JP2004114665A - Antistatic adhesive or paint, and laminated product comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive or paint, which is transparent, water resistant and highly antistatic throughout low- to high-humidity conditions, and demonstrates an excellent antistatic property even in a state isolated by a resin film; and a laminated product comprising the same. <P>SOLUTION: The adhesive or paint containing 0.1 to 20 wt.% per total resin of a salt, which consists of an ammonium cation having a total carbon number of 4 to 20 and an anion having a fluorine atom, and the laminated product comprising the same. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides an adhesive or paint containing a specific salt, having excellent heat resistance, water resistance, transparency and antistatic properties, and a laminate formed using the same. Is what you do.
[0002]
2. Description of the Related Art In general, synthetic resins are electrically insulating and are easily charged, which hinders operability during processing and causes malfunctions and failures of electric and electronic equipment as a product. It may cause a serious disaster such as a fire.
[0003] Therefore, it is necessary to impart antistatic properties to a synthetic resin molded product. Conventionally, in order to impart antistatic properties, a so-called antistatic agent (conductive compound) has been kneaded into a synthetic resin or applied to the surface of a molded product.
As the conductive compound, conductive particles such as carbon powder and metal powder, metal oxides such as tin oxide, surfactants, and organic conductive polymers are used.
[0004] Carbon powder, metal powder, conductive polymer and the like impart excellent antistatic properties, but impair transparency and become colored. Surfactants do not impair coloring or transparency, but the presence of moisture is essential to exhibit antistatic properties, so antistatic properties at low humidity cannot be expected, and they are easily eluted by water. Antistatic properties are lost.
Further, even when an antistatic property is given to an adhesive layer which is present between the adherends and does not exist on the surface, such as an adhesive, even if the laminate joined with the adhesive has an antistatic property, Is usually difficult to provide. In addition, a paint with antistatic properties is coated on one side of a film or sheet to give antistatic properties to the other side, or a topcoat without antistatic material is applied on top of the paint containing antistatic agent. It is usually difficult to develop antistatic properties on the surface.
As described above, in addition to excellent antistatic properties, the layer having transparency (including non-coloring properties), water resistance, antistatic properties at low humidity, workability, and the like, and further containing a layer containing an antistatic agent. At present, there is no antistatic agent capable of expressing antistatic properties in a state of being isolated by a resin film, and there is no adhesive or paint using the antistatic agent.
[Reference Patent Document 1] JP-A-2002-054072
[Reference Patent Document 2] JP-A-11-256143
[0007]
[Problems to be Solved by the Invention] We have excellent transparency and water resistance, excellent antistatic properties from high humidity to low humidity, and excellent properties even when isolated by resin films such as films. It is an object of the present invention to solve the above-mentioned current problems by inventing an adhesive or a paint that exhibits antistatic properties.
[0008]
[Means for Solving the Problems] To solve the above problems, the present invention provides:
(1) A salt comprising an ammonium cation having no total hydrogen atom and having no hydrogen atom directly bonded to a nitrogen atom and a fluorine atom-containing anion and having a total carbon number of 4 to 20 is added in an amount of 0.1 to 20% by weight based on the total resin content. The adhesive or paint and the laminate (2) formed therefrom, having antistatic properties, characterized in that the salt is 1,3-dialkylimidazolium bis {(trifluoromethyl) sulfonyl} amide (1) An adhesive or paint having antistatic properties and a laminate formed therefrom (3) The adhesive or paint contains a polyurethane resin or a natural resin. It is intended to provide an adhesive or paint having the antistatic property of (1) and a laminate formed therefrom.
Hereinafter, the present invention will be described in more detail.
The ammonium cation having 4 to 20 carbon atoms and not containing a hydrogen atom directly bonded to a nitrogen atom according to the present invention is a quaternized nitrogen cation in which nitrogen is bonded to four carbon atoms. And an ammonium cation having a total carbon number of 4 to 20 contained in the bonding group (including the case where the nitrogen atom is a member of the ring).
When the total number of carbon atoms contained in the group bonded to nitrogen is less than 4 and there is a hydrogen atom directly bonded to the nitrogen atom, the salt formed from the ammonium cation has poor water resistance, and Ammonium salts having 20 or more carbon atoms have low conductivity, and none of them is suitable for the present invention. Preferably, it is an ammonium cation having a total carbon number of 5 to 15.
