JP4980562B2 - Coating agents and processed products - Google Patents

Description

  The present invention relates to a coating agent that provides moisture resistance and antistatic ability in a single solution, and a processed product coated with the coating agent.

  Conventionally, packaging containers for storing various foods, medicines, industrial materials and the like have been thermoplastic resins such as polyethylene terephthalate (hereinafter abbreviated as “PET”) and nylon 6 (hereinafter abbreviated as “Ny6”). It is produced by forming a film or paper. And when packing a product which dislikes moisture and electrification in these packaging containers, it is necessary to perform moisture proofing and antistatic processing.

For example, there is a method in which a moisture-proof layer is laminated on a base material in moisture-proof processing. As a lamination method, there are a method of melting and laminating a material having moisture proof performance, a method of laminating a material having moisture proof performance dissolved or dispersed in a medium, and the like. The latter is advantageous in terms of operation because it is easy to handle.
On the other hand, as an antistatic process, for example, in the case of a film, a film obtained from a resin kneaded with an antistatic agent or a film having an antistatic coating film formed on the surface has been put into practical use. However, for example, a film obtained from a resin kneaded with an antistatic agent needs to contain a large amount of the antistatic agent in order to improve the antistatic performance, and is not economical. . Furthermore, the latter is advantageous because there is a problem that the antistatic performance is remarkably lowered when it is laminated on a film to provide other functions.

  When applying moisture-proof performance and antistatic performance to a substrate, it is common to stack a moisture-proof layer on the substrate and then stack an antistatic layer, but perform moisture-proof processing and anti-static processing separately. Is cumbersome in operation, and development of a coating agent capable of simultaneously imparting moisture-proofing and antistatic performance by one processing is required. For example, Patent Document 1 discloses a method using an antistatic agent mainly composed of an acid-treated yeast cell wall fraction, and Patent Document 2 discloses a vinylidene chloride copolymer and liquid paraffin, paraffin wax, cationic or both. A topcoat agent comprising an ionic antistatic agent or the like is disclosed.

  Furthermore, there are two types of coating agents, depending on the type of medium, those using organic media and those using aqueous media. In recent years, environmental protection, resource conservation, dangerous goods regulations such as the Fire Service Act, workplace environment, etc. From the standpoint of improvement, the use of organic solvents is restricted and the use of aqueous media tends to be preferred.

JP 2002-38133 A JP-A-8-134242

  However, the invention described in Patent Document 1 does not have a specific description regarding moisture-proof performance. On the other hand, in the invention described in Patent Document 2, since there is no description regarding antistatic ability, and since a vinylidene chloride copolymer containing chlorine is used, harmful substances such as acidic gas are generated during incineration. It is not preferable.

  An object of the present invention is to solve the above-mentioned problems, to provide a coating agent capable of simultaneously imparting moisture-proofing and antistatic functions by a single processing, and to provide a processed product coated with this moisture-proof coating agent.

  As a result of intensive investigations to solve the above problems, the present inventors have found that a coating agent comprising a specific composition of polyolefin resin, natural wax, conductive material, and liquid medium has two functions of moisture prevention and antistatic in a single process. Was found to be excellent in stability, and the present invention was reached based on this finding.

That is, the gist of the present invention is as follows.
(1) a coating agent consisting of an unsaturated carboxylic acid unit and including polyolefin resin, natural wax, a conductive material and an aqueous medium, the polyolefin resin comprises a propylene component, butene component and an ethylene component, a propylene component, butene component When the total of ethylene components is 100 parts by mass, the propylene component is 9.5 to 90 parts by mass, the butene component is 9.5 to 90 parts by mass, the ethylene component is 0.5 to 40 parts by mass, and the polyolefin resin becomes Nde 0.5 to 10 wt% containing an unsaturated carboxylic acid unit with respect to 100 mass%, the polyolefin resin 100 mass parts per in the coating agent, conductive natural waxes and 1-100 parts by weight of 5 to 200 parts by weight A coating agent comprising a material.
( 2 ) The coating agent according to (1) , wherein the conductive material is a conductive polymer.
( 3 ) A composition obtained by removing a liquid medium from the composition described in (1) or ( 2 ).
( 4 ) The composition according to ( 3 ), wherein the water vapor transmission coefficient at 40 ° C. and 100% RH is 200 g · μm / m ² / day or less.
( 5 ) The composition according to ( 3 ), wherein the surface resistivity value at 20 ° C. and 60% RH is less than 10 ¹¹ Ω / □.
( 6 ) A processed product obtained by providing the composition according to ( 3 ) on a substrate.
( 7 ) The processed product according to ( 6 ), wherein the substrate is paper or synthetic paper.
( 8 ) A film in which a layer of the composition described in ( 3 ) is laminated on at least one surface of a thermoplastic resin film.
( 9 ) The film according to ( 8 ), wherein the haze is 20% or less.

  According to the coating agent of the present invention, a layer having moisture resistance and antistatic performance while being a thin film can be easily formed on various substrates at once with a simple apparatus. The pot life is also good. Furthermore, if an aqueous medium is used as the liquid medium of the coating agent of the present invention, it will be suitable for purposes such as environmental protection and compliance with dangerous goods regulations.

  Hereinafter, the present invention will be described in detail.

  The coating agent of the present invention comprises a polyolefin resin having a specific composition, a natural wax, a conductive material, and a liquid medium. The liquid medium is not particularly limited as long as it is liquid at room temperature and normal pressure, such as organic solvent, water, but storage stability, ease of handling, and environmental protection, resource saving, regulations on dangerous goods by the Fire Service Act, etc. From the standpoint of improving the work environment, the use of an aqueous medium is preferable. What contains 50 mass% or more of water with an aqueous medium is preferable, More preferably, it is 80 mass% or more. The solvent other than water contained in the aqueous medium is preferably a hydrophilic organic solvent, and specific examples thereof include alcohols such as methanol, ethanol, isopropanol, n-propanol, ethylene glycol-ethyl ether, and ethylene glycol-n-butyl ether. , Ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, methyl acetate, acetic acid-n-propyl, isopropyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate Such as esters, acetonitrile and the like, those having solubility in water at 20 ° C. of preferably 10 g / L or more, particularly preferably 50 g / L or more are used. Further, ammonia and diethylamine, triethylamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-diethanolamine, 3-methoxypropylamine, 3-diethylaminopropylamine, dimethylamino Examples include basic compounds such as organic amine compounds such as propylamine, morpholine, and methylmorpholine.

