JP2007327043A - Transparent non-antistatic polymer resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent non-antistatic polymer resin having sufficient mechanical strength as a packing material, etc. and having ≥10<SP>-11</SP>S/cm electric conductivity. <P>SOLUTION: A bicontinuous structure in which mutual phase separation between a transparent non-conductive polymer phase 2a and an ion-conductive polymer phase 3a in which electrolytic salt is dissolved is carried out is formed and a three-dimensional network structure is formed over whole resin by respective polymer phases to produce the transparent non-antistatic polymer 1a. The transparent non-antistatic polymer resin 1a has both of the properties result from transparency and mechanical properties of the transparent non-conductive polymer phase 2a and a property result from conductivity of the ion-conductive polymer phase 3a by the above bicontinuous structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a transparent and non-chargeable polymer resin material used for a packing material for protecting a product to be packed from static electricity.

Since the polymer resin material is a dielectric, it is charged by the generation of static electricity. For this reason, when electronic parts are packed with packing materials made of ordinary polymer resin material, the voltage exceeding the rating is applied to the packaged product due to the influence of static electricity, and the electronic parts that are unpacked products malfunction. Or destroy it. Therefore, a special polymer resin material that prevents charging of the packing material itself is used as a packing polymer resin material used for packing electronic parts and the like that need to be protected from static electricity. As such a polymer resin material, there have conventionally been a polymer resin material in which a metal thin film is coated on the front and back surfaces of a polymer resin film or a conductive resin material such as carbon black or metal powder is mixed (Non-Patent Document 1). reference).
Supervised by Kiyoshi Akamatsu, “Technology and Application of Antistatic Materials”, CM Publishing, 2002, p. 87-100

  However, in the case of a packing material in which a metal thin film is coated on the front and back surfaces of a polymer resin film, charges may be accumulated between the front and back metal thin films formed on the packing material. In addition, it is not desirable to form a metal thin film on the packaging material because the manufacturing cost increases.

By adding a small amount of a conductive substance such as carbon black or metal powder to the polymer resin material, the conductivity of the polymer resin material can be increased to a conductivity of about 10 ⁻² S / cm, which is sufficient for preventing charging. However, since the conductive substance in this kind of polymer resin material is simply held in the resin, there is a possibility that the conductive substance such as carbon black adheres to the packaged product during transportation of the packed product. There is a problem that there is.

  In addition, since these conventional non-charged polymer resin materials imparted with conductivity are all non-transparent, if the packaged product is packed with these resin films, the packaged product cannot be identified. There is a problem that the product must always be unpacked and inspected.

Transparent and antistatic polymer resin materials have also been developed. However, the electrical conductivity of the conventional transparent non-chargeable polymer resin material is 10 ⁻¹² S / cm or less. Therefore, it did not have a sufficient antistatic effect. In order to exhibit a sufficient antistatic effect, it is desirable that the conductivity of the polymer resin material is 10 ⁻¹¹ S / cm or more.

FIG. 12 is a schematic cross-sectional view of a conventional transparent non-chargeable polymer resin. The conventional transparent non-chargeable polymer resin 1b has a so-called sea-island structure as shown in FIG. That is, the ion-conductive polymer phase 3b which is an isolated island-like lump is formed in the transparent non-conductive polymer phase 2b having a three-dimensionally continuous network structure. The transparent non-chargeable polymer resin 1b is transparent because the transparent non-conductive polymer phase 2b having a relatively high mechanical strength forms a continuous three-dimensional network structure over the entire transparent non-chargeable polymer resin 1b. In addition, it has excellent mechanical properties. However, even if the ion conductive polymer phase 3b is finely dispersed uniformly, the electrical conduction always passes through the transparent non-conductive polymer phase 2b having an extremely low conductivity, so that the conductivity of the entire polymer resin material is 10%. It was difficult to set it to ^-11 S / cm or more. In addition, it is possible to produce a polymer resin in which the ion conductive polymer phase 3b is made into a continuous three-dimensional network structure and the transparent non-conductive polymer phase 2b is dispersed as an island-like lump. The mechanical strength is insufficient in practical use because the mechanical strength of the ion conductive resin phase 3b is low.

The present invention solves the above-mentioned conventional problems, has a conductivity of 10 ⁻¹¹ S / cm or more, has a sufficient non-charging effect, is transparent, and is a sufficient machine as a packaging material or the like. It is an object to provide a polymer resin material having sufficient strength and a method for producing the film.

In order to solve the above-mentioned problems, the transparent non-chargeable polymer resin material of the invention described in claim 1 is a polymer resin material comprising a mixture of an ion conductive polymer phase and a transparent non-conductive polymer phase that are phase-separated from each other. The electrolyte salt is dissolved in the ion conductive polymer phase, the ion conductive polymer phase and the transparent non-conductive polymer phase form a co-continuous structure, and each polymer phase is the entire polymer resin material. A three-dimensionally continuous network structure, an average transmittance of visible light in the wavelength range of 400 nm to 800 nm is 50% or more, and a DC conductivity at room temperature of 10 ⁻¹¹ S / Cm or more. Here, the co-continuous structure refers to a polymer phase mixed structure in which each polymer phase forms a three-dimensionally continuous network structure in a polymer resin material composed of a mixture of a plurality of phase-separated polymer phases. It is.

