JP2000108283A - Destaticizing laminate, packaging bag and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide sufficient destaticizing property under a low humidity and obtain utility by a method wherein the main component of a destaticizing layer is constituted of the mixture of polyaniline and/or a derivative thereof and a copolymerized polyester containing ionic group and/or a polyalkylene glycol component. SOLUTION: A destaticized layer, whose main component is the mixture of the polyaniline and/or a derivative thereof and a copolymerized polyester containing ionic group and/or polyalkylene glycol is provided. The polyaniline derivative is polyaniline or the like, obtained by doping sulfonated polyaniline protonic acid while the use rate of the sulfonated polyaniline copolymer is specified to be 0.01-10 pts.wt. based on 100 pts.wt. of solvent. On the other hand, the copolymerized polyester is specified to have the main chain or the side chain of the ionic group, such as sulfonic acid group, carboxyl group, polyacrylic acid group or the like, polyalkylene glycol component or the like and, further, the alkaline metal salt, alkali earth metal salt or the like thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic laminate, a packaging bag or a container made from the laminate. The antistatic laminate can be used not only for general packaging applications that dislike static electricity, but also as a packaging material for specific applications. Specific applications include storage media such as magnetic media, optical media, and magneto-optical media, passive elements, active elements, and integrated ICs (integrated circuits), LSIs (large-scale integrated circuits), and VLSIs (ultra-large scales). Integrated circuit), LCD
(Liquid crystal displays), parts such as plasma displays used in the electronic communication industry are used for packaging. In addition, the present invention provides a packaging container dedicated to mounting, transporting, transporting, storing, and assembling these components into a product or a semi-finished product, such as a carrier tape, a tray, a magazine bulk case, and the like. Belongs to the field of developing packaging bags and containers for packaging together.

[0002]

2. Description of the Related Art Conventionally, thermoplastic films such as polyester and nylon are excellent in heat resistance, dimensional stability, mechanical strength, etc., and therefore have been used in a large amount and in a wide range as packaging films and industrial films. I have. Polyethylene, polypropylene, polyvinyl chloride and the like are generally used as packaging materials because of their good moldability and low cost, although they have poor heat resistance. Since the synthetic resin is generally dielectric, static electricity is easily generated on the surface of the structure forming body made of the synthetic resin, and dust and the like are easily attached. Therefore, in the case of a synthetic resin packaging material, there is a danger that it is attracted to other articles due to static electricity, the content is sucked and cannot be taken out, and there is a danger that electric discharge occurs. Further, recent advances in electronic technology have required a higher degree of cleanliness for packaging materials, and there has been a problem of destruction of semiconductor elements due to static electricity.

As an antistatic agent for films, packaging materials, etc.
In general, a surfactant is used.
Has sufficient surface resistance to control the adhesion of dust, dust, etc.
(10 ^TenΩ / □ or less) as well as antistatic
The stopping power is easily changed by the influence of the surrounding moisture and moisture. Special
The surface resistance of the film reduced by the surfactant
Under humidity, the desired antistatic ability cannot be obtained due to a large increase.
There are drawbacks. This means that during the manufacturing process
High humidity, low humidity such as cure, and finally dry environment
For packaging materials that are often exposed to electronic materials
It is inconvenient.

[0004] For these reasons, there is a demand for a film free from static electricity in a low humidity environment. For this purpose, an antistatic agent which provides a surface resistance of 10 ¹⁰ Ω / □ or less under a low humidity is required. Appearance is desired. As a material giving such a low surface resistance value, a resin mixed with carbon black is often used. However, this is inferior in transparency, and is not suitable for visual inspection of contents and an underlayer or inspection by optical sensing. IT as a transparent and antistatic material
Although it is conceivable to use a vapor-deposited film of O (indium tin oxide) or SnO ₂ , or a resin obtained by mixing these powders, the use of a packaging material has a disadvantage of increasing the cost.

[0005] Conductive polymers such as polyaniline and polypyrrole are known as materials having similar characteristics. Both are soluble in a specific organic solvent, but are insoluble or indispensable in water or a mixed solvent of water / alcohol. Therefore, a method of bonding a sulfonic acid group to an aromatic ring is used. Furthermore, since these conductive polymers alone do not provide sufficient film properties, a method of mixing a water-soluble or water-dispersible resin has been used. However, when a resin having good compatibility with polyaniline or a derivative thereof or a sulfonated polyaniline is used, a predetermined surface resistance value is not obtained, and a resin having a predetermined surface resistance value is used. However, there has been a problem that the surface becomes cloudy and the original transparency of the film is impaired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a structural film having a thermoplastic film or sheet, especially a polyolefin, polyester or a polyester having a heat-adhesive sealant, and having a low humidity. An object of the present invention is to provide an antistatic laminate, a packaging bag, and a packaging container which have sufficient antistatic properties even underneath and have a versatile laminated structure and can be manufactured at low cost.

