Patent Application
20210214492
The present invention relates to a surface-treated polymer production method, and a polymer, a metal-plated polymer, an adhesion laminate, and a metal-plated polymer, and production methods therefor.
In order to process the surface of polymer by plating, adhering, or the like, the polymer may be surface-treated (surface-altered) in advance. For example, in order for the surface of the polymer to be metal-plated, it has been proposed to introduce a surfactant on the surface of the polymer (plastic), remove the surfactant with supercritical carbon dioxide (high-pressure fluid), and then plate (Patent Literature 1). It has also been proposed to surface-treat a polymer with high-pressure carbon dioxide in the same manner and then plating (Patent Literature 2).
In adhesion of the polymer with an adherend, the polymer has been treated to enhance its adhesiveness in advance (e.g., Patent Literatures 3 and 4)
However, the methods of Patent Literatures 1 and 2 require high-pressure carbon dioxide, thereby lacking versatility.
Examples of the surface treatment (surface alteration) of the polymer include physical treatments such as a corona discharge treatment, a plasma discharge treatment, and a grafting treatment. However, these treatments involve problems of a complicated operation, treatment costs, and difficulty in reaction control. On the other hand, a chemical surface treatment includes a method using a heavy metal oxidizing agent. However, this method also involves problems of costs of the treatment with the heavy metal oxidizing agent. Further, both of the physical and chemical treatments involve a problem of versatility as in the treatments of Patent Literatures 1 and 2, and in particular, it is difficult to apply these treatments to bioplastics such as polylactic acid (PLA).
The method of Patent Literatures 3 and 4 uses a modified polymer. This method requires a specific treatment at the stage of polymer synthesis, and thus has a limitation in application range. For example, this method is not applicable to bioplastics such as polylactic acid (PLA). Other methods of enhancing the adhesiveness of the polymer include the surface alteration treatment, which involves the aforementioned problems.
Hence, the present invention is intended to provide a surface-treated polymer production method, a metal-plated polymer production method, and an adhesion laminate production method each of which can be performed in a simplified manner and at low cost, and provide a polymer, a metal-plated polymer, and an adhesion laminate each of which can be produced in a simplified manner and at low cost.
In order to achieve the aforementioned object, the surface-treated polymer production method according to the present invention includes: reacting a surface of a polymer with a halogen oxide radical to surface-treat the polymer, wherein in the surface-treating, a reaction system is not irradiated with light.
The polymer according to the present invention has an oxidized surface, and an amount of change X in contact angle with water represented by the following mathematical formula (1) of more than 0°,
X=A
0
−A (1)
A0: a contact angle of a non-oxidized surface of the polymer with water;
A: a contact angle of the oxidized surface of the polymer with water;
X: an amount of change in contact angle with water.
The metal-plated polymer production method according to the present invention includes: producing a surface-treated polymer by the surface-treated polymer production method according to the present invention; and plating a surface of the surface-treated polymer with a metal.
The adhesion laminate production method according to the present invention includes: producing a surface-treated polymer by the surface-treated polymer production method according to the present invention; and adhering an adherend to a surface of the surface-treated polymer.
The metal-plated polymer according to the present invention includes: the polymer according to the present invention, the polymer according to the present invention having a metal-plated surface.
The adhesion laminate according to the present invention includes: an adhesion laminate producing polymer of the polymer according to the present invention and an adherend; and the adherend adhered to a surface of the adhesion laminate producing polymer.
The present invention is intended to provide a surface-treated polymer production method, a metal-plated polymer production method, and an adhesion laminate production method each of which can be performed in a simplified manner and at low cost, and provide a polymer, a metal-plated polymer, and an adhesion laminate each of which can be produced in a simplified manner and at low cost.
The present invention will be described below in more detail with reference to illustrative examples. The present invention, however, is by no means limited thereby.
Herein, the method for producing a surface-treated polymer according to the present invention (surface-treated polymer production method according to the present invention) may be merely referred to as the “production method according to the present invention”. Hereinafter, unless otherwise stated, the “polymer according to the present invention”, and the “surface-treated polymer according to the present invention” are not limited to the polymer according to the present invention (the polymer having an oxidized surface, and an amount of change in contact angle with water of more than 0°, the amount of change X being represented by the mathematical formula (1)), and includes all polymers produced by the surface-treated polymer production method according to the present invention.
The method for producing a metal-plated polymer according to the present invention (metal-plated polymer production method according to the present invention) can also be referred to as a method for metal-plating the polymer (a metal-plating method of the polymer).
The method for producing an adhesion laminate of a polymer and an adherend according to the present invention (adhesion laminate production method according to the present invention) can also be referred to as a method for adhering the polymer to the adherend. The adherend may be, for example, a metal.
The use of the polymer according to the present invention is not particularly limited, and the polymer may be used as an adhesion laminate producing polymer of the metal-plated polymer or the polymer and the adherend. Herein, the polymer according to the present invention, for use in metal plating is also referred to as the “metal plating polymer according to the present invention” or the “metal plating polymer.” Further, hereinafter, the metal-plated polymer according to the present invention is also merely referred to as the “metal-plated polymer.” Herein, the polymer according to the present invention, for use in production of an adhesion laminate of a polymer and an adherend is also referred to as the “adhesion laminate producing polymer according to the present invention” or the “adhesion laminate producing polymer.” Further, herein, the adhesion laminate of a polymer and an adherend according to the present invention is also referred to as the “adhesion laminate according to the present invention” or merely the “adhesion laminate.”
In the present invention, the polymer can be altered by the surface-treating. Herein, the surface-treating may also be referred to as a “alteration treatment” or a “alternation method.” The surface-treating including oxidizing the polymer can be referred to as a method for oxidizing the polymer.
In the surface-treated polymer production method according to the present invention, the reaction system in the surface-treating may be, for example, either a gas reaction system or a liquid reaction system.
In the surface-treated polymer production method according to the present invention, the halogen oxide radical may be, for example, a chlorine dioxide radical.
In the present invention, an open chain compound (e.g., an alkane, an unsaturated aliphatic hydrocarbon) or a chain substituent derived from the open chain compound (e.g., an alkyl, a hydrocarbon group such as an unsaturated aliphatic hydrocarbon group) may be, for example, of a straight-chain or branched, and the carbon number is, as a non-limiting example, 1 to 40, 1 to 32, 1 to 24, 1 to 18. 1 to 12, 1 to 6, or 1 to 2, and in the case of the unsaturated hydrocarbon group, 2 to 40, 2 to 32, 2 to 24, 2 to 18, 2 to 12, or 2 to 6. In the present invention, the number of ring members (the number of atoms constituting the ring) of a cyclic compound (e.g., a cyclic saturated hydrocarbon, a non-aromatic cyclic unsaturated hydrocarbon, an aromatic hydrocarbon, a heteroaromatic compound) or a cyclic group derived from the cyclic compound (e.g., a cyclic saturated hydrocarbon group, a non-aromatic cyclic unsaturated hydrocarbon group, an aryl, a heteroaryl) is, as a non-limiting example, 5 to 32, 5 to 24, 6 to 18, 6 to 12, or 6 to 10. In addition, in the case in which the substituent has an isomer thereof, the particular isomer is included without being mentioned specifically, as a non-limiting specific example, a 1-naphthyl or a 2-naphthyl when merely referred to as a “naphthyl.”
In the present invention, non-limiting examples of the salt include an acid addition salt and a base addition salt. The acid forming the acid addition salt may be, for example, an inorganic acid or an organic acid, and the base forming the base addition salt may be, for example, an inorganic base or an organic base. Non-limiting examples of the inorganic acid include sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluorous acid, hypochlorous acid, hypobromous acid, hypoiodous acid, fluorous acid, chlorous acid, bromous acid, iodous acid, fluorine acid, chloric acid, bromic acid, iodine acid, perfluoric acid, perchloric acid, perbromic acid, and periodic acid. Non-limiting examples of the organic acid include p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, and acetic acid.
Non-limiting examples of the inorganic base include ammonium hydroxide, alkali metal hydroxide, alkaline-earth metal hydroxide, carbonate, and bicarbonate, and more specific examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium hydrogen carbonate, calcium hydroxide, and calcium carbonate. Non-limiting examples of the organic base include ethanol amine, triethylamine, and tris(hydroxymethyl)aminomethane.
An embodiment of the present invention will be described below in more detail with reference to illustrative examples. The present invention, however, is by no means limited thereby.
(1) Polymer
Non-limiting examples of the form of the polymer include a solid form, a crystalline form, and an amorphous form, or an unmolded body and a molded body. The unmolded body is, for example, a polymer itself. The molded body is, for example, a molded body molded from the polymer. In the present invention, for example, an unmolded body may be molded after altering it in the surface-treating, or a surface of a molded body obtained by molding a polymer may be altered. The kind of polymer contained in the polymer is, as a non-limiting example, one, or a mixture of two or more kinds. The polymer may be, for example, a polymer alloy or a polymer compound. The polymer may be, for example, a composite material containing material other than the polymer. Non-limiting examples of the other material include materials contained in commonly used polymers, an inorganic substance, and an organic substance. Examples of the inorganic substance include calcium carbonate, clay, talc, carbon fibers, glass fibers, aramid fibers, silicone, and zinc oxide. The other material may also be, for example, an additive such as a flame retardant and an antistatic agent.
Non-limiting examples of the solid polymer, the crystalline polymer, and the amorphous polymer include a polymer having a melting point of room temperature or higher, a polymer which is solid, crystalline, or amorphous at room temperature or higher, and a polymer which is solid, crystalline, or amorphous at 0° C. or higher. If the polymer has a glass-transition temperature, the glass-transition temperature is, as a non-limiting example, −150° C. or higher. The polymer may have a relatively high degree of crystallinity, for example. The polymer having a melting point of the above-mentioned condition has the degree of crystallinity of, for example, 20% or higher, 30% or higher, or 35% or higher. A molded body of the polymer can be obtained by a known molding method of melting by heating, shaping, and cooling, for example. In the present invention, the polymer may be, for example, a polymer having fluidity or a semisolid polymer. For example, in the plating or the adhering, the polymer may be brought into a semisolid state or a state having fluidity by heating or the like, and the polymer may be solid or amorphous without heating.
The form of the polymer may be selected, as appropriate, according to, for example, the application, use, and the like after alteration and after production of the surface-treated polymer.