  In addition, as a form in which the polyolefin resin, natural wax and conductive material are contained in the liquid medium, there is a form of a solution or a dispersion, but a dispersion is preferable, and storage stability, ease of handling, environment An aqueous dispersion is particularly preferred for reasons such as protection.

  The polyolefin resin needs to be configured to contain 50 to 100% by mass of unsaturated hydrocarbon having 3 to 6 carbon atoms as a copolymerization component, and is preferably 60 to 100% by mass from the viewpoint of moisture resistance. More preferably, it is 70-100 mass%, and it is further more preferable that it is 80-100 mass%. If the content of the unsaturated hydrocarbon having 3 to 6 carbon atoms is less than 50% by mass, the moisture resistance is remarkably lowered.

  When an aqueous medium is used as the liquid medium, the copolymer component of the polyolefin resin is 50 to 99.5% by mass of unsaturated hydrocarbons having 3 to 6 carbon atoms and 0.5 to 5% of unsaturated carboxylic acid units. It is preferable to contain 10 mass%. When the unsaturated hydrocarbon having 3 to 6 carbon atoms exceeds 99.5% by mass, the mixing stability with the natural wax may be lowered. Further, when the content of the unsaturated carboxylic acid unit is less than 0.5% by mass, stable aqueous dispersion becomes difficult, and when the content of this unit exceeds 10% by mass, adhesion to materials such as PET and Ny6 Tend to decrease.

  Examples of the unsaturated hydrocarbon having 3 to 6 carbon atoms include alkenes such as propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene and 1-hexene. From the viewpoint of ease of resin production, moisture proofing, and ease of aqueous resin formation, it is preferably a propylene component or a butene component (1-butene, isobutene, etc.). You can also

  Moreover, it is preferable that the polyolefin resin used by this invention contains 2-50 mass% of ethylene components other than above-mentioned C3-C6 unsaturated hydrocarbon. By containing an ethylene component, the moisture resistance is further improved, and further, the resin is easily made water-based.

  In order to develop better moisture resistance, the unsaturated hydrocarbon component of the polyolefin resin is composed of three components, a propylene component, a butene component, and an ethylene component, and the ratio of the three components is 100 parts by mass. It is preferable that the propylene component is 9.5 to 90 parts by mass, the butene component is 9.5 to 90 parts by mass, and the ethylene component is 0.5 to 40 parts by mass.

  In the polyolefin resin, the copolymerization form of each component is not limited, and examples thereof include random copolymerization and block copolymerization. From the viewpoint of ease of polymerization, random copolymerization is preferable. Moreover, you may mix 2 or more types of polyolefin resin so that it may become the structural component ratio of this invention.

  In addition to the above components, other components may be contained in an amount of about 20% by mass or less, preferably 2 to 15% by mass, based on the whole polyolefin resin. Examples of other components include carbon numbers such as 1-octene and norbornenes. More than 6 alkenes and dienes, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate (Meth) acrylates such as stearyl (meth) acrylate, maleate esters such as dimethyl maleate, diethyl maleate, dibutyl maleate, dilauryl maleate, dioctyl maleate, didodecyl maleate, distearyl maleate , (Meth) acrylic amides, methyl vinyl ether, ethyl vinyl Alkyl vinyl ethers such as ether, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, and vinyl alcohol obtained by saponifying vinyl esters with basic compounds, 2- Examples thereof include hydroxyethyl acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and the like, and a mixture thereof can also be used.

  When an aqueous medium is used as the liquid medium, it is more preferable that 0.1 to 15% by mass of (meth) acrylic acid esters is included in the total amount of the polyolefin resin in view of ease of making the resin aqueous. The content is more preferably 5 to 15% by mass, and particularly preferably 1 to 10% by mass. Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

  The weight average molecular weight of the polyolefin resin is preferably in the range of 10,000 to 150,000, more preferably 20,000 to 120,000 from the viewpoint of making the resin aqueous, and 20,000 to 100,000. Is more preferably 30,000, particularly preferably 30,000 to 90,000, and most preferably 40,000 to 80,000. When the weight average molecular weight is less than 10,000, the obtained coating film tends to be brittle even if it is hard. When the weight average molecular weight exceeds 150,000, the viscosity of the coating agent becomes high and handling becomes difficult. In addition, the weight average molecular weight of resin can be calculated | required on the basis of polystyrene resin using a gel permeation chromatography (GPC).

  When an unsaturated carboxylic acid component is copolymerized with a polyolefin resin, the acid value can also be used as a measure of the amount of copolymerization. The acid value of the polyolefin resin is preferably 5 to 100 mgKOH / g from the viewpoint of dispersibility. This range is more preferably 10 to 100 mgKOH / g, further preferably 10 to 90 mgKOH / g, particularly preferably 15 to 85 mgKOH / g, and most preferably 15 to 80 mgKOH / g. When the acid value is less than 5 mgKOH / g, it tends to be difficult to make the polyolefin resin aqueous. On the other hand, when the acid value exceeds 100 mgKOH / g, it becomes easy to make the resin aqueous, but PET and Ny6 There exists a tendency for the adhesiveness with respect to such materials to fall.

  Unsaturated carboxylic acid units that can be copolymerized with the polyolefin resin can be introduced into the polyolefin resin by unsaturated carboxylic acid or its anhydride. Specific examples thereof include acrylic acid, methacrylic acid, maleic acid, Maleic anhydride, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, allyl succinic acid, etc., as well as unsaturated dicarboxylic acid half esters, half amides, etc. A compound having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit) can be used. Of these, maleic anhydride, acrylic acid, and methacrylic acid are preferred, and maleic anhydride is more preferred from the viewpoint of ease of introduction into the polyolefin resin. The form of copolymerization is not limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization. Incidentally, the acid anhydride unit introduced into the polyolefin resin tends to take an acid anhydride structure in a dry state, and in the aqueous medium containing the basic compound, part or all of the acid anhydride units are opened to form a carboxylic acid or It tends to be the salt structure.

