention to provide a conductive laminate having sufficient antistatic ability to overcome static electricity damage and not losing transparency.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have completed the present invention. That is, the present invention is a conductive laminate in which at least one surface of an inorganic or organic substrate is coated with a conductive composition containing suspended particles or colloid particles of a conductive polymer and a thermoplastic resin.

In a preferred embodiment of the present invention, the substrate is a film or sheet, more preferably a molded product of polyester, and the coated surface of the substrate has a surface resistance at 10 ° C. and 15% RH of 10 ⁵ to 10 ^12. Ω / □, and the charge decay time is 2 seconds or less. Surface resistance value is 10 ¹² Ω / □
If it is larger and the charge decay time is longer than 2 seconds, sufficient antistatic properties cannot be obtained, which is not suitable for use in packaging films such as ICs and semiconductors. In a preferred embodiment of the present invention,
The conductive polymer is a polyaniline or a polyaniline copolymer doped with a protonic acid, or a sulfonated polyaniline, and more preferably a sulfonated polyaniline containing aminoanisolesulfonic acid as a main component. In a preferred embodiment of the present invention, the thermoplastic resin contains an ionic group and / or a polyalkylene glycol. In a more preferred embodiment, the thermoplastic resin contains 1 to 10 mol% of 5-sulfoisophthalic acid units. It is.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The inorganic base material used in the present invention refers to a formed body made of an inorganic material, for example, a metal plate such as an aluminum plate, a steel plate, a stainless steel plate, a metal thin film such as an aluminum foil, an aluminum vapor-deposited film, a silicon oxide, an oxide Examples thereof include an inorganic oxide vapor-deposited film of aluminum or the like and an inorganic laminate such as a sol-gel film.

The organic base material used in the present invention refers to a molded article mainly composed of an organic substance, for example, a single body, a mixture or a laminate of thermoplastic resins such as polyester, nylon, polypropylene, polyethylene, polystyrene and polyurethane. And a molded article composed of a three-dimensional crosslinked product such as a thermosetting polyester or a polyolefin crosslinked product, and molded products such as films, sheets, cards, synthetic papers, fibers, woven fabrics, and plastics. Further, a void-containing fiber obtained by stretching at least uniaxially a fibrous or sheet-like material obtained by mixing an incompatible thermoplastic resin or inorganic particles or organic particles with the thermoplastic resin,
Films and sheets may be used.

The conductive polymer in the present invention is applicable to the present invention as long as it is soluble in water or an organic solvent. For example, polyaniline and its derivatives, preferably water-soluble sulfonated polyaniline, organic solvent-soluble polypyrrole, Examples include polypyrrole, polythiophene, and derivatives thereof having a chain alkyl group substituent.

Further, a polyaniline or polyaniline copolymer solution obtained by doping a dispersion of polyaniline or a copolymer thereof with a protonic acid, for example, an inorganic acid or a compound containing a sulfonic acid group, may be mentioned. At this time, examples of the inorganic acid include hydrochloric acid, perchloric acid, sulfuric acid, and nitric acid, and examples of the sulfonic acid group-containing compound include benzenesulfonic acid, naphthalenesulfonic acid, and polystyrenesulfonic acid. Among them, sulfonated polyaniline is suitable for the present invention because of its good solubility in water.

The sulfonated polyaniline is a polyaniline or a polyaniline copolymer in which a predetermined amount of a sulfonic acid group is bonded to a benzene ring, and the production method is not particularly limited. Sulfonated polyaniline containing aminoanisolesulfonic acid as a main component is preferred. Specific examples of aminoanisolesulfonic acids include 2-aminoanisole-3
-Sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4 -Sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-aminoanisole-6-sulfonic acid, 4-aminoanisole-2-sulfonic acid, 4-aminoanisole-3-sulfonic acid, and the like.

It is also possible to use a compound in which the methoxy group of anisole is substituted by an alkoxy group such as an ethoxy group or an iso-propoxy group. However, 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid,
-Aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-
Sulfonic acid and 3-aminoanisole-6-sulfonic acid are preferably used.

The sulfonated polyaniline is a copolymer having a sulfonic acid group of 70% or more, preferably 80% or more, more preferably a homopolymer of 100% or more based on the aromatic ring. Further, even if an aromatic ring containing a sulfonic acid group and an aromatic ring not containing a sulfonic acid group are mixed or alternately arranged in the copolymer, the object of the present invention is not hindered.