The kind of the polymer to be treated is not particularly limited. The surface-treating may modify the polymer to be treated as mentioned above. The surface-treating may change, for example, the side chain or main chain (straight chain) of the polymer. The change of the main chain may be, for example, a change of the end or the inside of the main chain. Examples of the change (also referred to as modification) include oxidation and halogenation. The side chain is a chain (branched chain) branched from the main chain. Specifically, for example, the main chain is a chain of carbon atoms and/or hetero atoms, and the side chain is a chain linked to any of the carbon atoms or hetero atoms constituting the main chain and is branched from the main chain.
As a non-limiting example, the polymerized form of the polymer may be a homopolymer or a copolymer. Non-limiting examples of the copolymer include a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. The copolymer uses two or more kinds of repeating unit (monomer), for example. Further, the polymer may be, for example, a linear polymer, a branched polymer, or a network polymer.
In a preferred embodiment, the polymer contains carbon and hydrogen and has a carbon-hydrogen bond, for example. The surface-treating modifies (e.g., oxidizes) the carbon-hydrogen bond in the polymer, for example. Non-limiting specific examples of the polymer include a Polymer A, which will be described later, and, in addition, perfluoroalkoxyalkane polymers, perfluoroethylene propene copolymers, ethylene tetrafluoroethylene copolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene.
The polyolefin may be, for example, a polymer (polyolefin) of olefin monomers with a carbon number of 2 to 20. Examples of the polyolefin include polyethylenes (PE) such as low-density polyethylene and high-density polyethylene, and polypropylene (PP). The polyolefin may be, for example, a copolymer.
The polymer having a side chain to be modified may be, for example, a polymer having, as a side chain, a hydrogen group, a hydrocarbon group, or a derivative group thereof. Further, the polymer having a side chain to be modified is not limited to these, and may be, for example, a polymer having, as a side chain, any group (e.g., fluoro). In the present invention, “a polymer having a side chain to be modified” is hereinafter formally also referred to as “polymer A.”
Non-limiting specific examples of the polymer A having a side chain to be modified include: the polyolefin (e.g., polyethylene (PE) such as low-density polyethylene and high-density polyethylene, and polypropylene (PP)), polyvinyl chloride, polystyrene, polylactic acid, polyhydroxy butyric acid, a silicone polymer, natural rubber, a phenolic resin, an epoxy resin, a diallyl phthalate resin, polycarbonate (PC), polymethylmethacrylate (PMMA), polydimethylsiloxane (PDMS), polyarylate such as amorphous polyarylate, polyether sulfone, polyparaphenylene vinylene, polythiophene, polyfluorene, polyphenylene sulfide (PPS), liquid crystalline polyester, polyparaphenylene (PPP), a composite (PEDOT/PSS) of poly(3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS), polyaniline/polystyrene sulfonic acid, poly(3-hydroxy alkanoic acid), polyvinylidene chloride, a styrene copolymer (e.g., an acrylonitrile-butadiene-styrene copolymer (ABS), an acrylonitrile-styrene copolymer resin (AS), a styrene-butadiene copolymer), a methacrylic resin, polyimide, polyetherimide, poly(trans-1,4-isoprene), an urea resin, polyester (e.g., polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycaprolactone), polyamide (e.g., nylon (trade name)), polyether ether ketone, a cyclic cycloolefin polymer, polyethylene oxide, polypropylene oxide, polyacetal, a fluorine-containing polymer (e.g., Teflon (trade name), fluorine-containing synthetic rubber), and a protein (e.g., fibronectin, albumin, fibrin, keratin, cytochrome, cytokine).
As a non-limiting example, the polymerized form of the polymer A may be the same as mentioned for the polymer. For the homopolymer, the repeating unit (monomer) forming a straight chain has a side chain, for example. For the copolymer, as each repeating unit (each monomer) forming a straight chain, one kind of monomer has a side chain, or two or more kinds of monomers may each have a side chain, for example.
Non-limiting examples of the hydrogen group, the hydrocarbon group, and a derivative group thereof which is a side chain of the polymer A include monads of the following hydrocarbon groups and the derivatives thereof. The hydrocarbon may be, for example, non-aromatic or aromatic, saturated or unsaturated. Specifically, the hydrocarbon may be, for example, a straight-chain or branched, saturated or unsaturated hydrocarbon (e.g., a straight-chain or branched alkane, straight-chain or branched alkene, a straight-chain or branched alkyne). The hydrocarbon may also be, for example, a saturated or unsaturated hydrocarbon comprising a non-aromatic cyclic structure (e.g., cycloalkane, cycloalkene). The hydrocarbon may be an aromatic hydrocarbon. The hydrocarbon may or may not have, for example, one or more aromatic or non-aromatic rings, respectively, in its structure. The hydrocarbon may or may not have, for example, one or more hydrocarbon groups of a straight-chain or branched, saturated or unsaturated hydrocarbon, in its structure. The derivative of the unsaturated hydrocarbon may be, for example, a ketone, an ester, or an amide each having a carbonyl (—C(═O)—). Non-limiting examples of the carbon number of the hydrocarbon include 1 to 40, 1 to 32, 1 to 24, 1 to 18, 1 to 12, 1 to 6, and 1 to 2, and if the hydrocarbon is unsaturated hydrocarbon, the carbon number is, for example, 2 to 40, 2 to 32, 2 to 24, 2 to 18, 2 to 12, and 2 to 6. Specific examples of the hydrocarbon include methyl, ethyl, propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, vinyl, allyl, 1,3-butadiene-1-yl, ethynyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methycyclohexyl, cyclohexenyl, phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, mesityl, 1,2,4,5-tetramethylphenyl, biphenyl, 1-naphthyl, 2-naphthyl, methyl-1-naphthyl, methyl-2-naphthyl, anthryl, phenanthryl, pyrenyl, and styryl.
A “derivative” of the hydrocarbon is, for example, an organic compound containing a hetero element (an element other than carbon and hydrogen). Non-limiting examples of the hetero element include oxygen (O), nitrogen (N), sulfur (S), and halogen. Examples of the halogen include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). The derivative may be, for example, an organic compound having a structure in which a hydrocarbon group is bonded to any substituent or any atomic group. The derivative may be, for example, a compound having a structure in which a plurality of hydrocarbon groups are bonded by any atomic groups, and the hydrocarbon groups may or may not be substituted with one or more substituents Non-limiting examples of the hydrocarbon group include monovalent or bivalent groups in each of which hydrogen atoms of one of more hydrocarbons are replaced with atomic bonding. In the hydrocarbon group, one or more carbon atoms may be replaced with hetero atoms, for example. Specifically, for example, one carbon atom (and hydrogen atoms bonded thereto) of a phenyl may be substituted with a nitrogen atom to form a pyridyl. Non-limiting examples of the substituent or atomic group include hydroxy, halogen (fluoro, chloro, bromo, iodo), alkoxy, aryloxy (e.g., phenoxy), carboxy, alkoxycarbonyl, aryloxycarbonyl (e.g., phenoxycarbonyl), mercapto, alkylthio, arylthio (e.g., phenylthio), amino with or without substituent (e.g., amino, alkylamino, dialkylamino), an ether bond (—O—), an ester bond (—CO—O—), and a thioether bond (—S—).
In the present invention, when the polymer is the molded body, the surface-treating may be performed, for example, in the liquid reaction system (liquid phase) or in the gas reaction system (gas phase). For the polymer which is easily soluble in a liquid medium, the gas phase reaction system is preferred, for example. When the polymer is the molded body, for example, how to mold, the shape of the molded body, and the like are not limited in any way. Non-limiting examples of how to mold include known methods such as compression molding, transfer molding, extrusion molding, calendar molding, inflation molding, blow molding, vacuum molding, and injection molding. Non-limiting examples of the shape of the molded body include desired shapes (e.g., a sheet, a film, a plate, a tube, a pipe, a bar, a bead, a block). The molded body of the polymer may be, for example, a non-porous body, a porous body, a nonwoven fabric, or a woven fabric. For treating the molded body, the shape of the molded body is not limited in any way, for example, and may be, for example, a molded body having an exposed surface. Specifically, for example, the molded body is preferably a molded body having an exposed surface which can be in contact with the reaction system in the surface-treating. Non-limiting examples of the exposed surface of the molded body include a surface exposed to the outside, and a surface exposed to the inside, such as a tube and a porous body. For the polymer being the molded body, the surface-treating may also be referred to as alteration of the surface in the molded body of the polymer, for example.
In the present invention, when the polymer is the unmolded body, the surface-treating may be performed, for example, in the liquid reaction system (liquid phase) or in the gas reaction system (gas phase). For the surface-treating in the liquid phase, a component involved in a reaction (e.g., a radical), which will be described later, is preferably present in the liquid phase, for example. For the surface-treating in the gas phase, a component involved in the reaction is preferably present in a state of gas or mist in the gas phase, for example. For the solid polymer which is easily dissolved in a liquid medium, the solid polymer is preferably treated in the gas phase reaction system, for example.
(2) Halogen Oxide Radical
In the present invention, the halogen oxide radical is contained in a reaction system of the surface-treating. For example, the halogen oxide radical may be contained in the reaction system by generating in the reaction system or by adding, to the reaction system, the halogen oxide radical generated separately. How to generate the halogen oxide radical is not particularly limited. A specific example of the generation of the halogen oxide radical will be described later.
For example, as the halogen oxide radical, any one of them may be used, or two or more of them may be used in combination. The halogen oxide radical may be appropriately selected, for example, depending on the type of the polymer to be altered, the reaction conditions, and any other parameters.
Examples of the halogen oxide radical include halogen oxide radicals such as F2O. (oxygen difluoride radical), F2O2. (dioxygen difluoride radical), ClO2. (chlorine dioxide radical), BrO2. (bromine dioxide radical), and I2O5. (iodine (V) oxide).
(3) Reaction System
The reaction system in the surface-treating contains the polymer and the halogen oxide radical. The reaction system may be, as mentioned above, for example, either a gas reaction system or a liquid reaction system. In the production method according to the present invention, as mentioned above, the reaction system is not irradiated with light in the surface-treating. In the production method according to the present invention, the polymer and the halogen oxide radical can be reacted with each other without irradiating the polymer with light. No irradiation of the polymer with light allows safety to be improved, and costs to be reduced, for example. For example, a halogen oxide radical may be generated by light irradiation in a radical generation reaction system which is different from the reaction system of the surface-treating so as not to irradiate the reaction system of the surface-treating with light. Note that how to generate the halogen oxide radical itself is not particularly limited as mentioned above, and the halogen oxide radical may be generated without light irradiation. In the present invention, “no light irradiation” for the reaction system and derivatives thereof includes, but is not limited to, blocking light for preventing light entering the reaction system. In the present invention, “no light irradiation” for the reaction system and derivatives thereof may or may not include blocking light for preventing light entering the reaction system, for example. In the present invention, “no light irradiation” for the reaction system and derivatives thereof may include the state where natural light or room light enters the reaction system in the state where the reaction system is not actively irradiated with light using a light source, for example. For example, no irradiation of the reaction system with light allows the reaction to be performed in a simplified manner and at low cost.