Specific examples of the ammonium cation species of the present invention include:
Quaternary ammonium such as trimethylhexylammonium and trimethyloctylammonium, imidazolium substituted with alkyl at the 1,3-position such as 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium, N-butylpyridinium And N, N-dialkylpyrrolidinium such as N-methyl-N-butylpyrrolidinium, and N, N-dialkylpiperidinium such as N-methyl-N-butyl-piperidinium. Can be done.
The fluorine atom-containing anion of the present invention is an inorganic or organic anion containing a fluorine atom. For example, PF ₆ , BF ₄ ,
An imide anion represented by N (SO ₂ C _n F _{2n + 1} ) ₂ (where n is an integer of 0 to 4), for example, N (SO ₂ F) ₂ , N (SO ₂ CF ₃ ) ₂ ,
N (SO ₂ C ₂ F ₅ ) ₂ , and further, CF ₃ SO ₂ —N—COCF _{3 and the} like can be given. These fluorine atom-containing anions have excellent heat resistance and oxidation resistance as compared with other halogen atom-containing anions and other inorganic anions.
Organic imide-based anions such as N (SO ₂ CF ₃ ) ₂ are also preferable in that they have good affinity with synthetic resins.
Preferred salts according to the combination of the specific ammonium cation and the fluorine-containing anion of the present invention include 1-ethyl-3-methylimidazolium bis {(trifluoromethyl) sulfonyl} amide and 1-ethyl-3-methyl Examples thereof include imidazolium bis {(pentafluoroethyl) sulfonyl, N-methyl-N-propylpiperidinium bis} (trifluoromethyl) sulfonyl} amide.
In the present invention, the adhesive is used between the adherends and the adherends to join them together, and includes a binder (binder), an anchor coat agent (undercoat), and an adhesive. Agents and the like. These are usually applied in a liquid form dissolved or dispersed in a solvent or water, and after drying the solvent or water, they are often heated or pressed without heating. Or hot-melt adhesive that is applied in the molten state, film-like adhesive that is sandwiched between adherends in the form of a film, and that is heated or pressed without heating. Adhesive). The present invention can be applied to any of the above.
In the present invention, the paint is used to cover the surface of an object, and includes a coating agent, an overcoat agent, ink, spray and the like. The paint is also applied to the surface of the object by dissolving or dispersing it in a solvent or water, drying the solvent or water, and further heating or forming a film (or film) without heating. There is also a powder coating which is coated with powder and heated and fused. The present invention can be applied to any of the above.
These adhesives and paints include, in addition to resin components, solvents, water and other media, dyes, pigments, fillers, antioxidants, polymerization initiators, release agents, other metal salts, and the like. May be included at all.
The amount of the salt added to the adhesive or paint in the present invention is 0.1 to 20% by weight based on the total resin. If the amount is less than 0.1% by weight, antistatic properties are not sufficiently exhibited, and if the amount exceeds 20% by weight, adhesiveness and cohesion as an adhesive or paint are impaired. It is preferably from 2 to 10% by weight, particularly preferably from 3 to 6% by weight.
As the resin used for the adhesive and the paint of the present invention, vinyl resins such as polyvinyl acetate, polyvinyl chloride, polymethyl methacrylate, thermoplastic polyester resin, thermoplastic polyamide resin, polyurethane resin, epoxy resin, phenol resin , Unsaturated polyester resin, acrylic heat (and / or light) curable resin, rubber resin, natural resin, and copolymer resins thereof. Examples of natural resins include cellulosic resins, guar gum, tamarind, locust bean gum, xanthan gum, carrageen, and derivatives thereof.
Examples of the adherend or substrate to which the adhesive or paint of the present invention is applied include molded articles (fiber, knitted fabric, nonwoven fabric, film) made of metal, glass, ceramic, wood, paper, synthetic resin and the like. , Sheets, plates, and their processed products). In particular, it is well applied to fabrics, films, sheets, boards made of synthetic resins and their processed products.