[0007]

The antistatic laminate of the present invention comprises polyester generally used as a packaging material,
Using a polyolefin or polyester sealant with thermal adhesion in a laminated configuration, on one or both sides,
A mixture of polyaniline and / or a derivative thereof (preferably sulfonated polyaniline) and a copolyester containing an ionic group and / or a polyalkylene glycol component (preferably a polyester containing a sulfonic acid group). Is provided.

As the "polyaniline and its derivative", any can be used, but it is preferable that the polyaniline is doped from the viewpoint of antistatic properties. As polyaniline derivatives,
For example, sulfonated polyaniline, polyaniline doped with a protonic acid and the like can be mentioned. A mixture of polyaniline and a polyaniline derivative such as a sulfonated polyaniline, or a single substance of each, is suitably used. Hereinafter, “polyaniline and its derivatives” are also collectively referred to as “polyanilines”.

As the sulfonated polyaniline, a sulfonated alline-based copolymer containing an alkoxy group-substituted aminobenzenesulfonic acid as a main component is suitable as a basic material of the antistatic laminate of the present invention. Acids are preferred. Furthermore, in terms of the applicability of the solution for forming the antistatic layer, the spreadability, and the hardness of the applied body,
It is more preferable to use the copolymerized polyester containing 4 to 10 mol% of 5-sulfoisophthalic acid unit in combination.

Here, specific examples of aminoanisolesulfonic acids include 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, and 2-aminoanisole-sulfonic acid. 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- Examples thereof include 2-sulfonic acid and 4-aminoanisole-3-sulfonic acid. 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.

Preferably, 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 and 3-aminoanisole-6-sulfonic acid are used. Thus, a sulfonated polyaniline copolymer containing aminoanisolesulfonic acid as a main component is used as one component of the antistatic layer.

As described above, the sulfonated polyaniline copolymer used in the antistatic laminate of the present invention has a sulfonic acid group bonded to the number of aromatic rings constituting the sulfonated polyaniline copolymer. The ratio of the number of aromatic rings
% Or more, preferably 80% or more, more preferably 10% or more.
0%. In addition, there is no problem in achieving the object of the present invention, even if the aromatic ring containing a sulfonic acid group and the aromatic ring not containing a sulfonic acid group are mixed or alternately arranged. If the sulfonic acid group content of the sulfonated polyaniline copolymer is less than 70%, the solubility or dispersibility of the copolymer in water, alcohol or a mixed solvent system thereof becomes insufficient, and as a result, As a result, the applicability and spreadability to the substrate are deteriorated, and the antistatic property of the obtained coating film tends to be significantly reduced. The number average molecular weight of the sulfonated polyaniline copolymer is 300 to 50,000
0, and 1000 or more is preferable in view of solubility in the solvent and strength of the coating film.

The use ratio of the sulfonated polyaniline copolymer is 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the solvent.
Parts by weight, preferably 0.1 to 2 parts by weight. When the use ratio of the sulfonated polyaniline copolymer is less than 0.01 part by weight, the long-term storage property of the solution is deteriorated, pinholes are easily generated on the surface coating layer (coating film), and the antistatic property of the coating surface is reduced. Is significantly inferior. On the other hand, if the use ratio exceeds 10 parts by weight, the solubility and dispersibility of the copolymer in water or a mixed system of water and an organic solvent and the coating property of the coat layer tend to be deteriorated, 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. However, use of a mixed solvent with water or an organic solvent such as water / alcohol is preferred. In some cases, the coating properties on the support and the antistatic property are improved. Organic solvents include alcohols such as methanol, ethanol, propanol, and isopropyl alcohol,
Acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, methyl cellosolve, cellosolves such as ethyl cellosolve, propylene glycols such as methyl propylene glycol and ethyl propylene glycol, dimethylformamide, amides such as dimethylacetamide, N-methylpyrrolidone, Pyrrolidones such as N-ethylpyrrolidone are preferably used. These are used by being mixed with water at an arbitrary ratio. Specific examples of this include water / methanol, water / ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol, and the like. The ratio of water / organic solvent is preferably 1/10 to 10/1.