  According to the first aspect of the present invention, since the transparent non-conductive polymer phase and the ion conductive polymer phase form a co-continuous structure, each of the transparent non-conductive polymer phase and the ion conductive polymer phase. Forms a three-dimensionally continuous network structure throughout the polymer resin material. Therefore, due to the action of the transparent non-conductive polymer phase, the transparency of the entire polymer resin and the mechanical strength sufficient for practical use as a packaging material and the like are ensured. At the same time, the electrical conduction path of the polymer resin does not use the transparent non-conductive polymer phase with low conductivity as the electrical conduction path, and forms a network structure throughout the polymer resin material. Consists only of the sex polymer phase. As a result, the polymer resin material is transparent as a whole, and the transparent non-chargeable polymer resin material has a non-charge property sufficient to protect a packaged product such as an electronic component from static electricity with a relatively high conductivity. .

The transparent non-chargeable polymer resin material according to claim 2 is the transparent non-chargeable polymer resin according to claim 1, wherein the ion conductive polymer phase is made of polyethylene glycol methacrylate represented by the formula (1). The electrolyte salt is Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and at least one cation of ionic liquid and ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ SO _{3. ^{-, NO 3 -, Cl -}} , Br -, I -, n (RSO 2) 2 - and ^{_{C (RSO 2) 3 - (}} R is, -CF _3, or, - at (CF _{2) n} CF _3, It consists of at least one or more types of anions selected from n ≧ 1).

  According to the second aspect of the present invention, the conductivity of the ion conductive polymer phase is improved by the action of the electrolyte salt dissolved in the polyethylene glycol methacrylate represented by the formula (1) which becomes the ion conductive polymer phase. . As a result, combined with the above-described co-continuous structure, the conductivity of the entire polymer resin material is improved.

  A transparent non-chargeable polymer resin material according to a third aspect of the present invention is the transparent non-chargeable polymer resin according to the second aspect, wherein the transparent non-conductive polymer phase is made of polymethyl methacrylate. .

  According to the invention described in claim 3, the entire polymer resin material has a relatively high mechanical strength and becomes transparent by the action of polymethyl methacrylate.

  The transparent non-chargeable polymer resin material according to claim 4 is the transparent non-chargeable polymer resin according to claim 3, wherein R of the polyethylene glycol methacrylate is H and n is 9 or less. And

The transparent non-chargeable polymer resin material according to claim 5 is the transparent non-chargeable polymer resin according to claim 3, wherein R of the polyethylene glycol methacrylate is CH ₃ and n is 7.8 or less. It is characterized by that.

  According to the invention described in claim 4 and claim 5, even when the ratio of the ion conductive polymer phase of the polymer resin material is relatively low, the polymer resin material as a whole is transparent and relatively high conductivity is obtained. It is done.

  The transparent non-chargeable polymer resin material according to claim 6 is the transparent non-chargeable polymer resin according to claim 2, wherein the transparent non-conductive polymer phase is made of a styrene acrylonitrile random copolymer. To

  The transparent non-chargeable polymer resin material according to claim 7 is the transparent non-chargeable polymer resin according to claim 2, wherein the transparent non-conductive polymer phase is made of amorphous polylactic acid. To

  According to the inventions described in claims 6 and 7, even when the ratio of the ion conductive polymer phase of the polymer resin material is relatively low, the conductivity of the polymer resin material as a whole can be made relatively high. As a result, the non-charging property of the polymer resin material is improved.

In the method for producing a transparent non-chargeable polymer resin according to claim 8, the average transmittance of visible light in the wavelength range of 400 nm to 800 nm is 50% or more, and the DC conductivity at room temperature is 10 ⁻¹¹ S / A method for producing a transparent non-chargeable polymer resin having a size of cm or more, wherein a solvent in which polymethyl methacrylate or styrene acrylonitrile random copolymer is dissolved, a solvent in which polymethyl methacrylate or styrene acrylonitrile polymer is dissolved, Li ⁺ , At least one cation selected from Na ⁺ , K ⁺ , NH ₄ ⁺ and ionic liquid and ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ⁻ , NO ₃ ⁻ , Cl ^{− , Br -, I -, N} (RSO 2) 2 - and ^{_{C (RSO 2) 3 - (}} R is, -CF _3, or, - (CF _{2) A} slurry is prepared by mixing a liquid composed of an ethylene glycol methacrylate monomer in which an electrolyte salt composed of at least one anion of _n CF ₃ and n ≧ 1) is dissolved, and the slurry is cast on a substrate. And heating to dissipate the solvent and polymerize the ethylene glycol methacrylate monomers.

The method for producing a transparent non-chargeable polymer resin according to claim 9 has an average transmittance of visible light in the wavelength range of 400 nm to 800 nm of 50% or more, and a DC conductivity at room temperature of 10 ⁻¹¹ S / A method for producing a transparent non-chargeable polymer resin having a size of cm or more, comprising a solvent in which polymethyl methacrylate or styrene acrylonitrile random copolymer is dissolved, and a monomer of ethylene glycol methacrylate in which NaClO ₄ or KClO ₄ is dissolved To prepare a slurry, cast this slurry on a substrate, and at a temperature of 100 ° C. or higher and 160 ° C. or lower, or by adding a radical polymerization accelerator at a temperature of 40 ° C. or higher and 160 ° C. or lower. Heating dissipates the solvent and superimposes the ethylene glycol methacrylate monomer. Characterized by

  According to invention of Claim 8 and Claim 9, the transparent nonelectroconductive polymer phase which consists of polymethyl methacrylate or a styrene acrylonitrile random copolymer, and the ion conductive polymer phase which consists of polyethyleneglycol methacrylate mutually phase-separated. As well as forming a mixture of states, each polymer phase forms a network structure that is three-dimensionally continuous throughout the polymer resin material. As a result, it is possible to produce a transparent non-chargeable polymer resin material that is transparent and has sufficient mechanical strength as a packaging material or the like and has a higher electrical conductivity than the conventional transparent non-chargeable polymer resin 1b.