If the sulfonic acid group content of the sulfonated polyaniline polymer is less than 70%, the solubility or dispersibility of the polymer in water, alcohol or a mixed solvent system thereof becomes insufficient. The coatability and spreadability to the substrate are deteriorated, and the conductivity of the obtained coating film tends to be significantly reduced. The number average molecular weight of the sulfonated polyaniline polymer used in the present invention is not particularly limited.
0 to 500,000, and 1,000 or more is preferable in terms of solubility in the solvent and strength of the coating film.

The conductive composition according to the present invention contains colloidal particles or suspension particles of a thermoplastic resin in addition to the above-mentioned conductive polymer. Here, colloid particles are particles that exist in the form of a dispersed colloid (particle colloid) or latex in a dispersion system and have a particle size of 1 nm to 0.1 μ. The particles have a particle size of 10 μm. These are all dispersed in a uniform medium, for example, water alone or a water / alcohol mixture, and preferably form a single film when the medium is removed by evaporation or the like. The thermoplastic resin forming such particles includes styrene-based, acrylic-based, urethane-based, vinyl-based, and ester-based thermoplastic resins. Among them, the ester-based thermoplastic resin is preferable from the viewpoints of film forming properties and strength of the coating film surface.

The thermoplastic resin in the present invention preferably has an ionic group and / or a polyalkylene glycol. Many of the above-mentioned water-dispersible copolymerized polyesters forming colloidal particles or suspended particles have carboxyl groups,
Copolyesters having ionic groups such as sulfonic acid groups, or their alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, phosphonium salts, polyalkylene glycols, polyacrylic acids, etc. in the main chain or side chain It is. The mode of copolymerization may be any of random, block and graft, and is not particularly limited.

The thermoplastic resin used in the present invention contains, for example, an aromatic dicarboxylic acid component having a sulfonic acid group or a salt thereof, for example, a 5-sulfoisophthalic acid unit in a proportion of 1 to 10 mol% based on the total acid component. The copolyester prepared in this manner is preferable because it gives the conductive laminate of the present invention a high surface hardness.

The dicarboxylic acid component used in the polyester copolymer may be an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, but is preferably terephthalic acid,
Isophthalic acid, phthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl, 4,4′-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, Adipic acid, sebacic acid, cyclohexane-1,4-dicarboxylic acid and the like can be mentioned. From the viewpoint of improving the surface hardness of the conductive laminated film of the present invention, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are particularly preferable.

As the glycol component, aliphatic and ethylene glycols are mainly used. In addition, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexane dimethanol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol And polyalkylene glycols such as polytetramethylene glycol. Among them, when polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like is used as a copolymer component, the compatibility with the sulfonated polyaniline is improved, and the surface resistance of the coating film surface is improved.
It is preferable in terms of improving strength and transparency. Also, the effect of preventing cracks on the coating film surface in the film or fiber stretching step is large.

The transparency and adhesion can be further improved by graft-polymerizing a vinyl monomer having a hydrophilic group on the side chain of the polyester. Vinyl monomers having a hydrophilic group that can be grafted to polyester include a carboxyl group, a hydroxyl group,
Examples include those containing a sulfonic acid group, an amide group, and the like, and those containing an acid anhydride group, a glycidyl group, a chloro group, and the like as groups that can be converted into a hydrophilic group. Among them, those having a carboxyl group are most preferred.

For example, monomers containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n
Alkyl acrylates such as -butyl acrylate and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-
Alkyl methacrylate such as butyl methacrylate, 2
Hydroxy-containing monomers such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N -Methoxymethyl methacrylamide, N, N-dimethylolacrylamide,
Examples include amide group-containing monomers such as N-phenylacrylamide and epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate.