"Copolymerized polyester containing ionic group and / or polyalkylene glycol component" (hereinafter sometimes referred to as ionic group-containing copolymerized polyester)
Include ionic groups such as sulfonic acid groups, carboxyl groups, and polyacrylic acid groups, and copolyesters having a polyalkylene glycol component or the like in the main chain or side chain, and further include alkali metal salts and alkaline earth metal salts thereof. , Quaternary ammonium salts, phosphonium salts and the like. The mode of copolymerization may be random, block, or graft,
There is no particular limitation.

Among these ionic group-containing copolymerized polyesters, sulfonic acid group-containing copolymerized polyesters (hereinafter referred to as sulfonic acid group-containing copolymerized polyesters) are preferred. The sulfonic acid group-containing copolymerized polyester is a polyester in which a sulfonic acid component of at least one compound selected from the group consisting of sulfonic acid and an alkali metal salt thereof is bonded to a part of a dicarboxylic acid component and / or a glycol component. . Further, among the sulfonic acid group-containing copolymerized polyesters, copolymers prepared using an aromatic dicarboxylic acid component containing a sulfonic acid component of at least one compound selected from the group consisting of sulfonic acid and an alkali metal salt thereof. Polyester, which is prepared by using an aromatic dicarboxylic acid component at a ratio of 4 to 10 mol% with respect to the total acid component, is preferable in that the surface hardness of the antistatic layer is high. As an example of such a dicarboxylic acid component, sodium 5-sulfoisophthalate is preferred.

Other dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid,
4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid, cyclohexane-1,
4-dicarboxylic acid and the like. From the viewpoint of improving the surface hardness of the antistatic layer, terephthalic acid and isophthalic acid are preferred.

Ethylene glycol is mainly used as a glycol component for preparing the copolymerized polyester. In addition, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, and ethylene oxide adduct of bisphenol A are also used. , Polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol and the like can be used. Among them, the use of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexane dimethanol, or the like as a copolymer component is preferred in that compatibility with polyanilines such as sulfonated polyaniline is improved.

In addition, the copolymer component may contain a small amount of a dicarboxylic acid component or a glycol component containing an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like. Furthermore, in order to improve the surface hardness of the coating film obtained by applying the composition forming the antistatic layer to the substrate,
Polycarboxy group-containing monomers such as trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride can be used as a copolymer component of the polyester at a ratio of 5 mol% or less. 5
If it exceeds mol%, the resulting sulfonic acid group-containing copolymerized polyester becomes thermally unstable and tends to gel, which is not preferable as a component of the antistatic layer.

The sulfonic acid group-containing copolyester is prepared, for example, by a transesterification reaction or a polycondensation reaction using the above-mentioned dicarboxylic acid component, the above-mentioned glycol component, and if necessary, the above-mentioned polycarboxyl group-containing monomer. It is obtained by performing a reaction or the like. The obtained sulfonic acid group-containing copolymerized polyester is heated and stirred with a solvent such as n-butyl cellosolve, and can be used as an aqueous solution or aqueous dispersion by gradually adding water while further stirring.

The content ratio of the sulfonic acid group-containing copolymerized polyester is from 50 to 2 parts by weight based on 100 parts by weight of the polyaniline, based on the antistatic property and mechanical properties of the obtained antistatic layer.
000 parts by weight, more preferably 100 to 1
500 parts by weight, most preferably 200 to 1000 parts by weight.

The antistatic layer is formed from a composition mainly composed of a mixture of the above-mentioned polyaniline and an ionic group-containing copolymerized polyester (hereinafter, this composition is also referred to as an antistatic composition). You. The antistatic composition is dissolved or dispersed in a 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). The use of water or a mixed solvent of water and an organic solvent is not only preferable in terms of use environment but also sometimes improves the antistatic property of the obtained antistatic layer.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, methyl propylene glycol and ethyl propylene glycol. And amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone. These organic solvents can be used by being mixed with water at an arbitrary ratio. Examples of mixing include water / methanol,
Water / ethanol, water / propanol, water / isopropanol, water / methylpropylene glycol, water / ethylpropylene glycol, and the like. The mixing ratio of water / organic solvent is preferably 1/10 to 10/1.