  In order to graft copolymerize an unsaturated carboxylic acid with a polyolefin resin, for example, a method in which a polyolefin resin and an unsaturated carboxylic acid are heated and melted to a temperature higher than the melting point of the polyolefin resin in the presence of a radical generator, An example is a method in which the reaction is carried out by heating and stirring in the presence of a radical generator after dissolution in an organic solvent. Examples of the radical generator used for graft copolymerization include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, Examples thereof include organic peroxides such as cumene hydroperoxide, tert-butyl peroxybenzoate, ethyl ethyl ketone peroxide, and di-tert-butyl diperphthalate, and azonitriles such as azobisisobutyronitrile. These may be appropriately selected and used depending on the reaction temperature.

  When an unsaturated carboxylic acid is introduced into the polyolefin resin, it is preferable to use a basic compound. A part of the carboxyl group is neutralized with a basic compound, and the dispersion stability of the resin is improved.

  Examples of natural waxes used in the present invention include plant waxes such as candelilla wax, carnauba wax, rice wax, and wax, animal waxes such as shellac wax and lanolin wax, mineral waxes such as montan wax and ozokerite, paraffin wax, Examples thereof include petroleum waxes such as microcrystalline wax. Of these, candelilla wax, carnauba wax, and paraffin wax are preferable because they exhibit excellent moisture resistance, and candelilla wax and paraffin wax are particularly preferable.

  The blending ratio of the polyolefin resin and the natural wax in the coating agent of the present invention needs to be 5 to 200 parts by mass of the natural wax with respect to 100 parts by mass of the polyolefin resin in order to maintain the strength of the composition layer. Yes, preferably 10 to 100 parts by mass, more preferably 10 to 60 parts by mass, and particularly preferably 15 to 45 parts by mass. If it is less than 1 part by mass, moisture resistance may not be sufficiently exhibited. Further, the natural wax component tends to improve the moisture resistance as the amount thereof increases. However, even if it is used in excess of 200 parts by mass, the moisture resistance performance is hardly improved. When the amount exceeds 200 parts by mass, the composition layer becomes brittle and adhesion to the substrate may be reduced.

The water vapor transmission coefficient of the composition layer obtained from the coating agent of the present invention under 40 ° C. and 100% RH needs to be 200 g · μm / m ² / day or less, and 150 g · μm / m ² / day or less. Preferably, it is 120 g · μm / m ² / day or less, more preferably 100 g · μm / m ² / day or less, and more preferably 70 g · μm / m ² / day or less. Particularly preferred. When the water vapor transmission coefficient exceeds 200 g · μm / m ² / day, the moisture-proof performance is insufficient, and the coating amount (thickness) increases to give the predetermined moisture-proof property.

  On the other hand, the conductive material used in the present invention is not particularly limited, and examples thereof include inorganic conductive materials such as tin oxide, antimony-doped tin oxide, indium-doped tin oxide, tin oxide-doped indium, and aluminum-doped zinc oxide, polypyrrole. Examples include conductive polymers such as polyaniline, polythiophene, and polyethylenedioxythiophene. Excellent antistatic performance in a small amount from the standpoint of balance with moisture-proof performance material and maintenance of transparency of composition layer. Conductive polymers exhibiting are preferred.

  In order to maintain the strength of the composition layer, the blending ratio of the polyolefin resin and the conductive material in the coating agent of the present invention needs to be 1 to 100 parts by mass of the conductive material with respect to 100 parts by mass of the polyolefin resin. Yes, preferably 3 to 50 parts by mass, more preferably 5 to 35 parts by mass, and particularly preferably 7 to 25 parts by mass. If it is less than 1 part by mass, the antistatic performance may not be sufficiently exhibited. In addition, as the amount of the conductive material increases, the antistatic performance tends to improve. However, addition of more than necessary is uneconomical, and the transparency of the composition layer is lowered. There are things to do.

The surface resistivity of the composition layer obtained from the coating agent of the present invention at 20 ° C. and 60% RH needs to be less than 10 ¹¹ Ω / □, and preferably less than 10 ¹⁰ Ω / □, More preferably, it is less than 10 ⁹ Ω / □, more preferably less than 10 ⁸ Ω / □, and particularly preferably less than 10 ⁷ Ω / □. If the surface resistivity exceeds 10 ¹¹ Ω / □, it cannot be said that it has antistatic ability.

  In the coating agent of the present invention, the content of the surfactant generally used to disperse the hydrophobic compound in the aqueous medium is determined from the solid content (polyolefin resin, natural wax in the coating agent) from the viewpoint of moisture resistance. The total amount of conductive material) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, still more preferably 5 parts by mass or less, and substantially no content with respect to 100 parts by mass. (For example, 0.1 parts by mass or less) is particularly preferable. Since the surfactant is difficult to remove by heating or reduced pressure, it remains in the composition layer and may deteriorate the properties of the composition layer. Those which do not substantially contain a surfactant have excellent coating film characteristics, particularly moisture resistance, and their performance hardly changes in the long term.

  Examples of the surfactant in the present invention include a cationic surfactant, an anionic surfactant, a nonionic (nonionic) surfactant, an amphoteric surfactant, a fluorosurfactant, and a reactive surfactant. In addition to those generally used for emulsion polymerization, emulsifiers are also included. For example, anionic surfactants include sulfates of higher alcohols, higher alkyl sulfonic acids and salts thereof, alkyl benzene sulfonic acids and salts thereof, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide. -Compounds having a polyoxyethylene structure such as propylene oxide copolymer and sorbitans such as polyoxyethylene sorbitan fatty acid ester It includes conductors, and examples of the amphoteric surfactant, lauryl betaine, lauryl dimethyl amine oxide, and the like. Examples of reactive surfactants include alkylpropenylphenol polyethylene oxide adducts and their sulfate esters, allyl alkylphenol polyethylene oxide adducts and their sulfate esters, allyl dialkylphenol polyethylene oxide adducts and their sulfate esters, etc. Examples thereof include compounds having a reactive double bond.