Other monomers having a hydrophilic group include, for example, monomers containing an epoxy group such as allyl glycidyl ether, monomers containing a sulfonic acid group or a salt thereof such as styrenesulfonic acid, vinylsulfonic acid and salts thereof, and croton. Examples include monomers containing a carboxyl group or a salt thereof, such as acids, itaconic acid, maleic acid, fumaric acid and salts thereof, and monomers containing acid anhydrides, such as maleic anhydride and itaconic anhydride. These can be used in combination with other monomers. Other monomers, for example, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride, and the like,
Copolymerization can be carried out using one or two or more of these. The ratio of the monomer having a hydrophilic group to the other monomer is 30 / 70-100 / molar ratio.
A range of 0 is preferred. If the ratio of the monomer having a hydrophilic group is less than 30 mol%, the effect of increasing the transparency of the coating film cannot be sufficiently exhibited.

As a method of grafting a monomer having a hydrophilic group to the polyester, a known graft polymerization method can be used. The following method is mentioned as a typical example. For example, a radical polymerization method in which radicals are generated in the polyester of the main chain by light, heat, radiation, or the like, and then the monomers are graft-polymerized, AlCl ₃ , TiCl
_{There is} a cation polymerization method in which cations are generated using a catalyst such as ₄ or an anion polymerization method in which anions are generated using metal Na, metal Li, or the like.

Further, there is a method in which a polymerizable unsaturated double bond is introduced in advance into the polyester of the main chain, and a vinyl monomer is reacted with the polymerizable unsaturated double bond. Examples of the monomer having a polymerizable unsaturated double bond used in this method include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 2,5-norbornene dicarboxylic anhydride,
Examples thereof include tetrahydrophthalic anhydride. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid.

Further, there is a method in which a polyester having a main chain having a functional group introduced into a side chain is reacted with a branch polymer having a group which reacts with the functional group at the terminal. For example the side chain -OH group, -SH group, -NH ₂ group, -COOH group, -
A polymer substance having a hydrogen donating group such as a CONH ₂ group, and one end having a —N ＝ C ＝ O group, a —C ＝ C ＝ O group, For example, a method of reacting with a vinyl polymer which is a hydrogen accepting group, and a method of reacting in a reverse combination.

The weight ratio of the main chain polyester to the grafted vinyl monomer is in the range of 40/60 to 95/5, more preferably in the range of 55/45 to 93/7, most preferably 60/40. ９０90/10. If the weight ratio of the polyester in the main chain is less than 40%, the graft-polymerizable vinyl monomer remains without completely reacting, thereby impairing the inherent properties of the polyester, such as heat resistance and processability. Further, when the weight ratio of the main chain polymer substance exceeds 95%, the conductivity, which is the object of the present invention,
The effect of improving transparency is not sufficiently exhibited.

In addition, as a polyester copolymer component,
A dicarboxylic acid component containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like, or a glycol component may be contained. It is also possible to bond acrylic acid, methacrylic acid, styrene sulfonic acid, acrylamide, or the like to the main chain of the polyester in the form of graft copolymerization. Further, in order to improve the surface hardness of the conductive layer of the obtained laminate of the present invention, a multi-carboxy group-containing monomer such as trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride is used.
It is also possible to use it as a copolymer component of the above-mentioned polyester in a ratio of not more than mol%. If it exceeds 5 mol%, the resulting sulfonic acid group-containing copolymerized polyester becomes thermally unstable and easily gelates, which is not preferable as a component of the conductive layer of the present invention.

The above-mentioned copolymerized polyester is further subjected to a transesterification reaction, a polycondensation reaction or the like by a conventional method using, for example, the above-mentioned dicarboxylic acid component, the above-mentioned glycol component and, if necessary, the above-mentioned polycarboxyl group-containing monomer. Can be obtained by grafting or the like. The obtained copolymerized polyester is heated and stirred together with a solvent such as n-butyl cellosolve, and further added with water while stirring to form an aqueous dispersion of suspended particles or colloidal particles of the copolymerized polyester. It can be used in the present invention.

The ratio of the solid content of the suspended particles or colloid particles made of the thermoplastic resin such as polyester is determined based on the conductivity and mechanical properties of the obtained conductive laminated film with respect to 100 parts by weight of the conductive polymer. 50-2000
Parts by weight are preferred, and 100 to 1500 are more preferred.
Parts by weight, most preferably from 200 to 1000 parts by weight. If the amount exceeds 2,000 parts by weight, the performance of the conductive polymer is not exhibited. If the amount is less than 50 parts by weight, the adhesion of the conductive polymer to the substrate is poor, and the scratch resistance becomes insufficient.