The method for producing a transparent antistatic polymer resin of the invention described in claim 10 is the average transmittance of visible light in the wavelength range of 800nm from 400nm is 50% or more, the DC conductivity at room temperature ^{10 -11} S / A method for producing a transparent non-chargeable polymer resin having a size of at least cm, wherein a solution made of an ethylene glycol methacrylate monomer in which NaClO ₄ or KClO ₄ is dissolved in a solvent in which polylactic acid is dissolved is added to a base material. Casting and heating at a temperature of 100 ° C. or higher and 160 ° C. or lower, or adding a radical polymerization accelerator and heating at a temperature of 40 ° C. or higher and 160 ° C. or lower, to dissipate the solvent, The ethylene glycol methacrylate monomer is polymerized, and further quenched after heat treatment at a temperature of 170 ° C. or higher. It is characterized in that the re-lactic acid is made amorphous.

  According to the invention described in claim 10, the polylactic acid is made amorphous and transparent by performing a heat treatment that is rapidly cooled by a rapid cooling after the heat treatment at an amorphous temperature of 170 ° C. or more, A transparent non-chargeable polymer resin can be produced.

According to the present invention, it is possible to produce a resin having a conductivity higher than that of a conventional transparent non-chargeable polymer resin while being transparent, and having a conductivity of 10 ⁻¹¹ S / cm or more. The packaged product can be effectively protected from static electricity. Moreover, since it is transparent at the same time, it is possible to identify the packaged product in a packed state, so that it is not necessary to unpack the product in customs inspection.

  Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to FIGS. FIG. 1 is a schematic cross-sectional view of a transparent non-chargeable polymer resin according to the present invention. As shown in FIG. 1, a transparent non-chargeable polymer resin 1a according to the present invention is a polymer resin material composed of a mixed polymer in which a transparent non-conductive polymer phase 2a and an ion-conductive polymer phase 3a that are phase-separated from each other are mixed. . An electrolyte salt is dissolved in the ion conductive polymer phase 3a. The ion conductive polymer phase 3a is a polymer phase having high conductivity because electrolyte ions act as carriers for electric conduction.

  In the transparent non-chargeable polymer resin 1a of the present embodiment shown in FIG. 1, each of the transparent non-conductive polymer phase 2a and the ion conductive polymer phase 3a is continuously connected in a three-dimensional manner throughout the entire polymer resin material. The network structure is formed. The network structure of each polymer phase, which is continuously connected in a three-dimensional manner throughout such a polymer resin material, is single or plural. A polymer phase that is an isolated island-like lump like the sea-island structure shown in FIG. 12 may exist in any of the transparent non-conductive polymer phase 2a and the ion-conductive polymer phase 3a. Not necessary but not necessary. Since FIG. 1 is a cross section of the transparent non-chargeable polymer resin 1a, there are portions that appear to be separated in the respective polymer phases of the transparent non-conductive polymer phase 2a and the ion conductive polymer phase 3a. The polymer phase is a part of the three-dimensional network structure described above. Therefore, the transparent non-conductive polymer phase 2a and the ion conductive polymer phase 3a form the above-described co-continuous structure.

The transparent non-chargeable polymer resin 1a of the present embodiment has a visible wavelength range of 400 nm to 800 nm because the transparent non-conductive polymer phase 2a and the ion conductive polymer phase 3a form a very fine co-continuous structure. The average light transmittance is 50% or more, and the DC conductivity at room temperature is 10 ⁻¹¹ S / cm or more. In the transparent non-chargeable polymer resin 1a of the present embodiment, the relative relationship between the transparent non-conductive polymer phase 2a and the ion-conductive polymer phase 3a is realized so as to realize such an extremely fine co-continuous structure and to exhibit the above characteristics. The specific weight ratio is determined.

The transparent non-conductive polymer phase 2a has a sufficiently high average transmittance of visible light having a wavelength of 400 nm to 800 nm. The conductivity of the transparent non-conductive polymer phase 2a is extremely low, and the conductivity is 10 ⁻¹² S / cm or less. The transparent non-conductive polymer phase 2a has a relatively high mechanical strength. Examples of polymer materials constituting the transparent non-conductive polymer phase 2a include polymethyl methacrylate (hereinafter referred to as “PMMA”) represented by the formula (2), and a styrene acrylonitrile random copolymer represented by the formula (3) (hereinafter referred to as “polymethyl methacrylate”). "SAN"), polylactic acid represented by the formula (4) (hereinafter referred to as "PLLA"), and the like. The electrical conductivity of these polymer materials at room temperature is 10 ⁻¹² S / cm or less, and the average transmittance of visible light having a wavelength of 400 nm to 800 nm is 85% or more.

The ion conductive polymer phase 3a is composed of an electrolyte salt serving as an ion conductive carrier and a polymer material dissolving the electrolyte salt. Examples of the electrolyte salt include Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and at least one cation of an ionic liquid cation, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ^{−. _{, CF 3 SO 3 -, NO}} 3 -, Cl -, Br -, I -, N (RSO 2) 2 - and ^{_{C (RSO 2) 3 - (}} R is, -CF _3, or, - (CF _{2) An} electrolyte salt composed of at least one anion of _n CF ₃ and n ≧ 1) can be used. Among these, an ionic liquid that can be used as a cation includes a compound ion represented by the following formulas (5) to (12) (wherein R is a hydrogen atom, or a substituted or unsubstituted hydrocarbon). Group).