(3A) Gas Reaction System
For the reaction system being a gas reaction system, for example, the polymer may be placed in the gas reaction system containing the halogen oxide radical to perform the surface-treating. The gas reaction system may contain the radical, for example, and non-limiting examples of the kind of the gas phase in the gas reaction system include air, nitrogen, noble gas, and oxygen.
In the present invention, for example, the halogen oxide radical may be introduced or generated in the gas reaction system prior to or in parallel to the surface-treating. In the former case, for example, a gas containing the halogen oxide radical may be introduced into the gas phase. In the latter case, for example, as will be described later, the halogen oxide radical generated in the radical generation reaction system in a liquid phase may be introduced by transferring the halogen oxide radical to a gas phase.
As a specific example, for the halogen oxide radical being the chlorine dioxide radical, for example, the chlorine dioxide radical may be present in the gas phase by introducing a chlorine dioxide gas into the gas phase. The chlorine dioxide radical may be generated in the gas phase by an electrochemical method, for example.
(3B) Liquid Reaction System
For the reaction system being the liquid reaction system, the liquid reaction system contains an organic phase, for example. The liquid reaction system may be a single-phase reaction system containing only the organic phase, or a double-phase reaction system containing the organic phase and an aqueous phase, for example. For the single-phase reaction system containing only the organic phase, for example, as will be described later, an aqueous phase containing a source of the halogen oxide radical may be prepared separately to generate the halogen oxide radical in the aqueous phase, the organic phase may then be mixed with the aqueous phase to dissolve (extract), in the organic phase, and the halogen oxide radical generated in the aqueous phase.
(3B-1) Organic Phase
The organic phase contains the polymer placed therein, as mentioned above, and is, for example, a phase of an organic solvent containing the halogen oxide radical and the polymer placed therein.
The organic solvent is not particularly limited. As the organic solvent, one kind may be used, or a plurality of kinds may be used in combination, for example. In the present invention, examples of the organic solvent include a halogenated solvent and a fluorous solvent, as mentioned above. For the liquid reaction system being the double-phase reaction system, the organic solvent is, for example, preferably, a solvent capable of forming the double-phase system, i.e., a solvent which separates from the aqueous solvent, which will be described later, constituting the aqueous phase, or a solvent slightly soluble or insoluble in the aqueous solvent.
The “halogenated solvent” refers to a solvent in which all or most of hydrogen atoms of hydrocarbon have been substituted with halogen, for example. The halogenated solvent may be, for example, a solvent in which 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of hydrogen atoms of the hydrocarbon are substituted with halogen. Non-limiting examples of the halogenated solvent include methylene chloride, chloroform, carbon tetrachloride, carbon tetrabromide, and a fluorous solvent, which will be described later.
The “fluorous solvent” is a kind of the halogenated solvent, and refers to a solvent in which all or most of hydrogen atoms of hydrocarbon are substituted with fluorine atoms, for example. The fluorous solvent may be, for example, a solvent in which 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of hydrogen atoms of hydrocarbon are substituted with fluorine atoms. In the present invention, the use of the fluorous solvent is advantageous in reducing or preventing side reactions due to the low reactivity of the fluorous solvent itself, for example. Examples of the side reactions include an oxidation of the solvent, a hydrogen abstraction reaction of the solvent with the radical, halogenation (e.g., chlorination), and a reaction of a radical derived from a raw material compound and the solvent (e.g., a reaction of an ethyl radical and the solvent, for the hydrocarbon group in the side chain or at the terminal of the polymer being an ethyl group). The fluorous solvent is suitable for forming the double-phase reaction system due to its low miscibility with water, for example.
Examples of the fluorous solvent include solvents represented by the following chemical formulae (F1) to (F6). Among them, the fluorous solvent is, for example, preferably CF3(CF2)4CF3 having the following chemical formula (F1) where n=4.
The boiling point of the organic solvent is not particularly limited. The organic solvent may be appropriately selected, for example, depending on the temperature conditions in the surface-treating. For the high reaction temperature set in the surface-treating, a high boiling point solvent may be selected as the organic solvent. Note that, for example, as will be described later, heating is not essential in the present invention, and the present invention can be implemented at ordinary temperature and normal pressure, for example. In such a case, the organic solvent need not be, for example, a high boiling point solvent, and a solvent having a not very high boiling point may be used from the viewpoint of ease of handling.
The organic phase may contain, for example, only the polymer, the halogen oxide radical, and the organic solvent, and may further contain other components. Non-limiting examples of the other components include Bronsted acid, Lewis acid, and oxygen (O2). In the organic phase, the other components may be, for example, in a state of being dissolved or undissolved in the organic solvent. In the latter case, the other components may be, for example, dispersed or precipitated in the organic solvent.
The organic phase contains the halogen oxide radical as mentioned above. The organic phase may contain the halogen oxide radical by generating the halogen oxide radical in a phase other than the organic phase and extracting the halogen oxide radical, for example. Specifically, for the reaction system being a single-phase reaction system containing only an organic phase, for example, the halogen oxide radical is generated separately in a phase other than the organic phase being the reaction system, the generated halogen oxide radical is extracted with the organic phase, and the organic phase containing the extracted halogen oxide radical as the reaction system can be used for the surface-treating. The generation of the halogen oxide radical may be performed in the aqueous phase provided separately, as will be described later, for example. On the other hand, for the liquid reaction system being a double-phase system containing the organic phase and the aqueous phase, for example, the halogen oxide radical is generated in the aqueous phase, the generated halogen oxide radical is extracted from the aqueous phase in the organic phase, and an organic phase containing the aqueous phase and the halogen oxide radical can be used for the surface-treating as the double-phase reaction system.
The polymer is placed in the organic phase. For the polymer being the molded body, the molded body is preferably fixed in the organic phase such that a portion of the molded body to be surface-treated is immersed in the organic phase and is not exposed from the organic phase, for example.
(3B-2) Aqueous Phase
The aqueous phase is, for example, an aqueous solvent. The aqueous solvent is, for example, a solvent which is separated from a solvent used in the organic phase. Examples of the aqueous solvent include water such as H2O and D2O.
The aqueous phase may contain, for example, any components such as Lewis acid, Bronsted acid, and a radical generation source, as will be described below. The components in the aqueous phase may be, for example, in a state in which they are dissolved or undissolved in the aqueous solvent. In the latter case, the components may be, for example, in a state in which they are dispersed or precipitated in the aqueous solvent.
(4) Surface-Treating
The surface-treating is reacting a surface of the polymer with a halogen oxide radical, as mentioned above. In the surface-treating, the reaction system of the reaction is not irradiated with light, as mentioned above. As mentioned above, no irradiation of the polymer with light allows safety to be improved, and costs to be reduced, for example.
The reaction system contains the polymer placed therein, and the polymer may be altered. Specifically, the present invention allows the polymer to be altered easily in the presence of the halogen oxide radical. The present invention allows the degree of modification of the polymer (e.g., the degree of alteration such as oxidation) to be easily adjusted through adjustment of the amount of the halogen oxide radical, the reaction time, and the like, for example. This can prevent degradation of the polymer caused by excessive oxidation, and avoid deterioration of the characteristics that the polymer originally has, for example.
For the side chain of the polymer being methyl, in the surface-treating, the methyl (—CH3) may be oxidized into at least one of, for example, a hydroxymethyl (—CH2OH), a formyl (—CHO), or a carboxyl (—COOH). This is assumed by the following mechanism. For example, the irradiation of the halogen oxide radical with light generates a radical of the halogen (e.g., a chlorine radical (Cl.)) and a molecule of the oxygen from the halogen oxide radical (e.g., a chlorine dioxide radical).
This light irradiation can be performed in a reaction system different from that of the surface of the polymer and the halogen oxide radical, for example, as mentioned above. Then, methyl of the polymer (—CH3) is modified into a carboradical (—CH2.) with a radical of the halogen (e.g., a chlorine radical (Cl.)) serving as a hydrogen-abstraction agent, and thereafter, the carboradical is modified into hydroxymethyl (—CH2OH) with a molecule of the oxygen (e.g., O2) serving as an oxidizing agent. Further, the hydroxymethyl (—CH2OH) is further oxidized into a formyl (—CHO) or a carboxyl (—COOH). The polymer being polypropylene (PP) allows oxidation in the following formula, for example.
For the side chain of the polymer being an ethyl in the surface-treating, the ethyl (—CH2CH3) is oxidized into, for example, a hydroxyethyl (—CH2CH2OH), an acetaldehyde group (—CH2CHO), or carboxymethyl (—CH2COOH).
The polymer being polyethylene (PE) allows oxidation in the following formula, for example. Specifically, for example, a main chain carbon atom to which a hydrogen atom is bonded is oxidized to hydroxymethylene (—CHOH—), carbonyl (—CO—), or the like as in the following formula. Also, for example, for the polymer being polypropylene (PP), in addition to or as substitute for the oxidation, oxidation as in the following formula may occur.
In the surface-treating, the conditions of the light irradiation of irradiating the halogen oxide radical with light in a reaction system different from the reaction system of the surface of the polymer and the halogen oxide radical are not particularly limited. As a non-limiting example, the wavelength of the irradiation light has a lower limit of 200 nm or more, and an upper limit of 800 nm or less. As a non-limiting example, the light irradiation time has a lower light irradiation of 1 second or more, and an upper limit of 1000 hours. As a non-limiting example, the reaction temperature has a lower limit of −20° C. or more, an upper limit of 100° C. or less or 40° C. or less, and has a range from 0° C. to 100° C., or from 0° C. to 40° C. As a non-limiting example, the atmospheric pressure during the reaction has a lower limit of 0.1 MPa or more, an upper limit of 100 MPa or less, 10 MPa or less, or 0.5 MPa or less, and a range from 0.1 to 100 MPa, from 0.1 to 10 MPa, or from 0.1 to 0.5 MPa. The reaction conditions during the surface-treating are, for example, a temperature from 0° C. to 100° C., or from 0° C. to 40° C., a pressure from 0.1 to 0.5 MPa. As described above, for example, the surface-treating itself may be performed without light irradiation. The present invention allows the surface-treating or all steps including the surface-treating to be performed at normal temperature (room temperature) and normal pressure (atmospheric pressure) without heating, pressurizing, and decompressing, for example. As a non-limiting example, the “room temperature” is from 5° C. to 35° C. For this reason, the present invention is applicable to the polymer having a low heat resistance, for example. Further, the present invention allows the surface-treating or all steps including the surface-treating to be performed in atmosphere without substitution with inactive gas, for example.