  The coating agent of the present invention may contain a crosslinking agent in order to improve performance such as solvent resistance. The blending ratio of the crosslinking agent is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. When the addition amount is less than 0.1 parts by mass, the effect of addition is small, and when it exceeds 30 parts by mass, the moisture resistance and antistatic performance tend to be lowered. As the crosslinking agent, a compound having a self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal salt having a polyvalent coordination site, and the like can be used. Melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents and the like are preferable. These crosslinking agents may be used alone or in combination of two or more.

  Furthermore, the coating agent according to the present invention includes organic / inorganic fillers, plate pigments, inorganic layered compounds, pigments, pigment dispersants, wetting agents, antifoaming agents, thickeners, freezing agents as long as the properties are not impaired. Melting stabilizers, coating aids, antiseptics, antifungal agents, anticorrosive agents, plasticizers, antioxidants, UV absorbers, radical scavengers, weathering agents, flame retardants, leveling agents, anti-cracking agents, etc. Can be added.

  The solid content in the coating agent of the present invention can be appropriately selected depending on the film forming conditions, the target coating amount and performance, etc., and is not particularly limited, but the viscosity of the coating composition is appropriately maintained and good. 1-60 mass% is preferable at the point which expresses a coating-film formation ability, 3-50 mass% is more preferable, 5-45 mass% is further more preferable, and 10-40 mass% is especially preferable.

  The production method for obtaining the coating agent of the present invention is not particularly limited as long as it is a method in which polyolefin resin, natural wax, and conductive material are uniformly mixed and dispersed or dissolved in a liquid medium. For example, as a method for producing an aqueous dispersion type coating agent, there is a method in which an aqueous dispersion of polyolefin resin, an aqueous dispersion of natural wax, an aqueous dispersion of conductive material or an aqueous solution prepared in advance is mixed. This method is preferable because an aqueous coating agent comprising a combination of various polyolefin resins, natural waxes, and conductive materials can be easily prepared.

  The preparation method of the aqueous dispersion of polyolefin resin used in the above-mentioned method includes (i) a method of preparing an aqueous dispersion such as polyolefin resin by emulsion polymerization, and (ii) making the polyolefin resin into a molten state or a solution state, A method of emulsifying by dispersing in the presence of a surfactant and finely crushing by a shearing force of stirring; (iii) a method of melt-kneading and emulsifying a polyolefin resin, water, a surfactant and / or a carboxy-modified wax with an extruder, (Iv) Any method of emulsifying by heating and stirring an aqueous medium containing a polyolefin resin, a basic compound, and the above-described water-soluble organic solvent in a sealed container under pressure may be used. Among these, the method (iv) is preferable because a surfactant is not required.

  The method (iv) can be prepared by heating and stirring using a known solid / liquid stirring device, an emulsifier, etc., preferably a device capable of pressurization of 0.1 MPa or more. The stirring method and the rotation speed of stirring are not particularly limited, but low-speed stirring that allows the resin to float in the medium may be used, and high-speed stirring (for example, 1,000 rpm or more) is not essential. Raw materials such as a polyolefin resin having a specific composition, a basic compound, and an aqueous medium are charged into such an apparatus, and then the temperature in the tank is 60 to 220 ° C, preferably 80 to 200 ° C, more preferably 100 to 190 ° C. Particularly preferably, the polyolefin resin is sufficiently aqueousized by continuing stirring until the coarse particles disappear (for example, 5 to 120 minutes) while maintaining the temperature at 100 to 180 ° C., and preferably under stirring. An aqueous dispersion can be obtained by cooling to 40 ° C. or lower. When the temperature in the tank is lower than 60 ° C., it becomes difficult to make the polyolefin resin aqueous. When the temperature in a tank exceeds 220 degreeC, there exists a possibility that the molecular weight of polyolefin resin may fall.

  The number average particle size of the resin particles in the aqueous dispersion of polyolefin resin is preferably 1 μm or less from the viewpoint of stability, and 0.5 μm or less from the viewpoint of moisture resistance, transparency of the coating film, and low-temperature film-forming property. More preferably, it is more preferably 0.3 μm or less, and particularly preferably 0.2 μm or less. When the number average particle diameter exceeds 1 μm, the stability of the coating agent is remarkably deteriorated, and the performance such as moisture resistance and transparency of the coating film is deteriorated. The volume average particle size is preferably 2 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, from the viewpoint of performance such as the stability of the coating agent, moisture resistance, and transparency of the coating film. .3 μm or less is particularly preferable. Further, although there is no lower limit to the particle diameter, both the number average particle diameter and the volume average particle diameter in the dispersion achieved by various production methods described later are about 0.01 μm. In addition, the number average particle diameter and volume average particle diameter of the polyolefin resin are measured by a dynamic light scattering method generally used for measuring the particle diameter of fine particles.

  The method for producing the aqueous dispersion of natural wax is not particularly limited, and commercially available products such as EMUSTAR series of Nippon Seiki Co., Ltd. can be used. It can be manufactured by operation. For example, using natural wax, a basic compound, and an aqueous medium as raw materials, the production conditions are preferably while maintaining the temperature at 45 to 200 ° C, preferably 60 to 150 ° C, more preferably 80 to 120 ° C. Can sufficiently disperse the natural wax by continuing stirring until coarse particles disappear (for example, for 5 to 120 minutes), and then preferably cooling to 40 ° C. or lower with stirring to obtain a dispersion. it can. When the temperature in the tank is lower than 45 ° C., it is difficult to disperse the wax. A reaction in which the temperature in the tank exceeds 200 ° C. is not preferable because it is uneconomical.

  In the dispersion state of the aqueous dispersion of natural wax thus obtained, the number average particle diameter is preferably 0.5 μm or less from the viewpoint of the mixing property with the polyolefin resin, and the mixing stability, moisture resistance, From the point of transparency, 0.3 μm or less is more preferable, and 0.2 μm or less is most preferable. Here, the number average particle diameter of the wax is measured by a dynamic light scattering method which is generally used for measuring the particle diameter of the fine particles.