(In the formula, n is an integer of 1 or more.)

As a specific example of the ionic liquid type cation represented by the formula (5), a cation of 1-ethyl-3-methylimidazolium BF ₄ salt (EImBF ₄ ) which is the ionic liquid represented by the formula (6) Ions.

  The ion conductive polymer phase 3a is made of a polymer material that dissolves the electrolyte salt. An example of such a polymer material is polyethylene glycol methacrylate (hereinafter referred to as “PMEO”) represented by the formula (1).

R, which is a terminal group of the side chain of PMEO represented by the formula (1), is H or CH ₃ . When R is H, n corresponding to the side chain length is preferably 9 or less. When R is CH ₃ , n is preferably 7.8 or less. This is because the smaller the n, the lower the conductivity of the transparent non-chargeable polymer resin 1a that constitutes PMEO as the ion conductive polymer phase 2a. Here, the value of n corresponding to the length of the side chain of PMEO is a value obtained by measurement for the PMEO polymer obtained after the polymerization, and is an average value for each PMEO polymer.

Among the electrolyte salts described above, an electrolyte salt that is particularly desirable as a constituent of the ion conductive polymer phase of the present invention is one that is not soluble in water that can be dissolved in the polymer resin and can reduce its hygroscopicity. For example, KClO ₄ is an electrolyte salt that is relatively insoluble in water, but dissolves relatively well in PMEO represented by the above formula (1) and dissolves more in water than in water. KClO ₄ is also dissolved in ethylene glycol methacrylate (hereinafter referred to as “MEO ₈ ”) represented by Formula (13), which is a monomer of PMEO.

  In the entire transparent non-chargeable polymer resin 1a shown in FIG. 1, the transparent non-conductive polymer phase 2a forms a three-dimensionally continuous network structure as described above. The transparent non-conductive polymer phase 2a is transparent due to the inherent properties of being transparent and excellent in mechanical strength and the structure of the transparent non-conductive polymer phase 2a in the transparent non-chargeable polymer resin 1a. The non-chargeable polymer resin 1a has an average transmittance of visible light having a wavelength of 400 nm to 800 nm of 50% or more.

The conductivity of the transparent non-chargeable polymer resin 1a is determined by the conductivity of the ion conductive polymer phase 3a forming a three-dimensionally continuous network structure throughout the interior. That is, the main electrical conduction of the transparent non-chargeable polymer resin 1a passes only through the ion conductive polymer phase 3a having a relatively high conductivity without passing through the transparent non-conductive polymer phase 2a having a low conductivity. Is. Therefore, like the conventional antistatic polymer material shown in FIG. 12, the electrical conductivity of the entire electrically conductive polymer material through the transparent non-chargeable polymer resin 1a having a low electrical conductivity interposed between the ion conductive polymer phases 3a. The contribution to is negligible. As a result, the conductivity of the transparent non-chargeable polymer resin 1a can be made higher than that of the transparent non-chargeable polymer resin 1b having the conventional sea-island structure shown in FIG. The conductivity of the transparent non-chargeable polymer resin 1a of the present invention is 10 ⁻¹¹ S / cm or more. When the transparent non-chargeable polymer resin 1a having a conductivity of 10 ⁻¹¹ S / cm or more is used as a packaging material, the packaged product can be protected from static electricity.

  Hereinafter, a method for producing the transparent non-chargeable polymer resin 1a of the present embodiment will be described. 2A to 2D are diagrams showing an outline of a method for producing a transparent non-chargeable polymer resin of the present embodiment. In the method of manufacturing the transparent non-chargeable polymer 1a of the present embodiment, PMMA represented by the formula (1) is used as the material for the transparent non-conductive polymer phase 2a, and the formula (9) is used as the material for the ion-conductive polymer phase 3a. An example of using PMEO represented by the following will be described.

When the ion conductive polymer phase 3a is composed of PMEO represented by the formula (1), first, as shown in FIG. 2 (a), the solution 11 in which PMMA is dissolved in the solvent 11 has the formula (11) which is a monomer of PMEO. A solution 12 in which the electrolyte salt is dissolved is added to the MEO ₈ shown. Here, the electrolyte salt includes Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and at least one cation of the ionic liquid represented by the formulas (5) to (12), ClO ₄ ⁻ , BF ₄ ^{−. _{, PF 6 -, AsF 6 -}} , CF 3 SO 3 -, NO 3 -, Cl -, Br -, I -, N (RSO 2) 2 - and ^{_{C (RSO 2) 3 - (}} R is, -CF ₃ Or — (CF ₂ ) _n CF ₃ and n ≧ 1) of at least one anion. As a solvent for dissolving PMMA, chloroform, acetone, benzene, chlorobenzene, chlorohexane, dioxane, methylene chloride, xylene and the like can be used.

Next, as shown in FIG. 2 (b), the mixed solution of the solution 11 and the solution 12 is sufficiently mixed by the stirrer 14a, and the PMMA contained therein and the MEO ₈ in which the electrolyte salt is dissolved are uniform. Slurry 13 dispersed in Next, as shown in FIG. 2 (c), the slurry 13 is cast on a Teflon (registered trademark) plate 15 that is a substrate having a groove on the inside, and the surface is leveled with a squeegee 16.