As a non-limiting example, the light source of the light irradiation is visible light included in natural light such as sunlight. The natural light allows excitation to be performed in a simplified manner, for example. Further, as the light source, for example, as a substitute for or in addition to the natural light, light sources such as a xenon lamp, a halogen lamp, a fluorescent lamp, a mercury lamp, and an LED lamp can be used. In the light irradiation, for example, a filter for cutting wavelengths other than the necessary wavelengths can further be used as appropriate.
For the polymer being the molded body in the present invention, for example, a region of the molded body is reacted with the halogen oxide radical to alter only the region, for example. As a non-limiting example of the control of such a selective reaction, only a region not to be reacted with the halogen oxide radical may be masked not to be in contact with the halogen oxide radical.
In the surface-treating, for example, for the reaction system being the liquid reaction system, the reaction may be performed while the liquid reaction system is in contact with air, and for the reaction system being the double-phase reaction system, the reaction may be performed in a state in which oxygen is dissolved in the aqueous phase. In addition, for the reaction system being the double-phase reaction system, for example, the reaction may be performed by irradiating only the aqueous phase with light.
The surface-treating of the present invention can modify the polymer by generating a radical of the halogen (e.g., a chlorine atom radical Cl.) and an oxygen molecule O2 through, for example, really simply bringing the surface of the polymer into contact with the halogen oxide radical to bring the polymer to react (e.g., oxidize). Then, for example, the present invention can change and modify the polymer efficiently in a simplified manner even under extremely mild conditions such as normal temperature and normal pressure.
The present invention allows the metal plating polymer altered or the adhesion laminate producing polymer of the polymer and the adherend to be obtained, without a toxic heavy metal catalyst, for example. Therefore, as mentioned above, for example, the polymer may be altered efficiently with the low load on the environment in addition to the reaction being performed under the very mild conditions.
As an oxidation of the polymer, addition of a compound such as maleic acid or acrylic acid to a polymer such as PE or PP using peroxide has been known. However, since these compounds are accompanied by a crosslinking reaction, a decomposition reaction, or the like of PE and PP, it is difficult to improve the content of the site to be oxidized in the polymer. On the other hand, the present invention can improve the content of the site to be oxidized in the polymer, relative to that in the past.
(5) Generating Halogen Oxide Radical
The present invention may further include generating a halogen oxide radical, for example. The generating a halogen oxide radical may be performed prior to or in parallel with the surface-treating, for example. How to generate the halogen oxide radical is not particularly limited.
In the generating a halogen oxide radical, for example, the halogen oxide radical may be generated in a radical generation reaction system. The reaction system in the surface-treating may be, for example, either the gas reaction system (gas phase) or the liquid reaction system (liquid phase). The radical generation reaction system after the generation of the halogen oxide radical may be used as it is as the liquid reaction system in the surface-treating, for example.
For the reaction system in the surface-treating being the gas reaction system, for example, the radical generation reaction system may be prepared separately from the reaction system in the surface-treating. The radical generation reaction system may be, for example, an aqueous phase containing a source of the halogen oxide radical. The aqueous phase includes, for example, a source of the halogen oxide radical, and in the generating the halogen oxide radical, the halogen oxide radical is generated from the source. The aqueous phase is, for example, a phase of an aqueous solvent, and the aqueous solvent is the same as mentioned above. For the halogen oxide radical generated in the aqueous phase being hydrophobicity, for example, the halogen oxide radical may be transferred into the organic phase using a double-phase reaction system containing the organic phase and the aqueous phase. As mentioned above, in the surface-treating performed in the gas reaction system, the halogen oxide radical generation reaction system may be for example, either only an aqueous phase or a double-phase reaction system of an aqueous phase and an organic phase. For the halogen oxide radical being hydrophobic, for example, the radical generated in the aqueous phase can be transferred directly into the gas phase. Thus, the radical generation reaction system may be only the aqueous phase.
For the reaction system in the surface-treating being the liquid reaction system which contains an aqueous phase, for example, the aqueous phase may be the radical generation reaction system. For the reaction system in the surface-treating being the gas reaction system, the aqueous phase may be, for example, the same as the radical generation reaction system. For the halogen oxide radical generated in the aqueous phase having hydrophobicity, for example, the halogen oxide radical may be transferred into the organic phase using a double-phase reaction system containing the organic phase and the aqueous phase.
The source of the halogen oxide radical (radical generation source) is not particularly limited, and may be selected, as appropriate, according to the kind of the halogen oxide radical, for example. One kind or a plurality of kinds of the source of the halogen oxide radical may be used in combination, for example.
The source of the halogen oxide radical is, for example, a compound containing oxygen and halogen, and can be halous acid (HXO2) or a salt thereof as a specific example. Non-limiting examples of the salt of the halous acid include a metal salt, and examples of the metal salt include alkaline metal salts, alkaline earth metal salts, and rare earth salts. The source of the halogen oxide radical may be, for example, a compound containing oxygen, halogen, and a Group 1 element (e.g., at least one selected from the group consisting of H, Li, Na, K, Rb, and Cs), and can be, for example, the halous acid or an alkaline metal salt thereof. For the halogen oxide radical being the chlorine dioxide radical, non-limiting examples of the source thereof include chlorous acid (HClO2) and salts thereof, and specific examples thereof include sodium chlorite (NaClO2), lithium chlorite (LiClO2), potassium chlorite (KClO2), magnesium chlorite (Mg(ClO2)2), and calcium chlorite (Ca(ClO2)2). Among them, from the viewpoint of cost, ease of handling, and the like, sodium chlorite (NaClO2) is preferred. For example, a similar way can be employed for sources of other halogen oxide radicals. Examples of the other sources include bromite such as sodium bromite and iodite such as sodium iodite.
The concentration of the source in the aqueous phase is not particularly limited. For the source being the compound, the concentration has, for example, a lower limit of 0.0001 mol/L or more, and an upper limit of 1 mol/L or less when converted in to the concentration of the halogen oxide ion, and has a lower limit of 1/100000 times or more, and an upper limit of 1000 times or less of the number of moles of the raw material when converted into the number of moles of the halogen oxide ion. For the source being the halous acid or a salt thereof (e.g., chlorous acid or a salt thereof), the concentration has, for example, a lower limit of 0.0001 mol/L or more, and an upper limit of 1 mol/L or less when converted into the concentration of the halous acid ion (e.g., chlorite ion (ClO2−)). The concentration of the source has, for example, a lower limit of 1/100000 times or more, and an upper limit of 1000 times or less of the number of moles of the raw material when converted into the number of moles of the halous acid ion (e.g., a chlorite ion (ClO2−)). For other sources, for example, the same concentrations may be used.
The aqueous phase may further contain, for example, at least one of Lewis acid or Bronsted acid, which may act on the halogen oxide ion to generate the halogen oxide radical. At least one of the Lewis acid or Bronsted acid is, for example, at least one of Lewis acid or Bransted acid containing the Group 1 element. The halogen oxide ion is, for example, a chlorite ion (ClO2−). The aqueous phase contains, for example, either one of or both of the Lewis acid or Bronsted acid, or one substance serving as both of the Lewis acid and Bronsted acid. Only one kind each of the Lewis acid and Bronsted acid may be used, or a plurality of kinds of the Lewis acid and Bronsted acid may be used in combination. In the present invention, the “Lewis acid” refers to, for example, a substance serving as Lewis acid for the source of the halogen oxide radical.
The concentration of at least one of the Lewis acid or Bronsted acid in the aqueous phase is not particularly limited and can be set, as appropriate, according to the kind of the polymer to be altered, for example. The concentration has, for example, a lower limit of 0.0001 mol/L or more, and an upper limit of 1 mol/L or less.
Non-limiting examples of the Bronsted acid include inorganic acids and organic acids, and specific examples thereof include trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, hydrofluoric acid, hydrogen chloride, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and phosphorous acid. The Bronsted acid has an acid dissociation constant pKa of, for example, 10 or less. As a non-limiting example, the pKa has a lower limit of, for example, −10 or more.
It is preferred that the aqueous phase contains, for example, the halogen oxide ion and the Bronsted acid, and is, for example, an aqueous phase obtained by dissolving the compound and the Bronsted acid (e.g., hydrochloric acid) in an aqueous solvent. As a specific example, for the halogen oxide radical being a chlorine dioxide radical, it is preferred that the aqueous phase contains, for example, chlorite ion (ClO2−) and Bronsted acid, and is, for example, an aqueous phase obtained by dissolving the sodium chlorite (NaClO2) and the Bronsted acid (e.g., hydrochloric acid) in an aqueous solvent.
In the aqueous phase, the Lewis acid, the Bronsted acid, the radical generation source, and the like may be, for example, in a state in which they are dissolved or undissolved in the aqueous solvent. In the latter case, these may be dispersed or precipitated in an aqueous solvent, for example.
As a non-limiting example, the generating a halogen oxide radical may be performed by bringing the source of the halogen oxide radical to be contained in the aqueous solvent to naturally generate the halogen oxide radical (e.g., a chlorine dioxide radical) from the halogen oxide ion (e.g., a chlorite ion). For example, it is preferred that in the aqueous phase, the source is dissolved in the aqueous solvent, and the aqueous phase is left to stand. In the generating a halogen oxide radical, the coexisting of at least one of the Lewis acid or the Bronsted acid in the aqueous phase allows the generation of the halogen oxide radical to be further promoted, for example. In the generating a halogen oxide radical, for example, the irradiation of the aqueous phase with light also allows the generation of the halogen oxide radical, but mere standing still of the aqueous phase also allows the generation of the halogen oxide radical.
The mechanism of generating the halogen oxide radical from the halogen oxide ion in the aqueous phase is presumed to be the same as in
For the reaction system being the liquid reaction system, and a double-phase reaction system of the organic phase and the aqueous phase, as mentioned above, the liquid reaction system after generation of the halogen oxide radical may be applied as it is to the surface-treating. Since the halogen oxide radical generated from the source in the aqueous phase in the reaction system is hardly dissolved in water, the halogen oxide radical is dissolved in the organic phase in the reaction system. For example, the liquid reaction system containing the halogen oxide radical generated may be irradiated with light to perform the surface-treating of modifying the polymer. In this case, for example, the generating a halogen oxide radical and the surface-treating can be performed continuously by irradiating only the aqueous phase of the liquid reaction system with light. In the present invention, the generating a halogen oxide radical and the surface-treating in the double-phase reaction system achieves higher reaction efficiency, for example.