Examples of the synthetic resin include polyolefin resins such as polyethylene and polypropylene, vinyl resins such as polystyrene, polyvinyl chloride, polymethyl methacrylate, and polyacrylonitrile; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyoxybenzoate; Polyamide resins such as polycaprolactam, polyhexamethylene adipate, poly-m-phenyleneisophthalamide, polyphenylene sulfide resins, polycarbonate resins, polysulfone resins such as polysulfone and polyethersulfone, and polyetherketones such as polyetheretherketone Resin, polyimide resin, epoxy resin, polyurethane resin, phenol resin, unsaturated polyester resin Etc. can be exemplified a system resin, both available commercially.
The adhesive or paint having antistatic properties of the present invention has excellent antistatic properties even on the surface of a laminate formed by using them, that is, on the surface separated by an adherend or a substrate. Has the feature that it can be expressed. If this is used, since the salt does not directly come out on the surface, the antistatic durability is improved, and the antistatic property can be imparted without inhibiting the characteristics of the surface. For example, it is conceivable to use salt in the anchor coat layer between the magnetic layer of the magnetic tape or floppy disk and the base film. Also, if salt is contained in the anchor coat layer between the base film and the polyolefin heat seal layer, the inside of the bag will have antistatic or anti-fog properties without the salt coming into direct contact with food etc. in containers such as bags processed from it. Can be given. Further, if an adhesive coating agent for an adhesive tape or an adhesive tape in which a salt is contained in the adhesive is applied to the surface of various objects, antistatic properties can be imparted to the surface.
[0022]
Embodiments of the present invention will be described below.
Tobacco ash adhesion test: Prepare a cigarette butt rubbed with your fingers. Rub the surface of the test object with a cotton cloth and approach the surface from the vertical direction of the ash dust, and when approaching a distance of 5 mm, observe whether or not ash dust has been sucked. Indicates that the antistatic property is developed).
[0023]
Example 1 An example of the synthesis of 1-ethyl-3-methylimidazolium bis-{(trifluoromethyl) sulfonyl} amide (EMI / TFSI) will be described.
37.0 gr (0.45 mol) of 1-methylimidazole was dissolved in 200 ml of 1,1,1-trichloroethane, and 98.1 gr (0.9 mol) of bromoethane was added dropwise over 1 hour while stirring at room temperature. Then, stirring was continued at 50 ° C. for 10 hours to carry out a reaction. The precipitate formed was separated, washed twice with 100 ml each of 1,1,1-trichloroethane, dried under vacuum at 70 ° C. for 2 hours, and white crystals of 1-ethyl-3-methylimidazolium bromide (EMIBr) 77 gr (90%) were obtained.
Next, potassium bis-{(trifluoromethyl) sulfonyl} amide (KTFSI) was dissolved in 100 ml of water at 70 ° C, and while stirring at 50 ° C, 19.1 gr (0.1 mol) of EMIBr obtained above was added to water. After the solution dissolved in 50 ml was added dropwise over 10 minutes, the mixture was further stirred for 30 minutes to carry out the reaction. The resulting oil layer was separated, washed twice with 50 ml of water each time, dried under vacuum at 100 ° C. for 2 hours, and liquid salt 1-ethyl-3-methylimidazolium bis-{(trifluoromethyl) sulfonyl at room temperature. 33.2 gr of amide (EMI-TFSI) (85% yield) was obtained.
The synthesized product was identified by IR spectrum and NMR spectrum.
The EMI / TFSI synthesized in this example exhibited excellent heat resistance when the pyrolysis temperature measured in argon was 350 ° C. or higher.
[0024]
Example 2 An adhesive solution was prepared by dissolving 1.25 gr of EMI / TFSI obtained in Example 1 and 25 gr of a thermoplastic polyester resin (Toyobo Byron 300) in 75 gr of a mixed solvent of toluene and methyl ethyl ketone (1: 1 by volume). did. This solution was applied to the surface of a 50 μm polyester film (Torel Miller T type) and then dried with hot air at 80 ° C. for 5 minutes to form an adhesive layer having a thickness of 20 μm. Another 50 μm polyester film is overlaid on the coated surface, 100 ° C., 10 kg / cm ² , 2 minutes, applying temperature, pressure and time, thermocompression bonding, and the two polyester films are laminated to obtain a colorless and transparent laminated film. Was. The peel strength (180 ° peel at 5 cm / min) was 1.3 kg / cm.
The laminated film was subjected to a cigarette ash adhesion test at 30% RH, 45% RH, and 60% RH. No adhesion of ash dust was observed on any surface on any humidity.