As described above, the slurry 13 layer formed on the Teflon (registered trademark) plate 15 is heated to dissipate the solvent contained in the slurry 13 and to polymerize MEO ₈ molecules contained in the slurry 13. To form PMEO. As a result, the transparent non-conductive polymer phase 2a, the PMMA phase, and the ion-conductive polymer phase 3a, the PMEO phase, form a co-continuous mixture that is phase-separated from each other. A transparent non-chargeable polymer resin film 13a having a three-dimensionally continuous network structure is formed. The manufactured transparent non-chargeable polymer resin film 13a is easily peeled off from the Teflon (registered trademark) plate 15 (see FIG. 2D). The method for producing the transparent non-chargeable polymer resin 1a described above is not limited to the transparent non-chargeable polymer resin film 13a, but can be applied to the production of a case made of the transparent non-chargeable polymer resin 1a.

In the method for producing the transparent non-chargeable polymer resin 1a of the present embodiment described above, the weight ratio of PMMA and PMEO is appropriately selected within a range in which the produced polymer resin satisfies a predetermined condition. That is, the transparent non-conductive polymer phase 2a made of PMMA and the ion conductive polymer phase 3a made of PMEO form a very fine co-continuous structure, and the transparent non-charged polymer resin 1a has a visible light wavelength range of 400 nm to 800 nm. The weight ratio of PMMA and PMEO is selected in such a range that the average transmittance is 50% or more and the characteristic that the DC conductivity at room temperature is 10 ⁻¹¹ S / cm or more is developed. The range of the weight ratio varies depending on whether the end group R of PMEO is H or CH ₃ and the size of n corresponding to the length of the side chain.

  The transparent non-chargeable polymer resin 1a can be manufactured as follows. FIG. 3 is a diagram showing an example of a method for producing the transparent non-chargeable polymer resin film of the present embodiment. In this manufacturing method, the slurry 13 is manufactured in the same manner as described above. In the manufacturing method shown in FIG. 3, the slurry 13 in the container 14 is mixed by the stirrer 14 a and stretched on the cast roll 20 that rotates at a constant speed, and rotates in synchronization with the cast roll 20 and the cast roll 20. By the rotation of the feed roll 21, the pump 19 supplies the hopper 17 fixed in contact with the Teflon (registered trademark) belt 18 that is fed at a constant speed. Since the slurry 13 staying in the hopper 17 is in contact with the Teflon (registered trademark) belt 18, a part of the slurry 13 forms a layer having a predetermined thickness and is fed at a constant speed. Move up.

The slurry 13 transferred to the Teflon (registered trademark) belt 18 passes through a furnace 22 that holds a heater 22a and a duct 22b therein. While the solvent contained in the slurry 13 is dissipated in the furnace 22, the molecules of MEO ₈ contained in the slurry 13 are polymerized to form PMEO represented by the formula (9). As a result, a transparent non-chargeable polymer resin film 13 a is formed on the Teflon (registered trademark) belt 18. The transparent non-chargeable polymer resin film 13 a is cooled by the fan 24 and taken up by the take-up roll 23. The thickness of the transparent non-chargeable polymer resin film 13a manufactured in this manufacturing method is adjusted to a predetermined thickness by controlling the viscosity of the slurry 13 and the feed speed of the Teflon (registered trademark) belt 18. In this manufacturing method, it is necessary to make the viscosity of the slurry 13 constant in order to keep the thickness of the transparent non-chargeable polymer resin film 13a constant. Therefore, chlorobenzene or the like having a relatively high boiling point and less volatile is suitable as a solvent for dissolving PMMA.

  When SAN or PLLA is used as the material for the transparent non-conductive polymer phase 2a, the transparent non-chargeable resin 1a can be manufactured by the same manufacturing method. However, when PLLA is used as the material for the transparent non-conductive polymer phase 2a, the PLLA constituting the transparent non-conductive polymer phase 2a of the resin manufactured by the above-described manufacturing method is non-transparent and crystalline. Therefore, in order to make PLLA transparent and amorphous, it is necessary to rapidly cool the resin produced by the above production method at a temperature of 170 ° C. or higher, and then rapidly cool it.

Hereinafter, the present invention will be described in detail based on examples. As an example of the present invention, a transparent non-chargeable polymer resin 1a was prepared which was made of PMEO in which the transparent non-conductive polymer phase 2a was PMMA and KClO ₄ was uniformly dissolved in the ion-conductive polymer phase 3a. In addition, an ion conductive polymer phase 3a made of PMEO in which NaClO ₄ was uniformly dissolved instead of KClO ₄ was also produced. The transparent non-chargeable polymer resin 1a of the example was produced by the following steps.

The transparent non-chargeable polymer resin 1a of the example is manufactured as follows. First, a solution 11 shown in FIG. 2 is prepared by dissolving PMMA (Mw = 350,000) represented by the formula (2) in chloroform as a solvent. Further mixing at a rate of KClO ₄ 5 moles relative _MEO 8 100 moles of the formula (13), to prepare a solution 12 shown in FIG. 2 was dissolved KClO ₄ in MEO _8.