The conductive composition used for producing the conductive laminate of the present invention is usually dispersed in water or an organic solvent, or a mixed solution of water / organic solvent, and applied to a desired substrate surface. As the solvent used here, any organic solvent can be used as long as it does not dissolve or swell the substrate (eg, a polyester film or the like). Water or a mixed solvent of water and an organic solvent is not only preferable in terms of use environment, but also
In some cases, the obtained antistatic property of the conductive laminate of the present invention is improved.

When the conductive polymer is dispersed in water or a water / organic solvent mixture together with suspended or colloidal particles of a thermoplastic resin and applied to the surface of a substrate, the ratio of the conductive polymer used is water or water. / 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the organic solvent mixture.
2 parts by weight. At this time, if the use ratio of the conductive polymer is less than 0.01 part by weight, the long-term storage property of the coating solution is poor,
In addition, a pinhole is easily generated in the coat layer on the surface of the base material, and as a result, the conductivity of the coat surface is extremely poor. Also,
If the use ratio exceeds 10 parts by weight, the solubility and dispersibility of the polymer in water or a water / organic solvent system and the coatability of the coat layer tend to deteriorate, which is not preferable.

As the solvent, any organic solvent can be used as long as it does not dissolve or swell a substrate such as a polyester film, but a mixed solvent with water or an organic solvent such as water / alcohol is preferable in terms of use environment. As well,
In some cases, the coatability and conductivity of the support may be improved. The organic solvent used in the present invention is methanol, ethanol,
Alcohols such as propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, propylene glycols such as methyl propylene glycol and ethyl propylene glycol, dimethyl formamide, dimethyl acetamide and the like Amides, pyrrolidones such as N-methylpyrrolidone, N-ethylpyrrolidone and the like having good compatibility with water are used. These are used by being mixed with water at an arbitrary ratio.

Specific examples of such a mixed solvent include water / methanol, water / ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol, and the like. The ratio used is water / organic solvent = 1/10
10/1 is preferred.

The conductive composition used in the production of the conductive laminate of the present invention has excellent coatability and spreadability on the surface of the substrate and excellent surface hardness of the obtained conductive layer even when only the above components are used. By using a surfactant soluble in a solvent in combination, application to a substrate having poor wettability becomes possible.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan fatty acid ester, and fluoroalkyl carboxylic acids, perfluorooalkyl carboxylic acids, and the like. Fluorinated surfactants such as perfluoroalkylbenzenesulfonic acid, perfluoroalkylquaternary ammonium, and perfluoroalkylpolyoxyethyleneethanol are used.

The amount of the surfactant used in the present invention is not particularly limited since it depends on the type of the conductive polymer.
01 parts by weight to 10 parts by weight. The surfactant is 10
If the amount exceeds the weight part, the surfactant in the coat layer exudes,
Various problems occur in secondary processing and the like.

The conductive layer of the conductive laminate of the present invention may contain various additives in addition to the above. Examples of such additives include titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), kaolin, and calcium carbonate (CaC).
O ₃ ), alumina (Al ₂ O ₃ ), barium sulfate (Ba)
Inorganic particles such as SO ₄ ), zinc oxide (ZnO), talc, mica, and composite particles, and organic particles composed of polystyrene, polyacrylate, or a crosslinked product thereof.

For the purpose of further improving the conductivity, powders of SnO ₂ (tin oxide) and ZnO (zinc oxide) and inorganic particles (TiO ₂ , BaSO ₄
), Carbon-based conductive fillers such as carbon black, graphite, and carbon fiber. The content of the additive is not particularly limited, but is preferably 4000 parts by weight or less based on 100 parts by weight of the conductive polymer. If it exceeds 4,000, the viscosity of the conductive layer may increase, which may cause uneven coating.

The method of laminating the conductive layer on the substrate includes a coating method, an immersion method, and a multilayer extrusion method.
It is necessary to select according to the form. The method of laminating the conductive layer in the case where the substrate is a thermoplastic film surface is described in detail below, but the method is not limited thereto.