  There is no limitation on the method for producing the aqueous dispersion or aqueous solution of the conductive material. For example, the conductive polymer can be produced by an appropriate method depending on the type of the conductive material, such as an electrolytic polymerization method, a method using a catalyst, or a method using an oxidizing reagent. They can be selected, and their dispersion and solution are not limited, and commercially available products can also be used. For example, as a polypyrrole-based aqueous dispersion, there is PPY-12 manufactured by Maruhishi Oil Chemical Co., Ltd., and as a polyethylenedioxythiophene-based dispersion aqueous solution, there is Orgacon S-300 manufactured by Japan Agfa-Gevart. Similarly, for inorganic conductive materials, for example, tin oxide ultrafine particles can be obtained by hydrolyzing or thermally hydrolyzing metallic tin and tin compounds, by alkaline hydrolysis of acidic solutions containing tin ions, and by ion exchange of solutions containing tin ions. Any method such as ion exchange using a membrane or an ion exchange resin can be used, and the dispersion method is not limited. Commercially available products can also be used. For example, as the tin oxide ultrafine particle aqueous dispersion, EPS-6 manufactured by Yamanaka Chemical Industry Co., Ltd., and as the antimony-doped tin oxide ultrafine particle aqueous dispersion, manufactured by Ishihara Sangyo Co., Ltd. As SN100D, tin oxide-doped indium ultrafine particles, ITO manufactured by CI Kasei Co., Ltd. is available.

  The solid content concentration of each aqueous dispersion obtained as described above can be appropriately adjusted by distilling off the aqueous medium (including stripping), diluting with an aqueous medium, or the like. In addition, any of the above-described methods for producing an aqueous dispersion does not require a surfactant for dispersion of polyolefin resin or candelilla wax, but in the case of dispersion of paraffin wax, as necessary. , And may be used within a range not exceeding the total amount described above.

  Next, the obtained aqueous dispersions of polyolefin, natural wax, and conductive material are mixed. In mixing, a known liquid / liquid mixing apparatus may be used as appropriate. Since the aqueous dispersion of the polyolefin resin, the aqueous dispersion of natural wax, the aqueous dispersion of the conductive material or the aqueous solution is excellent in dispersion and mixing, an extremely short time and a simple mixing operation are sufficient. Further, after mixing, the solid content concentration can be adjusted by the same method as described above.

  The coating agent of the present invention is excellent in coating properties to various substrates, paper, synthetic paper, thermoplastic resin film, plastic product, steel plate, aluminum foil, wood, woven fabric, knitted fabric, non-woven fabric, gypsum board, It can be used for coating or impregnation on a wooden board or the like, and a moisture-proof and antistatic layer can be laminated by removing the liquid medium. Especially, it is preferable to use for paper, a synthetic paper, and a thermoplastic resin film.

  Examples of thermoplastic resin films include polyester resins such as PET, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and polyhydroxycarboxylic acids such as polyglycolic acid and polylactic acid. Biodegradable resins represented by aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate), polyamide resins such as Ny6, nylon 66, nylon 46, PP, polyethylene, ethylene-vinyl acetate Examples thereof include films made of thermoplastic resins such as polyolefin resins such as copolymers, polyimide resins, polyarylate resins or mixtures thereof, and laminates thereof, among which polyester, polyamide, polyethylene Ethylene - vinyl acetate copolymer, consisting of polypropylene film can be suitably used. These base films may be unstretched films or stretched films, and the production method is not limited. Moreover, although the thickness of a base film is not specifically limited, Usually, what is necessary is just to be the range of 1-500 micrometers. Furthermore, you may perform what is called in-line coating which apply | coats the water-proof moisture-proof coating agent of this invention to an unstretched film, and extends | stretches the coat film.

  The thermoplastic resin film is preferably subjected to corona discharge treatment. Further, silica, alumina or the like may be deposited, and a gas barrier coat layer such as an oxygen gas barrier layer may be laminated.

  The film obtained by laminating the composition of the present invention has a haze of 20% or less. The transparency of the composition layer varies depending on the ratio of the polyolefin resin, natural wax, and conductive material. However, for applications such as packaging materials, the haze of the film is more preferably 15% or less, and even more preferably 10% or less. .

  Paper can also be used as the substrate. Examples of the base paper include craft paper, liner paper, art paper, coated paper, and carton paper.

  Moreover, a synthetic paper can be used as a base material. The structure of the synthetic paper is not particularly limited. Therefore, it may be a single layer structure or a multilayer structure. As the multilayer structure, for example, a two-layer structure of a base material layer and a surface layer, a three-layer structure in which a surface layer exists on the front and back surfaces, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be exemplified. Moreover, each layer may contain the inorganic or organic filler, and does not need to contain it. A microporous synthetic paper having a large number of fine voids can also be used.

  The method of applying the coating agent of the present invention to the substrate is not particularly limited, but gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating. The brush coating method can be employed. What is necessary is just to determine suitably about the application quantity of a coating agent with a base material. In the present invention, when the substrate is a thermoplastic resin film, the thickness of the composition layer is desirably at least 0.1 μm in order to sufficiently improve the moisture resistance. From the viewpoint of moisture resistance, it is better that the thickness of the moisture-proof composition layer is thicker, but the feature of the present invention is that moisture resistance is exhibited even if the thickness of the composition layer is thin. Therefore, the coating agent of the present invention is used. Thus, moisture resistance can be improved while utilizing the characteristics of the substrate. Therefore, the thickness of the composition layer of the present invention is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, and particularly preferably 0.3 to 7 μm.

Also, if the base material is a paper, woven fabric, knitted fabric, non-woven fabric, or other coating agent soaked, the coating amount is difficult to evaluate in terms of thickness. May be in the range of 1 to 200 g / m ² .

  In expressing the moisture-proof performance of the coating agent of the present invention, the drying temperature is preferably 50 to 240 ° C, more preferably 60 to 200 ° C, and still more preferably 90 to 180 ° C. When the drying temperature is less than 50 ° C., the aqueous medium cannot be sufficiently volatilized, or it takes time to volatilize, and it becomes difficult to obtain a composition layer. On the other hand, when the drying temperature exceeds 240 ° C., heating is uneconomical and the moisture-proof performance tends to decrease.