Next, the solution 12 is added to the solution 11 to make the slurry 13 shown in FIG. 2 containing KClO ₄ , MEO ₈ , PMMA, and chloroform, and mixed well with the stirrer 14a. The well-mixed slurry 13 is cast on a Teflon (registered trademark) plate 15 having a predetermined groove, and the surface is smoothed with a squeegee 6 (see FIG. 2C), and kept at 120 ° C. for 1 hour. Then, chloroform is dissipated and MEO ₈ is polymerized to form PMEO represented by the formula (9), and a film of a transparent non-chargeable polymer resin 1a having a predetermined thickness can be obtained. In this example, MEO ₈ was polymerized at 120 ° C., but this polymerization reaction proceeds if it is 100 ° C. or higher and 160 ° C. or lower. Moreover, in order to accelerate | stimulate superposition | polymerization, if radical polymerization promoter like azobisisobutyl nitrile (AIBN) is added, it can superpose | polymerize at the temperature of 40 to 160 degreeC. The weight ratio of PMMA and PMEO can be changed as appropriate. In the case where PMEO in which NaClO ₄ is uniformly dissolved is used instead of KClO ₄ , a film of the transparent non-chargeable polymer resin 1a is similarly produced.

The phase structure of the transparent non-chargeable polymer resin 1a manufactured by using the above-described manufacturing method and manufactured using PMMA and PMEO will be described below. FIG. 4 is a TEM photograph of the transparent non-chargeable polymer resin 1a of the example manufactured using PMMA and PMEO. In TEM observation, the sample thin film of this example is stained with iodine that is selectively adsorbed by PMMA. Therefore, in the TEM photograph of FIG. 4, the PMMA that is the transparent non-conductive polymer phase 2 a is a portion that looks black, and the white portion that is white is PMEO in which KClO ₄ that is the ion-conductive polymer phase 3 a is dissolved. R of the side chain of PMEO is H and n = 9. This transparent non-chargeable polymer resin 1a is prepared by polymerizing at 160 ° C. with a weight ratio of PMEO of 50%. The transparent non-chargeable polymer resin 1a has a conductivity of 1.2 × 10 ⁻¹¹ S / cm and an average visible light transmittance of 54%.

As can be seen from the TEM photograph in FIG. 4, the phases composed of PMMA and PMEO are phase-separated from each other. On the other hand, the width of each phase composed of PMMA and PMEO forms a fine polymer phase mixed structure that is about 100 nm shorter than the wavelength of visible light. This polymer phase mixed structure is not the sea-island structure of the conventional transparent non-chargeable polymer resin 1b shown in FIG. 12, but the polymer phase of the PMMA polymer phase and the PMEO polymer phase in which KClO ₄ is dissolved is apparently different from each other. A network structure that is three-dimensionally continuous is formed. These polymer phases form a very fine co-continuous structure. In the examples, such a very fine co-continuous structure was formed because the main chain structure of the PMMA polymer and the main chain structure of the PMEO polymer were the same, and thus the intermolecular affinity was relatively large. .

The measurement results of the characteristics of the transparent non-chargeable polymer resin 1a of the example manufactured using PMMA and PMEO will be described below with reference to FIGS. In the transparent non-chargeable polymer resin 1a of this embodiment, the weight ratio of PMMA and PMEO is 50:50, and KClO ₄ is dissolved in PMEO as an electrolyte salt. FIG. 5 is a diagram showing the measurement results of the transmissivity of the transparent non-chargeable polymer resin of the example manufactured using PMMA and PMEO. FIG. 6 and FIG. 7 are diagrams showing the results of measuring the DC conductivity and the results of measuring the AC conductivity of the transparent non-chargeable polymer resin of the example manufactured using PMMA and PMEO, respectively.

  As can be seen from FIG. 5, the film of the transparent non-chargeable polymer resin 1a of the present example having a thickness of 0.19 mm has a light transmittance of 90% or more in the visible light range of 400 nm to 800 nm. This transmittance, when used as a packaging material, is sufficient to identify a packaged product in a packaged state. Moreover, the transparent non-chargeable polymer resin 1a of the present embodiment has sufficient mechanical strength to be used as a packaging film material.

The measurement of DC conductivity and AC conductivity was performed using a sample having a thickness of 0.05 mm. The DC conductivity was measured by applying a DC voltage of 500 V to the sample film and measuring the flowing current. As can be seen from FIG. 6, the DC conductivity is maximized immediately after the voltage application and decreases with the influence of polarization with the lapse of time, but becomes substantially constant about 1 minute after the voltage application starts, and 2.1 × 10 ⁻⁸ S / cm. Since the direct current conductivity of PMMA itself is on the order of 10 ⁻¹⁴ S / cm, the direct current conductivity is 10 ⁶ times or more compared to PMMA.

The AC conductivity was measured by the AC complex impedance method in the frequency range from 100 Hz to 13 Mz. As can be seen from FIG. 7, the AC conductivity near room temperature is on the order of 10 ⁻⁸ S / cm, but the conductivity increases with increasing temperature. This is because the movement of K ⁺ and ClO ⁴⁻ , which are electrolyte ions dissolved in the ion conductive polymer phase 3a, is promoted by the thermal motion of the main chain of the ion conductive polymer phase 3a as the temperature rises. It is.

  The polymerization temperature, the side chain of PMEO, and the weight ratio of PMEO were changed by 50% or more, and the mixed polymer produced by using the production method of this embodiment using PMMA and PMEO, the conductivity at room temperature and the visible light The results of measuring the transmittance are shown in Table 1. Hereinafter, the value of conductivity is a measured value of the above-described DC conductivity.