On the other hand, for the reaction system in the surface-treating being the liquid reaction system, and a single-phase reaction system only containing the organic phase, for example, the halogen oxide radical is generated in the aqueous phase in the manner described above, the generated halogen oxide radical is dissolved (extracted) in the organic phase, the aqueous phase is then removed, and the organic phase containing the halogen oxide radical may be applied, as the single-phase reaction system, to the surface-treating.
In
Although
(6) Introducing Functional Group
The surface-treated polymer production method according to the present invention may further include, for example, introducing a functional group into a changed site of the polymer. Examples of the changed site (modified site) in the polymer include a site into which an element such as mentioned above has been introduced, and specific examples thereof include an oxidized site.
The surface-treated polymer production method according to the present invention can modify the polymer by the surface-treating, and can further change physical properties of the polymer by introducing a functional group, as mentioned above.
The surface-treated polymer production method according to the present invention can impart various functions to the polymer by further introducing a functional group, for example.
The surface-treated polymer production method according to the present invention can change physical properties of the polymer by introducing the functional group, for example.
Introducing a functional group includes, for example, applying an agent to the polymer. The changing of physical properties of the polymer in this manner, for example allows expansion of the applications of the polymer to a delivery material, a sustained release material, culture component of cells such as iPS cells, and the like, for example.
(7) Plating Metal
In the metal-plated polymer production method and the metal-plated polymer according to the present invention, non-limiting examples of the metal include Group 4 elements (e.g., titanium, zirconium, hafnium), Group 5 elements (e.g., vanadium, niobium, tantalum), Group 6 elements (e.g., chromium, molybdenum, tungsten), Group 7 elements (e.g., manganese, technetium, rhenium), Group 8 elements (e.g., iron, ruthenium, osmium), Group 9 elements (e.g., cobalt, rhodium, iridium), Group 10 elements (e.g., nickel, palladium, platinum), Group 11 elements (e.g., copper, silver, gold), Group 12 elements (e.g., zinc, cadmium, mercury), Group 13 elements (e.g., aluminium, gallium, indium, thallium), Group 14 elements (e.g., germanium, tin, lead), and Group 15 elements (e.g., arsenic, antimony, bismuth). One kind of the metal may be used, or an alloy of a plurality of kinds of the metal may be used. Non-limiting examples of the alloy include solder.
In the present invention, for example, the alteration of the polymer by the surface-treating allows the polymer to be easily plated with the metal, which is a different material. More specifically, for example, the hydrophilization of the surface of the polymer by the surface-treating exhibits, for example, an effect of easily supporting the plating catalyst on the surface of the polymer, thereby plating easily. Further, for example, the hydrophilization of the surface of the polymer by the surface-treating allows the plating metal itself to be easily supported on the surface of the polymer, thereby hardly peeling a metal coating after the plating.
The combination of the polymer to be surface-treated and the metal is not particularly limited. The following Tables 1 and 2 show examples of the combination of the polymer to be surface-treated and the metal. In Table 1 below, each of the listed polymers to be surface-treated can be combined with each of the metals described in the right column. Similarly, in Table 2 below, each of the listed polymers to be surface-treated can be combined with each of the metals described in the right column. The present invention is not limited to these combinations.
(8) Plating
In the metal-plated polymer production method according to the present invention, the plating is plating the surface of the polymer with the metal after the surface-treating.
Non-limiting examples of the plating include commonly used plating of the polymer and plating similar thereto. In the present invention, non-limiting specific examples of the plating include electroless plating, gas phase plating, electroplating, and melting plating. For example, the surface of the polymer after the surface-treating may be plated with a metal by electroless plating or gas phase plating, and the surface of the metal may then be further plated with a metal by electroplating or melting plating. Non-limiting examples of the specific plating of electroless plating, gas phase plating, electroplating, and melting plating include commonly used plating and the plating similar thereto.
As a non-limiting example, the plating can be performed as follows, for example, for the electroless plating. An example of the metal-plated polymer production method according to the present invention including the surface-treating and the plating will be described below. First, a polymer is provided. Next, a surface to be plated with a metal in the polymer (metal-plating surface) is surface-treated (surface-altered) by the surface-treating. Note that, although the metal-plating surface may be irradiated with light, the present invention is not limited to the light irradiation as mentioned above as long as the surface of the polymer can react with the halogen oxide radical. Further, after the surface-treating, introducing the functional group may be performed as required. Thus, an altered surface of the polymer (altered surface) is formed. The altered surface may be hydrophilized by, for example, oxidizing the surface of the polymer, or oxidizing the surface of the polymer and introducing a functional group.
Next, the plating is performed. That is, first, a catalyst is supported on the altered surface. Specifically, for example, first, the altered surface is brought into contact with a liquid containing a catalyst. More specifically, for example, the altered surface may be immersed in the liquid. The liquid may be, for example, an aqueous solution of the catalyst. The catalyst is not particularly limited and may be the same as a catalyst for the commonly used electroless plating, and examples thereof include a palladium catalyst and a silver catalyst. Examples of the palladium catalyst include palladium chloride (PdCl2), palladium sulfate (PdSO4), and palladium nitrate (Pd(NO3)2). One kind of the catalyst may be used, or a plurality of kinds of the catalyst may be used in combination. Further, the catalyst may or may not contain, for example, a cocatalyst. Non-limiting examples of the cocatalyst include a tin catalyst. The tin catalyst can be, for example, stannous chloride (SnCl2). Non-limiting examples of the concentration of the catalyst in the liquid include the concentration in commonly used electroless plating and the concentration similar thereto. As a non-limiting example, the time for bringing the altered surface into contact with the liquid is 0.01 minutes or more, 0.1 minutes or more, 0.5 minutes or more, 1 minute or more, or 10 minutes or more, and is 60 minutes or less, 45 minutes or less, 30 minutes or less, 20 minutes or less, or 15 minutes or less. In addition, at this time, the liquid may be, for example, heated, or may be at room temperature without heating. More specifically, non-limiting examples of the temperature of the liquid include 0° C. or more, 5° C. or more, 10° C. or more, or 20° C. or more, and 100° C. or less, 80° C. or less, 60° C. or less, or 40° C. or less. Thereafter, the altered surface is washed with, for example, water to remove excessive catalyst and the like. Thus, only a necessary amount of the catalyst remains supported on the altered surface. Note that, for example, contact and washing with the liquid containing the catalyst may be repeatedly performed a plurality of times. Alternatively, for example, contact and washing with each of a plurality of kinds of liquid containing the catalyst may be performed. Further, the altered surface on which the catalyst has been supported is plated with metal. Specifically, for example, first, the altered surface on which the catalyst has been supported is brought into contact with a liquid containing ions of the metal. Specifically, for example, the altered surface may be immersed in the liquid. The liquid may be, for example, an aqueous solution of the salt of the metal. Non-limiting examples of the salt of the metal include the salt commonly used in electroless plating and the salt similar thereto. Non-limiting examples of the concentration of the liquid include the concentration commonly used in electroless plating and the salt similar thereto. As a non-limiting example, the time for bringing the altered surface on which the catalyst has been supported into contact with the liquid containing ions of the metal is 0.01 minutes or more, 0.1 minutes or more, 0.5 minutes or more, or 1 minutes or more, and 10 minutes or less, 1500 minutes or less, 100 minutes or less, 50 minutes or less, 20 minutes or less, or 10 minutes or less. In addition, at this time, non-limiting examples of the temperature of the liquid containing ions of the metal include 0° C. or more, 10° C. or more, 20° C. or more, or 30° C. or more, and 100° C. or less, 90° C. or less, 80° C. or less, or 70° C. or less. Thus, the metal can be deposited on the altered surface on which the catalyst has been supported, thereby plating the altered surface.
An example of the commonly used electroless plating for the polymers will be shown below. First, a polymer is provided. Next, the polymer is immersed in an etchant (e.g., an aqueous solution of a heavy metal oxidizing agent such as chromic acid). Thus, at least one surface of the polymer is roughened, thereby forming a roughened surface. Further, the roughened surface is washed and dried to form a metal-plating surface. Then, the catalyst is supported on the metal-plating surface. Further, the metal-plating surface on which the catalyst has been supported is plated with the metal.
The metal-plated polymer production method according to the present invention can be performed without a heavy metal oxidizing agent, for example, as mentioned above. This can solve problems such as toxicity of the heavy metal catalyst, treatment cost of the heavy metal oxidizing agent, and load on the environment, for example, as mentioned above. Further, this can shorten the process and improve the production efficiency, for example, as compared with the commonly used electroless plating. In addition, the metal-plated polymer production method according to the present invention can be easily performed, is applicable to a wide range of polymers, and is, for example, applicable also to biomass plastics such as polylactic acid (PLA). Note that the above description is illustrative and does not limit the present invention.
The metal-plated polymer production method according to the present invention can, for example, pattern the surface of the polymer to plate part of the surface with a metal. Specifically, for example, the polymer is subjected to patterning and the surface-treating. Thus, a part of the metal-plating surface is altered by the surface-treating to form the altered surface. As a non-limiting example, how to perform patterning may be coating a surface other than the altered surface in the polymer with any substance (mask). Non-limiting examples of the material of the mask include glass, metal, paper, and clay. The reaction by light irradiation may be performed by irradiating a part other than the mask with light, for example. Further, the altered surface is plated with the metal in the plating, thereby producing a metal-plated polymer, a part of which has been plated. Such a method can impart electroconductivity to only a necessary part of the surface of the polymer, for example, and is thus suitable for an electronic device and the like. Note that the mask may be peeled from the polymer after the surface-treating or the plating.
The metal-plated polymer production method according to the present invention is applicable to a polymer of any shape as mentioned above. For this reason, it is also possible to plate a polymer of a complicated shape with a metal, for example. The metal-plated polymer production method according to the present invention can plate, for example, the polymer of a complicated shape which is difficult to be plated by a commonly used method, and can plate, for example, an inner surface of a tube. As described above, it is possible to plate the surface of the polymer of a complicated shape, and thus can produce a product with high designability, for example. For example, it is also possible to impart a function such as electroconductivity to the surface of the polymer.
(9) Adherend
In the present invention, non-limiting examples of the adherend to the polymer after surface treatment include metal, ceramic, another polymer, glass, cloth, and paper as mentioned above. Non-limiting examples of the metal include aluminum, nickel, iron, gold, silver, copper, and alloys such as duralumin, high tensile steel, and stainless steel. Non-limiting examples of the ceramic include zirconia, aluminum oxide, ferrite, barium titanate, boron nitride, silicon carbide, silicon nitride, and steatite. Non-limiting examples of the another polymer may include those shown as examples of the polymer, which will be described later. The polymer and the another polymer which is the adherend may be polymers of the same kind or polymers of different kinds.