The proportion of the solvent used is not particularly limited, but it is usually from 1000 to 2 parts by weight based on 100 parts by weight of the polyaniline.
0000 parts by weight. When the amount of the solvent used is extremely large, the film forming property of the antistatic layer may be deteriorated. Therefore,
Pinholes are likely to occur in the antistatic layer, and the antistatic property is significantly reduced, that is, the antistatic property may be reduced. On the other hand, when the amount of the solvent used is extremely small, the solubility or dispersibility of the polyaniline in the solvent becomes insufficient,
There is a possibility that the surface of the obtained antistatic layer becomes difficult to be flat.

The antistatic composition is excellent in film-forming properties and spreadability by using only the above-mentioned components, and has a good surface hardness of the obtained antistatic layer. By further using a polymer compound in combination, application to a thermoplastic film 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, perfluoroalkyl carboxylic acids, and perfluoroalkyl carboxylic acids. Fluorosurfactants such as fluoroalkylbenzene sulfonic acid, perfluoroalkyl quaternary ammonium, and perfluoroalkyl polyoxyethylene ethanol are used. The amount of the surfactant used is preferably 0.001 part by weight or more and 1000 parts by weight or less based on 100 parts by weight of the polyaniline. If the amount of the surfactant exceeds 1000 parts by weight, the surfactant in the coat layer may be set off on the uncoated surface of the base material, which may cause a problem in secondary processing or the like.

Examples of the above-mentioned high molecular compound include water-soluble resins such as polyacrylamide and polyvinylpyrrolidone in addition to the above-mentioned copolymerized polyester containing an ionic group and the like.
Water-soluble or water-dispersible copolymerized polyester containing a hydroxyl group or a carboxylic acid group, acrylic resins such as polyacrylic acid and polymethacrylic acid, acrylate resins such as polyacrylate and polymethacrylate, and polyethylene terephthalate , Ester resins such as polybutylene terephthalate, styrene resins such as polystyrene, poly-α-methylstyrene, polychloromethylstyrene, polystyrenesulfonic acid, and polyvinylphenol; vinyl ether resins such as polyvinyl methyl ether and polyvinyl ethyl ether; polyvinyl alcohol; and polyvinyl alcohol. For example, polyvinyl alcohols such as formal and polyvinyl butyral, and phenol resins such as novolak and resol may be used. Among them, water-soluble or water-dispersible copolymerized polyesters containing a hydroxyl group or a carboxylic acid group and polyvinyl alcohols are preferred from the viewpoints of compatibility with polyanilines and adhesion with a substrate made of polyester or the like. In addition, in the case of using any of the polymer compounds, it is possible to impart thermal adhesion to the antistatic layer by selecting one having a low softening point.

The amount of the high molecular compound is preferably 0 to 1000 parts by weight, more preferably 0 to 500 parts by weight, based on 100 parts by weight of the polyaniline. If the amount of the polymer compound exceeds 1000 parts by weight, the conductivity of the polyaniline does not appear, and the original antistatic function may not be exhibited.

The antistatic composition may contain various additives in addition to the above. As additives, TiO ₂ , Si
O ₂ , kaolin, CaCO ₃ , Al ₂ O ₃ , BaS
Examples include inorganic particles such as O ₄ , ZnO, talc, mica, and composite particles, and organic particles composed of polystyrene, polyacrylate, or a crosslinked product thereof. In order to further improve antistatic properties, SnO ₂ (tin oxide),
It is also possible to add ZnO (zinc oxide) powder, inorganic particles (TiO ₂ , BaSO _4, etc.) coated thereon, and carbon-based conductive fillers such as carbon black, graphite, and carbon fibers. The content of the above additive,
The ratio is preferably 4000 parts by weight or less based on 100 parts by weight of the polyaniline. If the amount exceeds 4,000 parts by weight, the coating of the antistatic layer may become uneven due to an increase in the viscosity of the coating solution.

As a method for laminating an antistatic layer on the surface of a thermoplastic film or a laminate containing the same and a packaging material comprising the same, a spray coating method, a gravure roll coating method, a liquor roll coating method, a knife coater method, a dip coating method And a spin coating method, but the coating method suitable for the antistatic composition is not particularly limited.
There is an in-line coating method in which the application to the film is performed simultaneously in the film forming process, and an offline coating method in which the film forming roll is manufactured independently after the production of the film forming roll, and can also be laminated using a printing technique. A preferred method can be selected, and there is no particular limitation. The sulfonated polyaniline used in the present invention is unstable at a high temperature of 250 ° C. or higher,
Since the thermal stability is good at 200 ° C. for about 3 minutes, heating at 200 ° C. for a short time usually does not adversely affect the antistatic property, depending on the type of the coexisting polymer compound and additives. Rather, in terms of improvement in antistatic properties, 3
Preferably, heating is performed within 0 seconds. The antistatic layer can be co-extruded and laminated with a laminating material shown below.