Table 1 shows the results of measuring the electrical conductivity at room temperature and the average transmittance of visible light for the prepared mixed polymer using PMMA and PMEO having a weight ratio of 50% or more. Table 1 shows that in the case of a mixed polymer manufactured using the manufacturing method of the present embodiment using PMMA and PMEO, the average visible light transmittance was 50% or more regardless of the weight ratio of PMEO. Moreover, it turns out that electrical conductivity is dependent on the length n of the side chain of PMEO, and the weight ratio of PMEO. That is, the conductivity is higher when n is smaller and the weight ratio of PMEO is higher. When the weight ratio of PMEO is 50% or more, all are 10 ⁻¹¹ S / cm or more.

FIG. 8 is a diagram showing the conductivity measurement results of a co-continuous structure resin produced by changing the polymerization temperature using PMEO (NaClO ₄ dissolution) in which the end group R of the side chain is H and n = 9 and PMMA. . FIG. 8 shows the result of measuring the conductivity by changing the weight ratio of PMEO. The electrical conductivity becomes 10 ⁻¹¹ S / cm or more when the polymerization temperature is 100 ° C. and 130 ° C., and the weight ratio of PMEO is 40% or more, which corresponds to the embodiment of the present invention. . Further, when the polymerization temperature is 160 ° C., it corresponds to the example of the present invention when the weight ratio of PMEO is 50% or more.

FIG. 9 shows the results of measuring the conductivity of a co-continuous resin prepared at a polymerization temperature of 160 ° C. using PMEO (NaClO ₄ dissolution) in which the end group R of the side chain is H and n is changed to 9 or less and PMMA. FIG. FIG. 9 shows the results of measuring the electrical conductivity by changing the weight ratio of PMEO. FIG. 9 shows the results of measuring the electrical conductivity by changing the weight ratio of PMEO. The electrical conductivity corresponding to the embodiment of the present invention is 10 ⁻¹¹ S / cm or more when the weight ratio of PMEO is 60% or more when n is 9.0, 5.7, or 3.5, respectively. This is the case of 40% or more and 20% or more. Therefore, it is easier to lower the conductivity when n is smaller, that is, when the side chain of PMEO is shorter.

FIG. 10 shows a production method according to this embodiment using PMEO (n = 9.0) having a side chain terminal group R of H, PMEO having a side chain terminal group R of CH ₃ (7.8), and PMMA. It is a figure which shows the electrical conductivity measurement result of resin produced by this. FIG. 9 shows the results of measuring the electrical conductivity by changing the weight ratio of PMEO. The electrical conductivity corresponding to the example of the present invention is 10 ⁻¹¹ S / cm or more because when the end group R of the side chain of PMEO is H and n = 9.0, the weight ratio of PMEO is 60%. This is the case. On the other hand, when the end group R of the side chain of PMEO is CH ₃ and n = 7.8, the conductivity corresponding to the example of the present invention is 10 ⁻¹¹ S / cm or more because the weight ratio of PMEO is This is the case of 20% or more.

  Next, examples prepared using PLLA and SAN as polymer materials for the transparent non-conductive polymer phase 2a will be described. Table 2 shows the electrical conductivity at room temperature and the average transmittance of visible light of the mixed polymer produced by using the production method of the present embodiment using each of PLLA and SAN and PMEO having a weight ratio of 50% or more. It is a result.

The mixed polymer resin produced using PMEO and SAN with R = H in the side chain and n = 9 has a visible light transmittance of less than 50% and does not fall under the transparent non-chargeable polymer resin material of the present invention. . On the other hand, a mixed polymer resin prepared using PMEO and SAN having a side chain R of CH ₃ and n = 2, and a mixed polymer resin prepared using PMEO and PLLA having a side chain R of H and n = 9 are: The visible light transmittance is 50% or more, and the conductivity is sufficiently high, which corresponds to the transparent non-chargeable polymer resin material of the embodiment of the present invention. When PLLA and SAN are used as the polymer material for the transparent non-conductive polymer phase 2a, a transparent non-chargeable polymer resin material corresponding to the embodiment of the present invention is prepared by appropriately selecting R and n of the side chain of PMEO Is possible.

  As described above, the transparent non-chargeable polymer resin 1a of this example is transparent and has sufficient mechanical strength as a packaging film material. Moreover, compared with the conventional transparent non-chargeable polymer resin 1b (see FIG. 12), the conductivity is high and the non-charge effect is excellent.

  Embodiment of this invention is not limited to a present Example, Aspect can be changed in the range which is not contrary to the main point.

It is a cross-sectional schematic diagram of the transparent non-chargeable polymer resin concerning this invention. (A) thru | or (d) is a figure which shows the outline of the manufacturing method of the transparent non-chargeable polymer resin of a present Example. It is a figure which shows an example of the manufacturing method of the transparent non-chargeable polymer resin film of this embodiment. It is a TEM photograph of the transparent non-chargeable polymer resin of the Example manufactured using PMMA and PMEO. It is a figure which shows the measurement result of the light transmittance of the transparent non-chargeable polymer resin of the Example manufactured using PMMA and PMEO. It is a figure which shows the measurement result of the direct-current conductivity of the transparent non-chargeable polymer resin of the Example manufactured using PMMA and PMEO. It is a figure which shows the measurement result of the alternating current conductivity of the transparent non-chargeable polymer resin of the Example made by the manufacturing method of this embodiment using PMMA and PMEO. It is a figure which shows the electrical conductivity measurement result of resin produced by the manufacturing method of this embodiment, changing the polymerization temperature using PMEO and PMMA where the terminal group R of the side chain is H and n = 9. It is a figure which shows the electrical conductivity measurement result of resin produced by the manufacturing method of this embodiment at the polymerization temperature of 160 degreeC using PMEO and PMMA which changed the terminal group R of the side chain to H and n was 9 or less. . Terminal group R of the side chain is a diagram showing the conductivity measurements of the resin produced by the production method of this embodiment using each and PMMA of PMEO terminal group R is CH ₃ of PMEO and the side chain of H. It is a cross-sectional schematic diagram of the conventional transparent non-chargeable polymer resin.