In the present invention, the polymer is altered by the surface-treating. For example, this allows the adherend which is a different material (e.g., a polymer, metal, or ceramic of a different kind) to be easily adhered to the polymer. More specifically, for example, the metal has a free electron and is hydrophilic. Thus, the hydrophilization of the surface of the polymer by the surface-treating allows the metal to be easily adhered thereto. For example, there is a possibility that the oxygen functional group introduced into the surface of the polymer by the surface-treating forms a coordinate bond with the metal, thereby allowing the polymer and the metal to easily adhere to each other. It is to be noted, however, that these descriptions are merely illustrative examples and by no means limit the present invention.
There is no particular limitation on the shape, size, and the like of the adherend. Examples of the shape include a sheet, a film, a plate, a tube, a pipe, a bar, a bead, a block, and a particle, a lysate, a sol, a gel, a woven fabric, a nonwoven fabric and a yarn. As a non-limiting example, the size of the adherend may be arbitrarily selected.
The adherend is not limited to, for example, a solid, and may be a flowable adherend. The flowable adherend may be, for example, a liquid or a solid. The flowable adherend refers to one solidified by drying or curing after applying, for example. Examples of the flowable adherend include a paint, an adhesive, an acrylic resin, a polyurethane, silicone, an epoxy resin, a phenolic resin, an urea resin, a melamine resin, a lysate, a sol, and a gel. For example, the flowable adherend may be applied to the surface of the polymer after the surface-treating to adhere (the adhering) to the surface of the polymer. The flowable adherend may be, for example, dried if necessary after the applying. In general, a paint applied to the surface of the polymer may be easily peeled off. This is particularly problematic for the polymer being polypropylene (PP). However, the surface-treating of the present invention allows the affinity between the flowable adherend (e.g., a paint) and the surface of the polymer to be enhanced, thereby avoiding peeling off of the adherend.
The combination of the polymer to be surface-treated and the adherend is not particularly limited. Examples of the adherend include metals and polymers. Examples of the combination of the polymer to be surface-treated and the adherend are shown in Table 3 below. In Table 3 below, each of the listed polymers to be surface-treated can be combined with each of the metals and polymers described in the right column. The present invention is not limited to these combinations.
(10) Adhering
In the adhesion laminate production method according to the present invention, the adhering is adhering the adherend to the surface of the polymer after the surface-treating. Non-limiting examples of the adhering include commonly used adhering of the polymer and the adherend and adhering similar thereto.
The adhering may include, for example, bringing the polymer and the adherend into direct contact with each other and then pressing them without a primer (undercoat layer), an adhesive, or any other agent. As a non-limiting example, the pressure during the pressing has a lower limit of 0.1 MPa or more, 0.5 MPa or more, 1 MPa or more, 5 MPa or more, or 10 MPa or more, and an upper limit of 100 MPa or less, 50 MPa or less, 40 MPa or less, 30 MPa or less, or 25 MPa or less. As a non-limiting example, the time for applying the pressure has a lower limit of 0.01 minutes or more, 0.1 minutes or more, 3 minutes or more, 5 minutes or more, or 10 minutes or more, and an upper limit of 60 minutes or less, 45 minutes or less, 30 minutes or less, or 20 minutes or less. As a non-limiting example, how to perform pressing may be pressing with a roller, or pressing with hands. One or both of the polymer and the adherend may be heated (heat-pressed) prior to the pressing or in parallel with the pressing, or the polymer and the adherend may be merely pressed without heating. As a non-limiting example, the heating temperature has a lower limit of 0° C. or more, 10° C. or more, 20° C. or more, 45° C. or more, or 60° C. or more, and an upper limit of 200° C. or less, 150° C. or less, 120° C. or less, 100° C. or less, or 90° C. or less. For the polymer having a high glass-transition temperature, heating at an appropriate temperature allows the polymer to be easily adhered to the adherend, for example. For the polymer being polylactic acid (PLA), the heating temperature has a lower limit of 30° C. or more, 40° C. or more, 50° C. or more, 55° C. or more, or 60° C. or more, and an upper limit of 120° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less, for example. For the polymer being polypropylene (PP), the heating temperature has a lower limit of 0° C. or more, 5° C. or more, 10° C. or more, or 15° C. or more, or 20° C. or more, and an upper limit of 100° C. or less, 90° C. or less, 80° C. or less, 60° C. or less, or 40° C. or less.
For an adhesion laminate of the polymer and the adhesion laminate obtained in the manner described above, as a non-limiting example, the peel strength between the polymer and the adherend has a lower limit of 0.001 N/mm2 or more, 0.01 N/mm2 or more, 0.1 N/mm2 or more, 1 N/mm2 or more, 5 N/mm2 or more, or 10 N/mm2 or more, and an upper limit of 1000 N/mm2 or less, 500 N/mm2 or less, 100 N/mm2 or less, 50 N/mm2 or less, or 20 N/mm2 or less.
In the adhesion laminate of the polymer and the adherend according to the present invention, for example, the adherend may be in direct contact with the surface of the polymer. The “direct contact” of the adherend to the surface of the polymer means that the adherend is in direct contact with the surface of the polymer without other layers such as an adhesive or a pressure-sensitive adhesive interposed therebetween.
A commonly used way to adhere the polymer and the adherend is, for example, as follows. First, a polymer is provided. Next, a part to be adhered to the adherend in the surface of the polymer is washed and dried, and a primer (undercoat layer) is applied to the part, which is again dried. Further, an adhesive is applied on the primer, and the adherend is bonded and then dried, and the polymer and the adhered are bonded. In this manner, an adhesion laminate of the polymer and the adherend is produced.
In contrast, the adhesion laminate production method according to the present invention is, for example, as follows. First, a polymer is provided, and a part to be adhered to the adherend in the surface of the polymer is altered by the surface-treating. Next, the altered surface obtained by the surface treatment of the polymer is brought into contact with an adherend, and is pressed as mentioned above, to adhere the polymer and the adherend (adhering). In this manner, an adhesion laminate of the polymer and the adherend is produced.
In the present invention, as mentioned above, the polymer can be altered by the surface-treating. Thus, for example, merely by pressing without using a primer, an adhesive, and the like, a polymer can be adhered to an adherend which cannot typically be adhered without these agents. This can shorten the adhering between the polymer and the adherend, and improve the production efficiency, for example. More specifically, for example, since the primer, adhesive, and the like are unnecessary, applying and drying these agents are unnecessary. Further, for example, since the primer, adhesive, and the like are unnecessary, a solvent is unnecessary, and effects such as the ease of a waste fluid treatment, improvement of recyclability, and a reduction in environmental burden can be obtained. The adhesion laminate production method according to the present invention is not limited thereto, and for example, a primer, an adhesive, and the like may be used as in the commonly used adhering way. In this case, non-limiting examples of the primer and the adhesive include, as mentioned above, those commonly used in the adhering or those similar thereto. The adhesion laminate production method according to the present invention alters the polymer by the surface-treating. This allows the affinity with a primer, an adhesive, and the like to be improved, and adhesion to be further facilitated, for example.
As mentioned above, for the flowable adherend, for example, the adherend may be applied to adhere to the polymer, for example. As a non-limiting example, how to apply the flowable adherend may be a commonly used way of applying the flowable adherend (e.g., a paint).
(11) Polymer
As a non-limiting example, the use of the polymer according to the present invention is not particularly limited, as mentioned above, and the polymer according to the present invention may be an adhesion laminate producing polymer for producing an adhesion laminate of a metal-plated polymer or the polymer and the adherend. The polymer according to the present invention has an amount of change X in contact angle with water represented by X=A0−A of more than 0°, for example, as mentioned above. As mentioned above, A0 is a contact angle of a non-oxidized surface of the polymer with water, and A is a contact angle of the oxidized surface of the polymer with water. The amount of change X in contact angle with water is, for example, 1° or more, 2° or more, 5° or more, 10° or more, 20° or more, or 30° or more, has an upper limit of 0° or less, and is, as a non-limiting example, 60° or less. As a non-limiting example, how to measure the contact angle with water and a measuring instrument therefor are as described in the Examples, which will be described later.
As a non-limiting example of a method for producing the polymer according to the present invention, a polymer to be treated in the surface-treating can be produced by altering through the surface-treating. The polymer to be treated is, for example, as mentioned above.
The polymer according to the present invention may be, for example, polypropylene having a ratio C═O/C—H of more than 0, the ratio C═O/C—H being a ratio of an area of a peak derived from C═O stretching at 1700 to 1800 cm−1 to an area of a peak derived from C—H stretching at 2800 to 3000 cm−1 in an infrared absorption spectrum of the oxidized surface. C═O/C—H is, for example, 0.0001 or more, 0.001 or more, 0.02 or more, or 0.03 or more, and is, for example, 1.0 or less, 0.4 or less, 0.3 or less, or 0.2 or less. As a non-limiting example, how to measure an infrared absorption spectrum (also referred to as an infrared spectrum, an IR spectrum, or merely IR) and a measurement instrument are described in the Examples, which will be described later.
The polymer according to the present invention contains, for example, but is not limited to, oxygen (α) and halogen (β). For example, the polymer according to the present invention may not contain the halogen (β).
Typically, as how to alter a polymer such as polyethylene and polypropylene, it has been known to introduce maleic anhydride using a radical reaction, for example. However, in such a typical way, for example, a crosslinking reaction and a decomposition reaction in the polymer may occur in parallel under commercially suitable conditions, and an introduction rate of maleic anhydride into the polymer is only about several percentages by weight in many cases. The introduction rate of a functional group into the polymer according to the present invention is preferably equal to or higher than that of such an example.
The polymer according to the present invention contains the oxygen (α) and the halogen (β) as, for example, functional groups. Examples of the functional group containing oxygen (α) include hydroxyl, carbonyl, and an amide group. Examples of the functional group containing halogen (β) include a chlorine group, a bromine group, an iodine group, an alkyl chloride group, an alkyl bromide group, and an alkyl iodide group.
For the polymer according to the present invention, the polymer containing oxygen (α) and halogen (β) (also referred to as a polymer skeleton) contains, for example, carbon and hydrogen and has a carbon-hydrogen bond. As the polymer, those described for the surface-treating may be used, and as mentioned above, examples thereof include polyolefin, polyester, and polycarbonate. Examples of the polyolefin include polyethylene and polypropylene. Examples of the polyester include polylactic acid.
The solid polymer according to the present invention may be, for example, an unmolded body or molded body, and may be used in combination with other polymers. As a form of the polymer according to the present invention, those described for the surface-treating may be used, for example.