Examples of a method for laminating a conductive layer on the film include a gravure roll coating method, a reverse roll coating method, a knife coater method, a dip coating method, and a spin coating method. There is no particular limitation. There are an in-line coating method in which application to a film is performed simultaneously in a film-forming process and an offline coating method in which coating is independently performed after the production of a film-forming roll. Since the conductive polymer used in the present invention generally has good heat resistance, heating at a high temperature for the purpose of scattering the solvent after coating is not a problem. For example, sulfonated polyaniline is unstable at a high temperature of 250 ° C. or higher, but has good thermal stability at 200 ° C. for about 3 minutes. Therefore, depending on the type of the coexisting thermoplastic resin and additives, it is usually short. Heating at 200 ° C. for a time does not adversely affect conductivity. Rather, in terms of improving conductivity, 200 ° C.
It is preferable to heat in the vicinity within 30 seconds.

[0042]

EXAMPLES Examples and comparative examples of the present invention will be described below, but the present invention is not limited to these examples. The methods for evaluating physical properties used in the examples and the like are shown below.

1) Presence / absence of whitening of the conductive layer The surface of the conductive layer was irradiated with light with bromolite, and the presence / absence of whitening was evaluated as follows.・ No whitened part on the surface of conductive layer: ○ ・ Part of the surface of conductive layer is whitened: ×

2) Surface resistance value and charging decay time The surface resistance value was measured with a surface resistance measuring device manufactured by Takeda Riken Co. under the conditions of an applied voltage of 500 V, 25 ° C. and 15% RH. The charge decay time was measured using a static decay meter manufactured by ETS in the United States at 25 ° C. and a 15% RH atmosphere. A sample was sandwiched between the electrodes, and a voltage of 5.0 KV was applied. Was grounded, and the time from the grounding until the applied voltage became 0.05 KV was measured.

3) Adhesion of the conductive layer to the thermoplastic film When the cellophane tape adhered to the surface of the conductive layer was peeled off from the surface, whether or not the conductive layer was peeled from the thermoplastic film was evaluated as follows. -The conductive layer does not peel off and does not adhere to the cellophane tape at all. : ○ ・ The conductive layer slightly peels off and adheres to the cellophane tape. : △ ・ The conductive layer completely peels off and adheres to the cellophane tape. : ×

4) Scratch resistance The surface of the conductive layer was rubbed 10 times with a gauze under a load of 200 g.
The degree of scratching on the surface of the conductive layer was evaluated as follows. -There is no scratch on the conductive layer surface. : ○ ・ Some small scratches are present on the conductive layer surface. : △ · The surface of the conductive layer has a clearly visible scratch. : ×

5) Set-off property The surface of the conductive layer and the opposite surface of the thermoplastic film are overlapped,
After applying a load of 170 kg / cm ² at room temperature for 10 minutes,
It was visually evaluated whether or not a part of the conductive layer had set off on the opposite surface.

6) Water resistance The surface of the conductive layer was wiped 10 times at a constant pressure using a commercially available tissue paper containing water, and whether or not the surface of the conductive layer was wiped was evaluated as follows.・ The conductive layer is not wiped at all: ○ ・ The conductive layer is slightly wiped: △ ・ The conductive layer is completely wiped: ×

(Synthesis Example 1) Preparation of sulfonic acid group-containing polyaniline coating solution 2-aminoanisole-4-sulfonic acid 100 mmol
Is dissolved in a 4 mol / L aqueous ammonia solution at 23 ° C. with stirring to obtain 100 mmol of ammonium peroxodisulfate.
Was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 23 ° C. for 10 hours, and the reaction product was separated by filtration, washed and dried to obtain 13 g of a powdery polymer. The volume resistivity of this polymer was 12 Ωcm. 3 parts by weight of the above polymer was stirred and dissolved at room temperature in 100 parts by weight of a 0.3 mol / liter sulfuric acid aqueous solution to prepare a conductive composition. 2.0 parts by weight of the sulfonated polyaniline was dissolved in 50 parts by weight of water and 50 parts by weight of isopropanol.

(Synthesis Example 2) Synthesis of Polyester (A) and Preparation of Its Water / Alcohol Dispersion (A _aq ) 46 mol% of dimethyl terephthalate, 47 mol% of dimethyl isophthalate and sodium 5-sulfoisophthalate as dicarboxylic acid components A transesterification reaction and a polycondensation reaction were carried out by a conventional method using 7 mol% of ethylene glycol and 50 mol% of diethylene glycol as glycol components to obtain a sulfonic acid group-containing polyester. The sulfonic acid group-containing polyester (300 parts) and n-butyl cellosolve (150 parts) were heated and stirred to form a viscous solution, and 550 parts of water was gradually added with stirring to obtain a uniform pale white solid having a solid content of 30% by weight. Was obtained. This dispersion was further added to a mixture of equal amounts of water and isopropanol to prepare an aqueous dispersion of a sulfonic acid group-containing polyester (A _aq ) having a solid content of 8% by weight.