As a material for lamination, polyester, copolyester, polyamide, adhesive polyolefin,
Polyethylene, polypropylene, polybutene, polymethylpentene, polystyrene, polystyrene-based copolymer,
Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, ethylene vinyl acetate copolymer, polyurethane, acrylic resin, polycarbonate resin, epoxy resin, ethylene vinyl alcohol copolymer, ionomer, cellophane, nitrocellulose, ethyl cellulose, Single or a mixture of cellulose acetate, fluorine resin, silicone resin and the like can be mentioned. There is no particular limitation on the method of forming these materials into a sheet or a film, and the material is formed by a melt extrusion molding, a casting method, an injection molding method, or the like, and if necessary, a stenter method, a roll stretching method, a blow stretching method, a rolling method. For example, uniaxial or biaxial orientation can be given. In the case of an incompatible raw material, a void-containing material can be obtained in this step. Further, heat shrinkability can be imparted depending on the alignment conditions. The thickness of the sheet or film is not specified, but may be up to 1 (m
m). In addition, lubricants,
Additives such as antioxidants, antiblocking agents, antistatic agents, pigments, flame retardants, UV absorbers, drying agents, etc. may be included.

The antistatic laminate of the present invention preferably has a polyester layer and a polyolefin layer,
This enables lamination and lamination such as multi-layering and multi-layering, and can provide thermal adhesion.

When the antistatic layer has insufficient sealing ability,
It is also possible to provide a sealant or an adhesive or tacky material suitable for the bonding partner on the antistatic layer only in the portion to be sealed in advance. Alternatively, a layer serving as a sealant may be provided below the antistatic layer, and the antistatic layer may be opened or exposed only in a portion to be sealed in advance. Further, the antistatic layer may be destroyed by the sealing treatment, and a sealant layer may be provided over the entire surface under the antistatic layer.

As a sealant to be laminated on the antistatic layer, a curable type (isobutene-isoprene rubber,
Chloro-sulfonyl-polyethylene, acrylic rubber, etc.), one-pack natural vulcanization type (silicone rubber, polysulfide rubber,
Urethane rubber, liquid isobutene-isoprene rubber, etc.), and two-pack natural vulcanization type (polysulfide rubber, urethane rubber, etc.). As the polyester layer laminated on the antistatic layer, a sealant layer made of a polyester resin is particularly desirable. This is because a polyester-based binder is often used for the antistatic layer, and thus, when a polyester-based resin is used as the sealant, the adhesive strength is increased.

In the antistatic laminate of the present invention, aluminum foil, paper, cloth, nonwoven fabric, copper foil, gold foil, iron foil, glass, inorganic thin film, inorganic oxide thin film, etc. may be used as other thin layers. Can be.

The method of laminating the antistatic laminate of the present invention is not particularly limited, and an appropriate method can be selected and used. For example, a co-extrusion lamination method, an in-line coating method, an off-line coating method, an extrusion lamination method, a hot melt lamination method, a dry lamination method, a wet lamination method, and the like are appropriately used, and if necessary, an anchor coat, a primer coat, a corona treatment, a flame Treatment, UV irradiation treatment and the like can be used together. Further, even after lamination, various orientations can be imparted to the laminate by the above-described appropriate method.
The laminating step may be performed at any stage, and may be performed before or after providing the antistatic layer.

The packaging bag and packaging container of the present invention are made from the above-mentioned sheets, films and laminates. For use as a packaging material, a printed layer for design, display, and inspection may be provided between any layers. The antistatic layer may also serve as the printing layer. In order to make a packaging bag, sealing is performed by conventional means. Bar sealing method,
Rotary roll seal method, impulse seal method, solvent seal method, fusing seal method, hot melt seal method, ultrasonic seal method,
There is a high frequency sealing method or the like, and an arbitrary method can be selected.

As the form of the obtained bag, an arbitrary form such as a pillow packaging bag, a three-side seal bag, a four-side seal bag can be selected according to the purpose. In addition, there is no limitation on a method for manufacturing a packaging container, and a typical method is a thermoforming method, for example, an injection molding method, a blow molding method, a drape molding method, a vacuum molding method, and using a bending process. Can also. As the form of the obtained container, a tray, a magazine,
There are bulk cases, carrier tapes, bottles, cups, cartons, boxes, blister packages and the like. Some lids and sheets for sealing these containers can be manufactured by the technique of the present invention. For example, a release sheet for a carrier tape, a cover tape, a tray, a lid of a cup, and the like can be given.