The polymer according to the present invention may be produced by the surface-treating or a method including the surface-treating and still other steps (e.g., introduction of a functional group), for example, as mentioned above.
(12) Application of Metal-Plated Polymer
The application of the metal-plated polymer according to the present invention is not particularly limited, and may be used in any application. The metal-plated polymer according to the present invention is applicable in various fields such as, for example, transportation materials (automobiles, aircraft), electronic devices, building materials, medical devices, and large structures. Specifically, in recent years, from the viewpoint of weight reduction of transportation materials, multi-materialization, and the like, demands for metal-plating of polymers have been increasing in interior, exterior, and the like in the fields of automobiles, aircraft, and the like. According to the present invention, for example, even a resin material (polymer) which is hydrophobic and poor in adhesiveness can be plated with a metal, and it is possible to meet the demands.
In the present invention, for example, polymers used in various fields are altered to have desired properties. Thus, the metal-plated polymer according to the present invention is applicable to the various fields. As a specific example, the metal-plated polymer according to the present invention is applicable to a field of organic electroluminescence (EL). In this case, for example, the polymer having insulation properties may be altered to have electroconductivity, or the polymer may be altered to increase or decrease the degree of the electroconductivity, and examples of the polymer include a phenolic resin, an epoxy resin, and a diallyl phthalate resin. Further, for example, a luminescent molecule can be introduced into the polymer so that the polymer has a luminescence, and examples of the polymer include polycarbonate (PC), polyarylate (PAR) such as amorphous polyarylate, and polyether sulfonic acid (PES). In addition, for the polymer being the molded body, the molded body can be altered into a light emission layer or a positive hole layer. Examples of the polymer to be altered into a light emission layer include polyparaphenylene vinylene (PPV), polythiophene (PAT), polyfluorene (PF), and polyparaphenylene (PPP). Examples of the polymer to be altered into a positive hole layer include PEDOT/PSS and polyaniline/PSS.
Examples of the field include fields of electrical and electronic materials (such as a printed board), automobile parts, washing parts, amusement, electromagnetic shielding materials, heat transfer materials, heat absorbing members, flexible devices, and wearable devices. Examples of the field further include optical fields such as cameras, players such as CDs and DVDs, televisions such as projection televisions, contact lens, eyeglasses, cells such as blood analysis cells, and covers for LED lens. Further, the field can further be, for example, regenerative medicine. Non-limiting examples of the polymer used in these fields include PBA, PET, PC, an epoxy resin, a liquid crystalline polyester, and fluoroplastic.
(13) Applications of Adhesion Laminate
The application of the adhesion laminate according to the present invention is not particularly limited, and may be used in any application. The adhesion laminate according to the present invention is applicable to various fields such as, for example, fields of transportation materials (automobiles, aircraft), electronic devices, building materials, medical devices, food packaging materials, pharmaceutical packaging materials, groceries, daily necessities, and large structures. Specifically, in recent years, from the viewpoint of weight reduction of transportation materials, multi-materialization, and the like, demands for adhesion with different materials have been increasing in the fields of automobiles, aircraft, and the like. According to the present invention, for example, even a resin material (polymer) which is hydrophobic and poor in adhesiveness can be adhered to different materials such as aluminum, and it is possible to meet the demands.
In the present invention, for example, polymers used in various fields are altered to have desired properties. Thus, the adhesion laminate according to the present invention is applicable to the various fields.
Examples of the present invention will be described below in more detail. The present invention, however, is by no means limited thereby.
A polypropylene (PP) film was subjected to alteration treatment (surface-treating) in a gas phase reaction system using a reaction system shown in a perspective view of
As shown in
As shown in
Polymer Co., Ltd.) at 160° C. and 20 MPa for 10 minutes to mold, and further cutting a resultant molded product into 50 mm in length×10 mm in width×0.2 mm in thickness. In this condition, the reaction container 22 was sealed with a lid 23, and the acidic aqueous hydrochloric acid (NaClO2) solution 21 was then irradiated with light at the power of 60 W from the side surface of the reaction container 22 for 5 minutes. A light source used was an LED lamp with a wavelength of 365 nm. The distance between the light source and the reaction container 22 was 20 cm. Chlorine dioxide radicals generated by the light irradiation were surface-treated by reacting with the surface of the PP film 11A. The reaction was carried out in air at room temperature in atmosphere, without pressurization and f. The reaction was completed when the yellow coloration of the NaClO2 solution derived from the ClO2 radicals disappeared. After completion of the reaction, the PP film 11A was washed with purified water and dried under reduced pressure overnight. In this manner, the PP film 11A was subjected to the alteration treatment (surface treatment), thereby producing a surface-treated polymer.
APP film 11A was subjected to alteration treatment (surface-treating) in the same manner as in Reference Example 1 except that the cylindrical container containing the PP film 11A in the reaction container 22 was covered with aluminum to shield from light, so that the PP film 11A was not exposed to light. Specifically, in this example, the surface-treating was performed with the reaction system in the surface-treating (the cylindrical container containing the PP film 11A in the reaction container 22) not irradiated with light and only the radical generation reaction system (the cylindrical container containing the acidic aqueous hydrochloric acid (NaClO2) solution 21 in the reaction container 22) irradiated with light. In this manner, the PP film 11A was subjected to an alteration treatment (surface-treating) to produce a surface-treated polymer according to the present invention.
(Measurement of IR Spectrum)
IR spectra (infrared absorption spectra) were measured for the PP films 11A of Reference Example 1 and Example 1 before (before the surface-treating) and after (after the surface-treating) the reaction. In this reference example and this example and all of the following reference examples and examples, FT/IR-4700 (trade name, manufactured by JASCO Corporation) with ATR PRO ONE (trade name, manufactured by JASCO Corporation) and a diamond prism attached was used as an IR spectrometer. As a result, in both of Reference Example 1 and Example 1, the peak intensity at around 2900 cm−1 decreased and the peak intensity at around 1700 cm−1 increased after the reaction as compared with those before the reaction. This result implies that the methyl on the surface of the PP film 11A was oxidized into the carboxy. Further, Example 1 demonstrates that in the surface-treating, the reaction proceeds without irradiation of the reaction system of the surface-treating with light, thereby producing the surface-treated polymer according to the present invention. In other words, this example demonstrates that the surface-treated polymer production method according to the present invention does not necessary to irradiate the surface of the polymer with light, thereby producing the surface-treated polymer according to the present invention in a simplified manner and at low cost.
The results of the measurement of the IR spectrum of Reference Example 1 are shown in Table 4 below. Table 4 shows the measurement results of the PP film 11A before the reaction as a control together with the results of changes in reaction time of the surface-treating to 10 minutes and 60 minutes. As shown in Table 4 below, the ratio C═O/C—H of an area of a peak derived from C═O stretching at 1700 to 1800 cm−1 to an area of a peak derived from C—H stretching at 2800 to 3000 cm−1 was considerably increased compared to the area before the reaction for the reaction time of both 10 minutes and 60 minutes.
(Measurement of Contact Angle with Water)
The contact angles of the PP films of Reference Example 1 and Examples 1 with water were measured using Drop Master DM300 (trade name, manufactured by Kyowa Interface Science Co., Ltd.). In the above measurement, 1 microliter of pure water was added dropwise on the surface of the object to be measured, and the contact angle after 2 seconds of the addition was calculated by a static contact angle method using FAMAS (trade name, manufactured by Kyowa Interfacial Science Co., Ltd.) as analysis software. In all of the following reference examples and examples, the contact angle with water was measured by the same method using the same device as in this example.
The measurement results of the contact angle with water in Reference Example 1 are shown in Table 5 below. Table 5 also shows the measurement results of the PP film 11A before the reaction as a control together with the results of changes in reaction time of the surface-treating to 10 minutes and 60 minutes. As shown in Table 5 below, the contact angle was about 20° or more smaller than that before the reaction at both 10 and 60 minutes of the reaction time. It was thus demonstrated that hydrophilicity of the PP film 11A was increased by the surface treatment.
Table 6 and Table 7 below show the results of the IR measurement and the measurement of the contact angle with water of the PP films of Reference Example 1 (with irradiation of the PP film 11A with light) and Example 1 (without irradiation of the PP film 11A with light). In Tables 6 and 7, the reaction time for the surface-treating was 10 minutes. As shown in Tables 6 and 7 below, neither Reference Example 1 nor Example 1 changed the C═O/C—H and the contact angle with water. This demonstrates that, in the surface-treating, the number of C═O bonds and hydrophilicity increased without irradiation of the PP film 11A with light as well as with the irradiation. In other words, in the surface-treated polymer production method according to the present invention, the same degree of the surface alteration effect as that with irradiation of the surface of the polymer with light can be obtained without the light irradiation. Thus, this example confirmed that the surface-treated polymer according to the present invention can be produced in a simplified manner and at low cost.
In the following manner, a polylactic acid (PLA) film was subjected to alteration treatment (surface-treating) in a gas phase reaction system.
An acidic aqueous hydrochloric acid (NaClO2) solution was placed in a small petri dish (30 mm in diameter×10 mm in depth) as a reaction container. As the acidic aqueous hydrochloric acid (NaClO2) solution, an aqueous solution obtained by mixing H2O (7 mL), NaClO2 (1000 mg), and 35% HClaq. (1000 μL) was used. This small petri dish and the polylactic acid (PLA) film were placed in a large petri dish (700 mm in diameter×180 mm in depth). The polylactic acid (PLA) film was obtained by heat pressing 3 g of polylactic acid pellets (trade name: 2003D (registered trademark), manufactured by Nature Works) at 170° C. and 10 MPa for 10 minutes. The PLA film cut into 50 mm in length×10 mm in width×0.3 mm in thickness was used. Thereafter, the large petri dish was covered with a lid and pre-heated at 70° C. for 5 minutes. Then, while the heating was continued, light of the power of 60 W was applied from above the lid for 5 minutes. A light source used was an LED lamp with a wavelength of 365 nm. The distance between the light source and the large petri dish was 20 cm. Chlorine dioxide radicals generated by the light irradiation were surface-treated by reacting with the surface of the PLA film. The reaction was carried out in air at room temperature in atmosphere, without pressurization and decompression. The reaction was completed when the yellow coloration of the NaClO2 solution derived from the ClO2 radicals disappeared. After completion of the reaction, the PLA film was washed with purified water and dried under reduced pressure overnight. In this manner, the PLA film was subjected to alteration treatment (surface-treating).