[0025]
COMPARATIVE EXAMPLE 1 A laminated film prepared in the same manner except that EMI / TFSI was not added to the adhesive solution of Example 2 showed adhesion of ash dust in any of the conditions under the cigarette ash adhesion test.
[0026]
EXAMPLE 3 25 gr of a thermoplastic polyester resin (Toyobo Byron 500), 3.75 gr of trimethylolpropane tolylene diisocyanate adduct, and 1.4 gr of EMI / TFSI obtained in Example 1 were mixed with toluene-methyl ethyl ketone (1: 1 volume ratio). ) Gr to prepare an adhesive (anchor coating agent) solution.
This solution was applied to one side of a 12 μm polyester film and dried at 80 ° C. for 3 minutes to form a 5 μm thick anchor coat layer.
The polypropylene resin was melted by an extruder, and a molten film extruded from a T-die at 230 ° C. was extruded and coated on the coated surface of the above-mentioned coated film adhered to a chill roll at 50 ° C. Next, it was pressed, cooled and solidified by a nip roll provided on a chill roll to prepare a laminated film of a polypropylene film and a polyester film having a thickness of 72 μm. The peel strength (180 ° peel at 5 cm / min) was 0.6 kg / cm. As a result of the cigarette ash adhesion test at 60% RH, adhesion of ash dust was not recognized on both surfaces.
[0027]
Example 4 25 gr of dipentaerythritol hexaacrylate, 1.3 gr of EMI / TFSI synthesized in Example 1, and 0.75 gr of ethylbenzoin ether were dissolved in 75 gr of ethylene glycol monomethyl ether to prepare a hard coat agent. The coating agent was applied to one side of a 4 mm-thick polymethyl methacrylate plate, dried at 50 ° C. for 10 minutes, and irradiated with a high-pressure mercury lamp at 0.7 mJ / cm ² . A colorless and transparent hard coat layer (5 μm) was formed on the surface.
This hard coat layer was no. It was rubbed with a steel wool of 0 at a pressure of 32 gr / cm ² , but was not scratched and was found to have abrasion resistance. Further, as a result of conducting a cigarette ash adhesion test at 60% RH, adhesion of ash dust was not recognized on the coated surface and the uncoated surface.
[0028]
Comparative Example 2 A hard coat polymethyl methacrylate prepared in the same manner as in Example 4 except that EMI / TFSI was added to the hard coat agent of Example 4 On the coated and uncoated surfaces, adhesion of ash dust was observed in the tobacco ash adhesion test.
[0029]
Example 5 25 gr of an acrylonitrile-butadiene copolymer (JSR N215SL) and 2.0 gr of 1-ethyl-3-methylimidazolium bis {(pentafluoroethyl) sulfonyl} amide synthesized in the same manner as in Example 1 were treated with methyl ethyl ketone. An adhesive solution dissolved in 75 gr was prepared. This solution was applied to a 25 μm polyester film and dried with hot air at 60 ° C. for 5 minutes. A polyester film having a 10 μm adhesive layer was obtained. As a result of conducting a cigarette ash adhesion test at 60% RH, no ash dust adhesion was observed on the polyester film surface. Therefore, it is possible to impart antistatic properties to the surface by sticking it to various surfaces via an adhesive layer. all right.
[0030]
According to the present invention, an adhesive or paint containing 0.1 to 20% by weight of a salt composed of an ammonium cation having a total carbon number of 4 to 20 and an anion containing a fluorine atom with respect to the total resin is colorless and transparent. It has excellent antistatic properties from low humidity to high humidity, and the same antistatic properties as described above can be imparted to the surface of a laminate formed therefrom.

Claims (3)

A salt consisting of an ammonium cation having no carbon atom directly bonded to a nitrogen atom and having a fluorine atom and a fluorine atom-containing anion having 4 to 20 carbon atoms in total and containing 0.1 to 20% by weight based on the whole resin. An adhesive or paint having antistatic properties and a laminate formed therefrom. 2. The antistatic adhesive or paint according to claim 1, wherein the salt is 1,3-dialkylimidazolium bis {(trifluoromethyl) sulfonyl} amide, and a laminate formed therefrom. The adhesive or paint and the laminate formed therefrom according to claim 1, wherein the adhesive or paint contains a polyurethane resin or a natural resin.