Explanation of symbols

1a, 1b Transparent non-chargeable polymer resin 2a, 2b Transparent non-conductive polymer phase 3a, 3b Ion-conductive polymer phase 11 Solution (PMMA + solvent)
12 solution (electrolyte salt + MEO ₈ )
13 Slurry (electrolyte salt + MEO ₈ + PMMA + solvent)
13a Transparent uncharged polymer resin film 14a Stirrer 15 Teflon (registered trademark) plate 16 Squeegee

Claims (10)

A polymer resin material comprising a mixture of an ion conductive polymer phase and a transparent non-conductive polymer phase that are phase-separated from each other,
The electrolyte salt is dissolved in the ion conductive polymer phase;
The ion-conductive polymer phase and the transparent non-conductive polymer phase form a co-continuous structure, and each polymer phase forms a network structure that is three-dimensionally continuous throughout the polymer resin material;
The average transmittance of visible light in the wavelength range of 400 nm to 800 nm is 50% or more, and
A transparent non-chargeable polymer resin material having a DC conductivity at room temperature of 10 ⁻¹¹ S / cm or more. In the transparent non-chargeable polymer resin according to claim 1,
The ion conductive polymer phase is made of polyethylene glycol methacrylate represented by the formula (1),
The electrolyte salt is Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and at least one cation of an ionic liquid and ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ^{− _{, NO 3 -, Cl -,}} Br -, I -, n (RSO 2) 2 - and ^{_{C (RSO 2) 3 - (}} R is, -CF _3, or, - at _{(CF 2) n CF 3,} n A transparent non-chargeable polymer resin material comprising at least one anion selected from ≧ 1).
The transparent non-chargeable polymer resin according to claim 2,
A transparent non-chargeable polymer resin material, wherein the transparent non-conductive polymer phase is made of polymethyl methacrylate. The transparent non-chargeable polymer resin according to claim 3, wherein R of the polyethylene glycol methacrylate is H and n is 9 or less. The transparent non-chargeable polymer resin according to claim 3, wherein R of the polyethylene glycol methacrylate is CH ₃ and n is 7.8 or less. The transparent non-chargeable polymer resin according to claim 2,
A transparent non-chargeable polymer resin material, wherein the transparent non-conductive polymer phase is made of a styrene acrylonitrile random copolymer. The transparent non-chargeable polymer resin according to claim 2,
A transparent non-chargeable polymer resin material, wherein the transparent non-conductive polymer phase is made of amorphous polylactic acid. A method for producing a transparent non-chargeable polymer resin having an average transmittance of visible light in a wavelength range of 400 nm to 800 nm of 50% or more and a DC conductivity at room temperature of 10 ⁻¹¹ S / cm or more,
Solvent in which polymethyl methacrylate or styrene acrylonitrile random copolymer is dissolved and at least one cation of Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ and ionic liquid and ClO ₄ ⁻ , BF ₄ ⁻ , PF _{^{6 -, AsF 6 -, CF}} 3 SO 3 -, NO 3 -, Cl -, Br -, I -, N (RSO 2) 2 - and ^{_{C (RSO 2) 3 - (}} R is, -CF ₃ or, ,-(CF ₂ ) _n CF ₃ and a liquid made of an ethylene glycol methacrylate monomer in which an electrolyte salt composed of at least one anion of n ≧ 1) is dissolved to produce a slurry,
The slurry is cast on a substrate and heated to dissipate the solvent and to polymerize the ethylene glycol methacrylate monomers,
A method for producing a transparent non-chargeable polymer resin. A method for producing a transparent non-chargeable polymer resin having an average transmittance of visible light in a wavelength range of 400 nm to 800 nm of 50% or more and a DC conductivity at room temperature of 10 ⁻¹¹ S / cm or more,
A solvent in which polymethyl methacrylate or styrene acrylonitrile random copolymer is dissolved;
A slurry is prepared by mixing with a solution of ethylene glycol methacrylate monomer in which NaClO ₄ or KClO ₄ is dissolved,
The slurry is cast on a substrate, and the solvent is dissipated by heating at a temperature of 100 ° C. or higher and 160 ° C. or lower, or by adding a radical polymerization accelerator and heating at a temperature of 40 ° C. or higher and 160 ° C. or lower. And polymerizing the ethylene glycol methacrylate monomer with
A method for producing a transparent non-chargeable polymer resin film. A method for producing a transparent non-chargeable polymer resin having an average transmittance of visible light in a wavelength range of 400 nm to 800 nm of 50% or more and a DC conductivity at room temperature of 10 ⁻¹¹ S / cm or more,
Cast a mixture of a solution of ethylene glycol methacrylate dissolved in NaClO ₄ or KClO ₄ in a solvent in which polylactic acid is dissolved,
By heating at a temperature of 100 ° C. or higher and 160 ° C. or lower, or by adding a radical polymerization accelerator and heating at a temperature of 40 ° C. or higher and 160 ° C. or lower, the solvent is dissipated and the ethylene glycol Polymerizing a monomer of methacrylate and further quenching after heat treatment at a temperature of 170 ° C. or higher to make the polylactic acid amorphous;
A method for producing a transparent non-chargeable polymer resin film.