Synthesis Example 3 Synthesis of acrylic graft polyester (B) and preparation of aqueous dispersion (B _aq ) 5 mol of dimethyl terephthalate in a stainless steel autoclave equipped with a stirrer, thermometer and partial reflux condenser 4.5 mol of dimethyl isophthalate, 6.5 mol of ethylene glycol, 3.5 mol of neopentyl glycol
Mol and 0.002 mol of tetra-n-butyl titanate, and transesterification was performed at 160 to 220 ° C. for 4 hours. Then, 0.5 mol of fumaric acid was added, the temperature was raised to 200 to 220 ° C. over 1 hour, and the pressure of the reaction system was gradually reduced. Then, the reaction was carried out for 1 hour and 30 minutes under a reduced pressure of 0.2 mmHg to obtain polyester (B ₀ ) Got.

Next, the polyester (B ₀ ) 3 was placed in a reactor equipped with a stirrer, a thermometer, a reflux device and a metered-drip device.
Then, 00 parts, 360 parts of methyl ethyl ketone and 120 parts of isopropyl alcohol were added, and the mixture was heated and stirred to dissolve the resin under reflux. After the resin is completely dissolved, acrylic acid 35
And a solution prepared by dissolving a mixture of 65 parts of ethyl acrylate and 1.5 parts of octyl mercaptan, and 6 parts of azobisisobutyronitrile in a mixture of 90 parts of methyl ethyl ketone and 30 parts of isopropyl alcohol over 1.5 hours. Then, each was dropped into a polyester solution and reacted for further 3 hours to obtain a graft polymer (B) solution. After the graft polymer solution was cooled to room temperature, 59 parts of triethylamine was added and neutralized, and then 800 parts of ion-exchanged water was added and stirred for 30 minutes. Thereafter, the solvent remaining in the solvent is distilled off by heating to form an aqueous dispersion. This dispersion is further added to a mixed solution of an equal amount of water and isopropanol, and an alcohol / water dispersion (B) having a solid content of 8% by weight is obtained. _aq ).

(Preparation of base film) Average particle size 0.5 μm
m of calcium carbonate fine particles dispersed at a concentration of 4000 ppm is melt-extruded at 290 ° C. and cooled with a cooling roll at 30 ° C. to a thickness of about 1 μm.
An unstretched film of 80 μm was obtained. The unstretched film was stretched 3.5 times in the longitudinal direction between a pair of rolls heated to 85 ° C. and having different peripheral speeds to obtain a base film.

Example 1 The solid content ratio of the sulfonated polyaniline obtained in Synthesis Example 1 to the sulfonic acid group-containing polyester obtained in Synthesis Example 2 was 10/9.
0 and further, a surfactant Emulgen 810 (manufactured by Kao) was prepared into a coating solution having a solid content of 4% so that the ratio to the sulfonated polyaniline was 8/100. The obtained thickness of about 5
The above coating solution was applied to a thickness of about 10 μm on a 0 μm base (PET) film, and further stretched 3.5 times in the horizontal direction to prepare a conductive laminate of the present invention.

Example 2 In Synthesis Example 2, 93 dimethyl terephthalate was used as the acid component.
Conductive laminate was obtained in the same manner as in Example 1 except that mol%, sodium 5-sulfoisophthalate was 7 mol%, ethylene glycol was 95 mol% as a glycol component, and polyethylene glycol having a molecular weight of 1000 was 5 mol%. Was.