As described above, the packaging bag and the packaging container of the present invention need to be sealed using heat softening or swelling with a solvent at the time of bag making and sealing. It is also worth considering that the composition of the ionic group etc.-containing copolymerized polyester in the antistatic layer is determined so as to be suitable for this treatment. For example, by using an aliphatic monomer to lower the glass transition point or melting point, or by changing the copolymerization ratio of isophthalic acid or neopentyl glycol to lower the crystallinity, the thermal adhesiveness can be improved, and at the same time, Swelling due to the solvent also tends to occur. In addition, the monomer type and the copolymerization ratio can be determined so that the solubility parameter of the solvent and the same parameter of the copolymerized polyester have an appropriate relationship for swelling.

[0040]

The present invention will now be described in detail with reference to examples and comparative examples. The evaluation method commonly used for each example is as follows. Tables 1 to 3 show the configurations, evaluation results, and the like of Examples and Comparative Examples.

(1-1) Thickness Measurement of Antistatic Layer by Wiping Method The operation is performed in a constant temperature and humidity room at 25 ° C. and 50% RH. After leaving the film, sheet or test piece provided with the antistatic layer for 3 days, static elimination is performed for 10 seconds with a static eliminator, and the weight is measured with an electronic balance that can measure up to 10 ^-5 (g). Thereafter, a solvent such as ethyl acetate, acetone, or methanol is applied to Bencott (made by Asahi Kasei Corporation), and the antistatic layer is wiped off and left for 3 days.
The static elimination is again performed for 10 seconds with the static eliminator, the weight is similarly measured with an electronic balance, the weight loss (g) before and after wiping is multiplied by 100, and the weight of the antistatic layer per 1 (m ² ) (g / m ² ). ² ) Calculate. The density of the antistatic layer is about 1.00,

{Thickness of antistatic layer} (μm) = 1.00 × {weight of antistatic layer per 1 (m ² )} (g / m ² ) Formula 1

Is calculated. As a test piece, a PET film, a silica plate, or the like is used.

(1-2) Measurement of thickness of antistatic layer based on absorbance Transparent sheet obtained by changing the thickness of several antistatic layers having the same composition,
It is provided on a film or a test piece, and the absorbance in the characteristic absorption band of the antistatic layer is determined by a spectrophotometer. The thickness of the antistatic layer is measured by wiping the samples.
｝ Plot the thickness of the antistatic layer by the wiping method｝ to ｛absorbance｝, create a weighing line by extrapolating the straight line part, and determine the thickness of the sample with unknown thickness of the antistatic layer by the absorbance of characteristic absorption. Anticipate. This method is used supplementally for samples where the wiping method is not suitable. When a baseline vibration due to interference appears in the chart at the time of measuring the absorbance, smoothing is performed to take an average.

(2) Measurement of Surface Resistance After the antistatic layer was formed, the sample was allowed to stand at 24 ° C. and 14% RH for one day, and the sample surface was applied with a surface resistance measuring device manufactured by Takeda Riken Co., Ltd., applied voltage 500 V, 24 ° C., 14% It was measured under the condition of RH.

Example 1 (a) Preparation of Sulfonic Acid Group-Containing Polyester and Its Aqueous Dispersion First, a sulfonic acid group-containing polyester was synthesized by the following method, and a dispersion thereof was prepared. Using 46 mol% of dimethyl terephthalate, 47 mol% of dimethyl isophthalate and 7 mol% of sodium 5-sulfoisophthalate as the dicarboxylic acid component and 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol as the glycol component, A transesterification reaction and a polycondensation reaction were carried out by the method. The glass transition temperature of the obtained sulfonic acid group-containing polyester was 69 ° C. Heating 300 parts of this sulfonic acid group-containing polyester and 150 parts of n-butyl cellosolve to form a viscous solution, and gradually adding 550 parts of water while stirring,
A uniform pale white aqueous dispersion having a solid content of 30% by weight was obtained.

(B) Preparation of sulfonic acid-containing polyaniline solution 100 mmol of 2-aminoanisole-4-sulfonic acid
Was stirred and dissolved in a 4 mol / l aqueous ammonia solution at 23 ° C., and 100 mmol of ammonium peroxodisulfate was dissolved.
of water. After the 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 copolymer. The volume resistivity of this copolymer was 12.3 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. At this time, the content of the sulfonic acid group of the sulfonated polyaniline is 10
It was 0%.