  The processed product (film, paper, synthetic paper) treated with the coating agent of the present invention can be used for packaging, for example, those which dislike moisture and static electricity. Specifically, an IC (integrated circuit), a transistor, It can be used for packaging of electronic parts such as diodes and capacitors.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Various physical properties were measured or evaluated by the following methods.
(1) Acid value of polyolefin resin Measured according to JIS K5407. The unit is mgKOH / g. Moreover, the copolymerization amount (mass%) of the unsaturated carboxylic acid unit was computed from the acid value.
(2) Acid value and saponification value of natural wax These are values determined by titration with KOH according to JIS K-0070, and the unit is mgKOH / g.
(3) Structure of polyolefin resin other than unsaturated carboxylic acid unit ¹ H-NMR and ¹³ C-NMR analysis (manufactured by Varian, 300 MHz) was performed at 120 ° C. in orthodichlorobenzene (d ₄ ). ^{In 13} C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.
(4) Weight average molecular weight of polyolefin resin Calibration curve prepared with polystyrene standard sample by dissolving the sample in tetrahydrofuran using GPC analysis (HLC-8020 manufactured by Tosoh Corporation, column is TSK-GEL) and measuring at 40 ° C. From this, the weight average molecular weight was determined.
(5) Solid Concentration of Aqueous Dispersion An appropriate amount of an aqueous dispersion of polyolefin resin or natural wax was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight. %).
(6) Dispersed particle diameter For the dispersed particles of polyolefin resin or natural wax in the aqueous dispersion, a Microtrac particle size distribution analyzer UPA150 (manufactured by Nikkiso Co., Ltd., MODEL No. 9340) was used, and the number average particle diameter (mn), volume The average particle size (mv) was measured.
(7) Pot life of coating agent The appearance when the prepared coating agent was allowed to stand at room temperature for 90 days was evaluated in the following two stages.
○: Solidification and aggregation were not observed. ×: Solidification and aggregation were observed. In the following evaluations (8) to (11), as the biaxially stretched PET film, Embrit PET12 (thickness: 12 μm) manufactured by Unitika Co., Ltd. ) As a biaxially stretched Ny6 film, an emblem (thickness: 15 μm) manufactured by Unitika Ltd. was used.
(8) Haze Based on JIS-K7361-1, the haze measurement of the moisture-proof processed film was performed using a turbidimeter (Nippon Denshoku Industries Co., Ltd. make, NDH2000), and transparency was evaluated. However, this evaluation value includes the turbidity of the base film used in each example (biaxially stretched PET film: 3.6%, stretched Ny6 film: 3.1%).
(9) Water vapor transmission rate, water vapor transmission coefficient After coating a predetermined amount of coating agent using a film applicator (Yasuda Seiki Seisakusho, 542-AB) with a Mayer bar installed on the non-corona surface of various films. The composition layer was formed by drying at 100 ° C. for 2 minutes.
Next, the water vapor permeability of the processed film at 40 ° C. and 100% RH was measured by a moisture permeability measuring device (PERMATRAN-W3 / 31 MW) manufactured by Mocon Co., Ltd., and Q _F was obtained.
On the other hand, the water vapor permeability coefficient P _C of the composition layer is determined by the above-mentioned Q _F , the water vapor permeability Q _B of the base film, and the thickness L of the composition layer (based on JIS-K7130, a thickness meter (ND282 manufactured by HEIDENNHAIN). ) Was calculated from the average thickness difference between the processed film and the base film) based on the following relational expression. The Q _B of the PET film was 60 g / m ² · day, and the Q _B of the Ny6 film was 600 g / m ² · day.
1 / Q _F = 1 / Q _B + L / P _C
However, Q _F : Water vapor permeability of processed product (g / m ² · day)
Q _B : Water vapor permeability of the substrate (g / m ² · day)
P _C : Water vapor transmission coefficient of composition layer (g · μm / m ² · day)
L: Composition layer thickness (μm)
(10) Surface specific resistance value Based on JIS-K6911, using a digital ultrahigh resistance / microammeter, R8340 manufactured by Advantest Co., Ltd. Measured below.

(Production of polyolefin resin P-1)
280 g of propylene-butene-ethylene terpolymer (manufactured by Huls Japan Co., Ltd., Bestplast 708, propylene / butene / ethylene = 64.8 / 23.9 / 11.3% by mass) was added to a stirrer, a cooling tube, and dropwise. In a four-necked flask equipped with a funnel, the mixture was heated and melted in a nitrogen atmosphere, and the temperature in the system was kept at 165 ° C. While stirring, 32.0 g of maleic anhydride as an unsaturated carboxylic acid and dicumyl as a radical generator A solution of 6.0 g of peroxide in 20 g of heptane was added over 1 hour, followed by reaction for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain polyolefin resin P-1.

(Production of polyolefin resin P-2)
Polyolefin resin P-, except that propylene-butene-ethylene terpolymer (Hels Japan, Bestplast 408, propylene / butene / ethylene = 12.3 / 82.2 / 5.5% by mass) was used. A polyolefin resin P-2 was obtained in the same manner as in the production of 1.

(Production of polyolefin resin P-3)
Propylene-butene-ethylene terpolymer (manufactured by Huls Japan, Bestplast 708, propylene / butene / ethylene = 64.8 / 23.9 / 11.3% by mass) 100 g, 500 g of toluene, agitator, cooling In a four-necked flask equipped with a tube and a dropping funnel, after being heated and melted in a nitrogen atmosphere, a solution of 1.0 g of dicumyl peroxide as a radical generator and a 20 g solution of heptane was maintained while maintaining the system temperature at 110 ° C. Is added dropwise over 1 hour, and 7.0 g of maleic anhydride, 10.0 g of octyl acrylate, and 10 g of heptane of 0.5 g of dicumyl peroxide are added dropwise over 1 hour. Reacted for hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted substances, and then dried under reduced pressure in a vacuum dryer to obtain polyolefin resin P-3.

  Table 1 shows the characteristics of the polyolefin resins P-1 to P-3.