Example 3 In Synthesis Example 2, 93 dimethyl terephthalate was used as the acid component.
Conductive laminate was prepared in the same manner as in Example 1 except that mol%, sodium 5-sulfoisophthalate was 7 mol%, ethylene glycol was 95 mol% as a glycol component, and polyethylene glycol having a molecular weight of 10,000 was 0.5 mol%. I got

Example 4 A conductive laminate was prepared in the same manner as in Example 1, except that dimethyl terephthalate was changed to 48 mol%, dimethyl isophthalate was changed to 50 mol%, and sodium 5-sulfoisophthalate was changed to 2%. I got

Comparative Example 1 A conductive laminate was obtained in the same manner as in Example 1 except that an aqueous polyvinyl alcohol solution was used instead of the copolymerized polyester.

Comparative Example 2 A conductive laminate was obtained in the same manner as in Example 1 except that an aqueous solution of sodium polyacrylate was used instead of the copolymerized polyester.

Comparative Example 3 A conductive laminate was obtained in the same manner as in Example 1 except that no copolymerized polyester was used.

Table 1 shows the evaluation results of the conductive laminates obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

[Table 1]

As can be seen from Table 1, all Examples were excellent in whitening property, surface resistance, adhesion, scratch resistance, set-off property and water resistance. On the other hand, Comparative Examples 1 and 2, although having transparency, had a higher surface resistance value than those of the Examples, insufficient water resistance, and set off of the surfactant. Further, Comparative Example 3 was only sulfonated polyaniline and did not contain a polymer substance, so that the coating properties were poor, the surface resistance was high, and the adhesion, scratch resistance, and water resistance were insufficient.

Example 5 A conductive laminate was obtained in the same manner as in Example 1 except that the dispersion of Synthesis Example 3 was used instead of the dispersion of Synthesis Example 2.

Example 6 A graft polymer was produced in the same manner as in Synthesis Example 3 except that the amount of acrylic acid was changed to 4.2 parts and the amount of ethyl acrylate was changed to 7.8 parts. An aqueous dispersion was obtained, and a conductive laminate was obtained in the same manner as in Example 1.

Comparative Example 4 In Example 1, instead of the aqueous dispersion of the graft polymer, the sulfonated polyaniline obtained in Synthesis Example 1 was dissolved in a polyester resin solution obtained by dissolving polyester (B ₀ ) in methyl ethyl ketone. A conductive laminate was obtained in the same manner as in Example 1 except that the obtained liquid was applied.

Table 2 shows the evaluation results of the films obtained in Examples 5 and 6 and Comparative Example 4.

[Table 2]

As can be seen from Table 2, all Examples were excellent in whitening property, surface resistance, adhesion, scratch resistance, set-off property and water resistance. On the other hand, in Comparative Example 4, the surface resistance was higher than that of the example, and other characteristics were insufficient.

[0068]

As described in detail above, the conductive laminate of the present invention has excellent transparency and exhibits excellent antistatic properties even under low humidity. Therefore, the conductive laminate of the present invention comprises various fibers such as polyester fibers, nylon fibers, polyethylene fibers, aromatic and heterocyclic polymer fibers and their woven fabrics, magnetic tapes, OHP films, shielding materials, L
Various industrial films such as CD conductive layers, carrier tapes, trays, magazines, various packaging films such as IC / LSI packages, magnetic layer binders, building adhesives,
It can be applied to plastics and the like.

Claims (8)

[Claims] 1. A conductive laminate in which at least one surface of an inorganic or organic base material is coated with a conductive composition containing suspended particles or colloid particles of a conductive polymer and a thermoplastic resin. 2. The base material is a film or a sheet,
The surface resistance of the coated surface of the substrate at 25 ° C. and 15% RH is 10 ⁵ to 10 ¹² Ω / □, and the charge decay time is 2
The conductive laminate according to claim 1, wherein the time is not more than seconds. 3. The conductive laminate according to claim 1, wherein the substrate is a molded article of polyester. 4. The conductive laminate according to claim 1, wherein the conductive polymer is polyaniline or a polyaniline copolymer doped with a protonic acid. 5. The conductive laminate according to claim 1, wherein the conductive polymer is a sulfonated polyaniline. 6. The conductive laminate according to claim 1, wherein the conductive polymer is a sulfonated polyaniline containing aminoanisolesulfonic acid as a main component. 7. The conductive laminate according to claim 1, wherein the thermoplastic resin has an ionic group and / or a polyalkylene glycol. 8. The conductive laminate according to claim 1, wherein the thermoplastic resin is a copolyester containing 1 to 10 mol% of 5-sulfoisophthalic acid units.