(C) Preparation of Coating Solution for Forming Antistatic Layer The solid content ratio of the sulfonated polyaniline to the sulfonic acid group-containing polyester was 30/70, and the surfactant Emulgen 810 (manufactured by Kao) was compared with the sulfonated polyaniline. Was 8/100. This is added to an equal volume mixture of water and isopropanol, and the total solid concentration is 1% by weight.
Was prepared.

(D) Preparation of antistatic laminated film or sheet Isophthalic acid was copolymerized with polyethylene terephthalate (PET) and 22 mol% of the acid component of the raw material monomer of polyethylene terephthalate to obtain an average particle size of 2.5 μm. A copolymer polyester to which 500 ppm of silica particles is added is prepared. 280 ° C to 2 in a multi-layer extruder with two extrusion barrels and a multi-manifold die
Extrusion and lamination at a temperature of 90 ° C.
(0 ° C.) and quenched to obtain a laminate in which the copolymerized polyester was laminated except for the ears of the PET sheet. At this time, the thickness of the PET layer was 110 μm, and the thickness of the copolymerized polyester layer was 31 μm. The sheet was heated to 85 ° C. and stretched 3.4 times in the sheet advancing direction between two sets of nip rolls having different rotation speeds. While heating the obtained uniaxially stretched film to 95 ° C. by a stenter method, 3.6.
The film was stretched twice, heat-fixed with 230 ° C. hot air while being relaxed by 5%, and wound. The thickness of the PET layer of the obtained film is 10
μm, and the copolyester layer was 2.6 μm. Next, the coating solution prepared in (c) was applied to the copolymer polyester layer side of this film by a bar coating method, and dried at 70 ° C. with hot air.

(E) Characteristic evaluation The thickness and surface resistance of the antistatic layer of the film obtained in (d) were measured. Table 1 shows the results. In a room with bright white light, the constants can be confirmed by looking through the film obtained in (d) and seeing a metal film resistor with a color code and a multilayer ceramic capacitor with a numerical value. Was.

(F) Preparation of packaging bag and packaging container The film obtained in (d) was three-side sealed by a heat sealing method with the antistatic layer facing inward. It became a bag without any problems.

Example 2 In the preparation of (d) the antistatic laminated film or sheet of Example 1, the coating solution prepared in (c) was applied to the PET layer side of the film and dried. The coating solution prepared in (c) was applied by a bar code method except for a portion to be sealed in advance, and dried at 70 ° C. with hot air.
Otherwise, the same procedure as in Example 1 was performed.

Examples 3 and 4 In Examples 3 and 4, the solid content ratio of the sulfonated polyaniline and the sulfonic acid group-containing polyester in (c) the preparation of the coating solution for forming the antistatic layer in Examples 1 and 2 was 10%, respectively. /
This is an example in which the same method as in Examples 1 and 2 is used except that 90 is used.

Comparative Examples 1 and 2 Comparative Examples 1 and 2 were the same as Examples 1 and 2 except that dodecylbenzenesulfonate was used instead of the sulfonated polyaniline in (c) preparing the coating solution for forming the antistatic layer. Is an example using the same method as in the first and second embodiments.

Example 5 A biaxially stretched polyester film (Toyobo polyester film, 25 μm thick, manufactured by Toyobo Co., Ltd.)
The coating solution obtained in (c) of Example 1 was applied by a bar coating method and dried at 70 ° C. with hot air. A polyethylene film (LIX-2, thickness 40 μm,
Toyobo Co., Ltd.) was laminated by an adhesive (base agent: AD590, curing agent: RT86, manufactured by Toyo Morton Co., Ltd.) by a dry lamination method to obtain an antistatic laminate. This was able to be made by the method of Example 1 (f) with the polyethylene side inside.

Example 6 The coating solution obtained in (c) of Example 1 was coated on the surface of a polyethylene film (LIX-2, thickness 40 μm, manufactured by Toyobo Co., Ltd.) by a bar coating method to seal a portion to be sealed later. The remaining coating was performed, followed by hot-air drying at 70 ° C. Next, separately from this, the coating solution obtained in (c) of Example 1 was applied to the surface of a biaxially stretched polyester film (Toyobo polyester film, thickness 25 μm, manufactured by Toyobo Co., Ltd.) by a bar coating method. And dried with hot air at 70 ° C. The surface opposite to the application surface of the polyethylene film and the surface opposite to the application surface of the biaxially stretched polyester film were bonded to each other by a dry lamination method using an adhesive (main agent: AD590, curing agent: RT86, Toyo Morton ( To obtain an antistatic laminate. This was made by the method of Example 1 (f) with the polyethylene side inside.