Reference example 1
(Preparation of aqueous polyolefin resin dispersion E-1)
60.0 g of polyolefin resin (P-1), 45.0 g of ethylene glycol-n-butyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 6 When 9 g of N, N-dimethylethanolamine (Wako Pure Chemical Industries, Ltd.) and 188.1 g of distilled water were charged into a glass container and stirred at a rotation speed of a stirring blade of 300 rpm, resin was precipitated at the bottom of the container. Was not observed and it was confirmed that it was floating. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky-yellow uniform polyolefin resin aqueous dispersion E-1 was obtained. There was almost no residual resin on the filter. Various characteristics of the aqueous dispersion are shown in Table 2.

Reference example 2
(Preparation of aqueous polyolefin resin dispersion E-2)
Using a stirrer equipped with a 1 L glass container that can be sealed with a heater, 60.0 g polyolefin resin (P-2), 90.0 g n-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), 7.8 g Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 142.2 g of distilled water were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm. It was confirmed that Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky-yellow uniform polyolefin resin aqueous dispersion E-2 was obtained. There was almost no residual resin on the filter. Various characteristics of the aqueous dispersion are shown in Table 2.

Reference example 3
(Preparation of aqueous polyolefin resin dispersion E-3)
Using P-3 as the polyolefin resin, a milky-yellow uniform polyolefin resin aqueous dispersion E-3 was obtained according to the method of Reference Example 2. Various characteristics of the aqueous dispersion are shown in Table 2.

Reference example 4
(Preparation of aqueous polyolefin resin dispersion E-4)
Except for adding 7 parts by mass of Neugen EA-190D (Daiichi Kogyo Seiyaku Co., Ltd., nonionic surfactant) as a surfactant with respect to 100 parts by mass of the solid content of the polyolefin resin when making the polyolefin resin aqueous. According to the method of Reference Example 1, a milky-yellow uniform polyolefin resin aqueous dispersion E-4 was obtained. Various characteristics of the aqueous dispersion are shown in Table 2.

Reference Example 5
(Preparation of aqueous polyolefin resin dispersion S-1)
An ethylene-acrylic acid ester-maleic anhydride copolymer {manufactured by Sumitomo Chemical Co., Bondine HX-8210, ethylene / ethyl acrylate / maleic anhydride = 91/6/3 (mass ratio)} was used as the polyolefin resin.
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g polyolefin resin (Bondaine HX-8210), 60.0 g isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.), 3.9 g N, N-dimethylethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 176.1 g of distilled water were charged into a glass container and stirred at a rotation speed of a stirring blade of 300 rpm. It was not recognized and it was confirmed that it was floating. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 60 minutes. Then, after cooling to room temperature (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion S-1 was obtained. Various characteristics of the aqueous dispersion are shown in Table 2.

Reference Example 6
(Preparation of aqueous polyolefin resin dispersion S-2)
As the polyolefin resin, an ethylene-acrylic acid copolymer {manufactured by Dow Chemical Company, Primacol 5980I, ethylene / acrylic acid = 80/20 (mass ratio)} was used.

  Using a stirrer equipped with a heat-resistant 1-liter glass container with a heater, 60.0 g of polyolefin resin (Primacol 5980I), 17.7 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and 222.3 g Distilled water was charged into a glass container and stirred at a rotational speed of the stirring blade of 300 rpm. As a result, precipitation of resin particles was not observed at the bottom of the container, and it was confirmed that it was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 60 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a slightly cloudy aqueous dispersion S-2 was obtained. Various characteristics of the aqueous dispersion are shown in Table 2.

  The properties of the polyolefin resin dispersions E-1 to 4 and S-1 to 2 are shown in Table 2.

Reference Example 7
(Preparation of candelilla wax dispersion W-1)
40.0 g of Candelilla wax (manufactured by Toa Kasei Co., Ltd., acid value: 15.8, saponification value: 55.4), 8 .8 g (2.0 times equivalent of the amount required for complete neutralization and saponification of wax) and 151.2 g of distilled water were charged in a glass container, and the stirring blade was rotated. When the speed was stirred at 400 rpm, no resin precipitation was observed at the bottom of the container, confirming that it was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 100 ° C. and further stirred for 10 minutes. Then, after cooling to room temperature (about 25 degreeC), stirring by air cooling with a rotational speed of 600 rpm, the pale yellow uniform wax aqueous dispersion W-1 was obtained. The solid content concentration was 20.0% by mass, and the number average particle size (mn) was 0.27 μm.
Reference Example 8

(Preparation of polyaniline aqueous solution A-1)
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 30 ml of water: acetonitrile 3: 7 solution of triethylamine at a concentration of 4 mol / L at 0 ° C., and cooled in 100 ml of water: acetonitrile 3: 7 solution containing 100 mmol of ammonium peroxodisulfate. It was dripped under. At this time, the dropping rate of the monomer solution was 100 mmol / hr, and the maximum temperature reached during the reaction of stirring power 0.7 Kw / m ³ was 15 ° C. when 0.5 equivalent of the monomer was dropped. Further, the pH in the reaction system was pH 3 at the start of dropping and pH 1.5 at the end of dropping, and the monomer dropping equivalent when the pH was 1.0 was 0.6 equivalent. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered with a centrifugal filter, washed with methyl alcohol and dried to obtain 17 g of polymer powder.

  5 parts by weight of the polymer was dissolved in 45 parts by weight of water with stirring at room temperature to obtain an aqueous polyaniline solution A-1.

Example 1
Polyolefin resin aqueous dispersion E-1, paraffin wax aqueous dispersion (manufactured by Nippon Seiki Co., Ltd., EMUSTAR-0135, containing anionic surfactant), polypyrrole aqueous dispersion (manufactured by Maruhishi Oil Chemical Co., Ltd., PPY-12) ) And 100/15/10 (solid content mass ratio) to obtain an aqueous coating agent J-1. The pot life of the aqueous coating agent J-1 and a predetermined amount of J-1 were applied to each base film and dried, and then evaluated for moisture resistance, antistatic performance, film thickness, and transparency. .

Examples 2-5
In the preparation of the aqueous coating agent, the ratios of polyolefin resin, natural wax, and polypyrrole are 100/15/15, 100/15/8, 100/30/15, and 100/10/10 (solid content mass ratio). Aqueous coating agents J-2 (Example 2), J-3 (Example 3), J-4 (Example 4), and J-5 (Example 5) were carried out in the same manner as Example 1 except that they were blended. It was prepared and various physical properties were evaluated.

Examples 6-8
In preparing the aqueous coating agent, aqueous coating agents J-6 to J-8 were prepared in the same manner as in Example 1 except that E-2 to E-4 were used as the aqueous polyolefin resin dispersion, and various physical properties were evaluated. Went.

Example 9
In the preparation of the aqueous coating agent, an aqueous coating agent J-9 was prepared in the same manner as in Example 1 except that the natural wax aqueous dispersion W-1 was used as the wax dispersion, and various physical properties were evaluated.

Example 10
In the preparation of the aqueous coating agent, a polyethylenedioxythiophene aqueous dispersion (Orgacon S-300 manufactured by Agfa Gebalto, Japan) was used as the conductive material aqueous dispersion, and the polyolefin resin, natural wax, polyethylenedioxythiophene An aqueous coating agent J-10 was prepared in the same manner as in Example 1 except that the ratio was 100/15 / 2.5 (solid content mass ratio), and various physical properties were evaluated.

Example 11
In the preparation of the aqueous coating agent, the polyaniline aqueous solution A-1 was used as the conductive material water dispersion, and the ratio of the polyolefin resin, natural wax, and polyaniline was 100/15/20 (solid content mass ratio). Produced an aqueous coating agent J-11 in the same manner as in Example 1 and evaluated various physical properties.

  The results of Examples 1 to 11 are shown in Table 3.

Comparative Example 1
In the preparation of the aqueous coating agent, the candelilla wax dispersion W-1 and the conductive material dispersion were not added. That is, various physical properties were evaluated using the polyolefin resin aqueous dispersion E-1 alone.

Comparative Examples 2 and 3
In the preparation of the aqueous coating agent, the ratios of polyolefin resin, candelilla wax, and conductive material are 100/15 / 0.5 (Comparative Example 2) and 100/1/15 (Comparative Example 3) (solid content mass ratio). Aqueous coating agents H-2 and H-3 were prepared in the same manner as in Example 1 except that they were blended, and various physical properties were evaluated.

Comparative Examples 4 and 5
In the preparation of the aqueous moisture-proof coating agent, the same procedure as in Example 1 was conducted except that S-1 (Comparative Example 4) and S-2 (Comparative Example 5) were used as aqueous polyolefin resin dispersions other than the polyolefin resin having a specific composition. Aqueous coating agents H-4 and H-5 were prepared and various physical properties were evaluated.

Comparative Example 6
In the preparation of the aqueous coating agent, an aqueous coating agent was used in the same manner as in Example 1 except that a polyethylene wax aqueous dispersion (manufactured by Nippon Seiki Co., Ltd., EMUSTAR-0443, containing an anionic surfactant) was used as the wax dispersion. H-6 was produced and various physical properties were evaluated.

Comparative Example 7
In the preparation of the aqueous coating agent, NeoRez R-972 (manufactured by Enomoto Kasei Co., Ltd., acrylic resin aqueous dispersion, solid content concentration: 42.0% by mass) diluted twice with water is used as the aqueous resin dispersion. A water-based coating agent H-7 was produced in the same manner as in Example 1 except that the physical properties were evaluated.

  The results of Comparative Examples 1-7 are shown in Table 4.

  In Examples 1 to 11, a film excellent in moisture resistance and antistatic performance was obtained regardless of the type of base film, and the pot life of each coating agent used at this time was good. When the addition amount of the conductive material was large, the tendency to improve the antistatic performance was recognized (Example 2), and when the addition amount of the conductive material was small, the tendency to decrease the antistatic performance was recognized (Example 3). On the other hand, if the addition amount of the wax was within the range of the present invention, no significant difference was observed in the moisture-proof performance (Examples 4 and 5). Moreover, the tendency for moisture-proof property to fall a little under the influence of surfactant used in the case of water-izing of polyolefin resin was recognized (Example 8).

  In contrast, Comparative Example 1 did not express moisture resistance and antistatic performance because it did not contain wax and conductive material. In Comparative Example 2, since the amount of the conductive material added was outside the range of the present invention, the moisture resistance was good, but the antistatic performance was poor. In Comparative Example 3, since the addition amount of the wax was outside the range of the present invention, the antistatic performance was good but the moisture resistance was inferior and the haze was high. In Comparative Examples 4 and 5, since the polyolefin resin was outside the scope of the present invention, moisture resistance was hardly exhibited. In Comparative Example 6, since the used wax was different from the natural wax defined in the present invention, the moisture resistance was inferior. In Comparative Example 7, since an acrylic resin outside the scope of the present invention was used as the resin, the moisture resistance was inferior and haze was high.

Claims (9)

Including polyolefin resin an unsaturated carboxylic acid unit, natural wax, a coating agent made of a conductive material and an aqueous medium, the polyolefin resin is a propylene component comprises a butene component and an ethylene component, a propylene component, butene component and an ethylene component When the total of 100 parts by mass is included, the propylene component is 9.5 to 90 parts by mass, the butene component is 9.5 to 90 parts by mass, the ethylene component is 0.5 to 40 parts by mass, and the polyolefin resin is 100% by mass. It becomes Nde 0.5 to 10 wt% containing an unsaturated carboxylic acid unit, a polyolefin resin 100 mass parts per in the coating agent, a natural wax and 1 to 100 parts by weight of the conductive material of 5 to 200 parts by containing relative A coating agent characterized by The coating agent according to claim 1 , wherein the conductive material is a conductive polymer. According to claim 1 or 2 composition obtained by removing the liquid medium from the composition according. The composition according to claim 3 , wherein the water vapor transmission coefficient at 40 ° C. and 100% RH is 200 g · μm / m ² / day or less. The composition according to claim 3 , wherein the surface specific resistance value at 20 ° C. and 60% RH is less than 10 ¹¹ Ω / □. A processed product obtained by providing the composition according to claim 3 on a substrate. The processed product according to claim 6, wherein the substrate is paper or synthetic paper. A film obtained by laminating a layer of the composition according to claim 3 on at least one surface of a thermoplastic resin film. The film according to claim 8 , wherein the haze is 20% or less.