Comparative Examples 3 and 4 In Comparative Examples 3 and 4, dodecyl benzene sulfonic acid salt was used instead of the sulfonated polyaniline of Example 1 (c) as the coating solution for forming the antistatic layer in Examples 5 and 6, respectively. This is an example using the same method as in Examples 5 and 6, except that.

Example 7 In (d) of Example 1, the coating solution prepared in (c) was applied to the PET layer side of the film when coating, and the copolyester layer was coated on the inner side during the preparation of the packaging bag in (f). The procedure was the same as in Example 1, except that heat sealing was performed for This was a packaging bag that could be handled in the same manner as a bag made of a general heat-sealable PET film.

Example 8 The coating solution obtained in (c) of Example 1 was applied to the surface of a polyethylene film (LIX-2, thickness 40 μm, manufactured by Toyobo Co., Ltd.) by a bar coating method. It dried with hot air at ° C. This was able to be made by the method of Example 1 (f) with the polyethylene side inside. This was a packaging bag that could be handled similarly to a bag made of a general polyethylene film.

Example 9 A film made of a saponified ethylene-vinyl acetate copolymer having a thickness of 25 μm (denoted as EVOH in Table 1) was provided on both sides thereof with an adhesive polyolefin having a thickness of 12 μm (denoted as an adhesive in Table 1). The thickness of each linear 40μm
A laminate was formed by laminating low density polyethylene (LLDPE). The coating solution prepared in (c) of Example 1 was applied to both surfaces of the outermost layer of this laminate to form a laminate sheet. This was able to be bag-formed by the fusing seal method.

Example 10 A polyamide (PA) film having a thickness of 50 μm was placed on both sides of an adhesive polyolefin having a thickness of 12 μm on both sides with a thickness of 40 μm.
μm linear low density polyethylene (LL
DPE) was formed. The coating solution prepared in (c) of Example 1 was applied to both surfaces of the outermost layer of the laminate except for the sealing portion in advance to form a laminate sheet. This was able to be made into a bag by a heat sealing method.

In the column of the laminated structure in the following Tables 1 to 3,
When the antistatic laminate is formed into a bag, the inside is the A side, and the outside is B.
Expressed as the surface side.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

The antistatic laminate of the present invention is excellent in antistatic properties even under low humidity, and can be used for packaging articles that dislike moisture, and for packaging in dry and cold regions. Furthermore, it is suitable for antistatic packaging bags and packaging containers for transporting and packaging semi-finished products such as electronic components that require a drying step and dry storage.

Further, since a polyester used for a general packaging material, a polyester sealant or a polyolefin having a heat adhesive property or a polyolefin can be used for a laminated structure, it can be supplied at a price comparable to a general packaging material. Since it also has the handling, sealing, and versatility of general packaging materials,
It can be used for multiple purposes with the same product. Further, by devising the lamination structure, it is possible to freely change the performance such as moisture proof property, gas barrier property, oil resistance, pinhole resistance, strength and transparency.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shigetsugu Konagaya 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory (reference) 3E086 AD01 BA04 BA15 BB35 CA31 4F100 AA20C AK41A AK41C AK42B AK42C AK80A AL01A AL05A AL07A BA03 BA07 BA10A BA10C CA18A EH201 EH462 EJ381 GB16 GB17 JG03 JG03A JL12B

Claims (6)

[Claims] 1. A laminate having a structure in which a polyester layer or a polyolefin layer is sequentially laminated on an antistatic layer, wherein the antistatic layer comprises polyaniline and / or a derivative thereof, an ionic group and / or a polyalkylene glycol. An antistatic laminate comprising, as a main component, a mixture with a copolymerized polyester containing a component. 2. The antistatic laminate according to claim 1, wherein the polyester layer is a sealant layer made of a polyester resin. 3. The antistatic laminate according to claim 1, wherein the polyaniline derivative is a sulfonated polyaniline. 4. The antistatic laminate according to claim 1, wherein the copolyester is a copolyester containing a sulfonic acid group. 5. The antistatic laminate according to claim 1, which has a polyester layer and a polyolefin layer. 6. A packaging bag or container made from the laminate according to any one of claims 1 to 5.