Under the reaction conditions of the surface-treating, the reaction was performed with the change in reaction time to 0 minutes (i.e., unreacted), 10 minutes, and 30 minutes, and then the IR measurement was performed. The conditions for IR measurement were the same as described above. The result confirmed that by the surface-treating, hydrophilic functional groups such as alcoholic hydroxyl (C—OH) and carboxy (COOH) increased on the surface of the PLA film.
A polypropylene (PP) film was subjected to alteration treatment (surface-treating) in a gas phase reaction system using a reaction system shown in a cross-sectional view of
As shown in
As shown in
(NaClO2) solution 101, ClO2 generated by reacting NaClO2 (200 mg) and HCl with each other is dissolved. In this state, air 106 was blown into the acidic aqueous hydrochloric acid (NaClO2) solution 101 at a flow rate of 0.2 L/min using an air pump as shown in
In this manner, in this example (Example 2), the ClO2 gas was activated by light irradiation to be chlorine dioxide radicals, while a reaction system containing chlorine dioxide radicals (halogen oxide radicals) and the PP film 111 (polymer) was not irradiated with light. Even in the case in which the length of the passage 105 was 1000 m (1 m), the surface of the PP film 111 could be altered by alteration treatment (surface-treating), thereby producing a surface-treated polymer according to the present invention.
A surface of a polypropylene (PP) film was plated with nickel in the following manner, thereby producing a metal-plated polymer.
In this example, liquids A, B, and C were used.
Liquid A: The liquid A was prepared by adding 35% HClaq. (0.1 mL) to purified water (50 mL), and further dissolving stannous chloride (SnCl2) (0.1 g) in the resultant solution.
Liquid B: The liquid B was prepared by dissolving palladium chloride (PdCl2) (0.01 g) in 35% HClaq. (0.1 mL) and further adding purified water (50 mL) to the resultant solution.
Liquid C: The liquid C was prepared by dissolving nickel sulfate hexahydrate (2.63 g), glycine (1.50 g), and sodium hypophosphite monohydrate (2.12 g) in purified water (95 mL) in this order, adjusting the pH of the resultant solution to 5.0, and then further adding purified water to adjust the total amount of the solution to 100 mL.
First, the PP film (the surface-treated polymer according to the present invention) which had been subjected to alteration treatment in Example 1 (after the surface-treating) was immersed in the liquid A for 2 minutes, washed with water, then further immersed in the liquid B, and further washed with water. This was repeated a total of two times, thereby supporting a catalyst (stannous chloride and palladium chloride) on the altered surface of the PP film. Thereafter, the catalyst-supported PP film was immersed in the liquid C which had been heated at 70° C., and then stood still for 1 hour (60 minutes), thereby precipitating metal nickel on the altered surface (catalyst-supported surface). In this manner, the surface of the PP film was plated with nickel (plating), thereby producing a metal-plated polymer.
As a comparative example, the same treatment was performed in the same manner as in Example 1 except that an untreated PP film (which had not been subjected to the surface-treating) was used as a substitute for the PP film of Example 1. As a result, the untreated PP film could not be plated while the PP film which had been subjected to alteration treatment in Example 1 (after the surface-treating) could be plated with nickel in this example. In other words, the result confirmed that the metal-plated polymer production method according to the present invention could plate, with metal, PP films which were difficult to be plated by a commonly used method.
Metal-plated polymers were produced in the same manner as in Example 1 except that the immersion time for the PP film in the liquid C was changed to 3 minutes, 10 minutes, 30 minutes, and 60 minutes.
The metal-plated polymers plated with nickel in this example were subjected to the cross-cut test. The test tape used was an adhesive tape defined in JIS Z 1522 (adhesive strength: about 8 N per 25 mm in width) with a nominal width of 12 to 19 mm. The test was specifically performed in the following steps (1) to (3). As a comparative example, the same treatment was performed in the same manner as in this example except that an untreated PP film (which had not been subjected to the surface-treating) was used, thereby producing metal-plated polymers, which were then subjected to the same cross-cut test.
(1) In a part to be subjected to a tape test in the plated surface, stripe cuts reaching the base (PP film) were made with a cutter so as to form a square having a side of 2 mm.
(2) A test tape adhered to the plated surface while leaving 30 to 50 mm of an non-taped part. At this time, while taking care not to form air bubbles, the test tape was pressed with a finger for about 10 seconds.
(3) The tape for the part left in the item (2) above was pinched with fingers, and pulled strongly in a direction perpendicular to the plated surface to peel off the tape instantaneously.
As a result of the cross-cut test, in the comparative example (untreated PP film), a metal nickel layer formed by the plating adhered to the tape and peeled off. In contrast, as a result of using the PP films which had been subjected to alteration treatment (after the surface-treating), each metal nickel layer that had been formed by plating was hardly peeled off at each of the immersion times of 3 minutes, 10 minutes, 30 minutes, and 60 minutes in the liquid C.
In the following manner, a polypropylene (PP) film and an aluminum plate adhered to each other, thereby producing an adhesion laminate.
As shown in the perspective view of
Further, the adhesion laminates of
The PP film which had been subjected to alteration treatment (reaction at room temperature for 10 minutes) in Example 1 and the PLA film which had been subjected to alteration treatment (reaction at 70° C. for 5 minutes) in Reference Example 2 were each cut into 4 mm in length×2 mm in width, and then adhered to each other by heat pressing at 50° C. and 10 MPa for 5 minutes, thereby producing an adhesion laminate of the PP film and the PLA film. Thus, in this example, the adhesion laminate could be produced by only pressing the PP film and the PLA film without a primer, an adhesive, and the like.
Further, an adhesion laminate was produced in the same manner except that one or both of the PP film and the PLA film was substituted with an unreacted film (which had not been subjected to alteration treatment). Then, the adhesion laminates were subjected to a tensile test in the same manner as in Example 5. The results of the tensile test are shown in Table 9 below. In Table 9, “PLA” and “PP” represents unreacted PLA and unreacted PP (which has not been subjected to the surface-treating). “Oxidized PLA” and “oxidized PP” represent PLA and PP, which have been subjected to alteration treatment (which have been subjected to the surface-treating to oxidize each surface). As shown in Table 9, the adhesion laminate of unreacted PLA and unreacted PP, and the adhesion laminate of oxidized PLA and unreacted PP were extremely weak in adhesive strength and peeled off immediately, and could not be subjected to the tensile test. In contrast, the adhesion laminate of PLA and oxidized PP and the adhesion laminate of oxidized PLA and oxidized PP exhibited a certain peel strength. This confirmed that that the adhering could be performed without a primer (undercoat layer) and an adhesive.
The surfaces of polymers (resins) shown in Tables 10 to 12 below were subjected to alteration treatment by the surface-treating according to the present invention (surface-treated polymer production method according to the present invention), thereby producing surface-treated polymers according to the present invention. In addition, the surface-treated polymers were plated with nickel or copper, thereby producing metal-plated polymers. In this example, the surfaces of the polymers were not irradiated with light in the surface-treating.
In this example, the surface-treating (surface-treated polymer production method) was performed in the same manner as in Example 2 except that the polymer was changed from the PP film to polymers shown in Tables 10 to 12. The size of each of the polymers was also the same as that of the PP film of Example 2.
In this example, nickel plating after the surface-treating was performed under the same conditions as in Example 3.
In this example, copper plating after the surface-treating was performed as follows. Specifically, first, a film (polymer) which had been oxidized (subjected to the surface-treating) was immersed, for 6 minutes, in a OPC-50 Inducer M solution (trade name, manufactured by Okuno Chemical Industries Co., Ltd.) heated at 45° C., and then immersed, for 5 minutes, in an OPC-150 Cryster RW solution (trade name, manufactured by Okuno Chemical Industries Co., Ltd.) at 25° C., thereby supporting the catalyst on the film. The film was then plated with copper by immersing, for 1 minute, in an ATS Adcopper IW solution (trade name, manufactured by Okuno Chemical Industries Co., Ltd.) at 25° C.
The combinations of the polymers used in this example and the metal (nickel or copper) used for plating are shown in Tables 10 to 12 below. In Tables 10 to 12 below, ∘ indicates that peeling was not found in the same cross-cut test as in Example 4, Δ indicates that partial peeling was found in the cross-cut test, but plating could be performed. This example confirmed that surface-treated polymers according to the present invention could be produced from various polymers by the surface-treating according to the present invention (the surface-treated polymer production method according to the present invention). This example further confirmed that metal-plated polymers could be produced through plating the surface-treated polymers by the metal-plated polymer production method according to the present invention.
The surfaces of polymers (resins) shown in Tables 13 to 18 below were subjected to alteration treatment by the surface-treating according to the present invention (surface-treated polymer production method according to the present invention), thereby producing surface-treated polymers according to the present invention. Adhesion laminates were produced by adhering surface-treated polymers to polymers or metals (adherends) shown in Tables 13 to 18 below. In this example, the surfaces of the polymers were not irradiated with light in the surface-treating.
In this example, the surface-treating (surface-treated polymer production method) was performed in the same manner as in Example 2 except that the polymer was changed from the PP film to polymers shown in Tables 13 to 18. The size of each of the polymers was also the same as that of the PP film of Example 2. In Tables 13 to 18 below, “SUS” indicates a stainless steel material.
In this example, regarding the adhering after the surface-treating, adhesion between the polymer and the metal was performed in the same manner as in Example 5, and adhesion between polymers was performed in the same manner as in Example 6.
In Tables 13 to 18 below, ∘ indicates that spontaneous peeling was not found after 24 hours of standing still due to firm adhesion, Δ indicates that although the polymer and the metal adhere to each other, spontaneous peeling was found partially after 24 hours of standing still, and x indicates that the polymer and the metal could not adhere to each other. In Tables 13 to 18 below, “Combination of Oxidized Polymers” indicates adhesion of polymers which have been subjected to the surface-treating, and “Combination of Untreated Polymers” indicates adhesion of (untreated) polymers which have not been subjected to the surface-treating. The adhesion of untreated polymers which had not been subjected to the surface-treating was performed under the same conditions as in the adhering of Example 6.
As shown in Tables 13 to 18, this example confirmed that surface-treated polymers according to the present invention could be produced from various polymers by the surface-treating according to the present invention (the surface-treated polymer production method according to the present invention). This example further confirmed that adhesion laminates could be produced through adhering various polymers or adhering various polymers and metals by the adhesion laminate production method according to the present invention. In contrast, as shown in Tables 13 to 18 below, the adhesive strength between the polymers which had not been subjected to the surface-treating was very weak and could not adhere to each other.
While the present invention has been described above with reference to exemplary embodiments and examples, the present invention is by no means limited thereto. Various changes and modifications that may become apparent to those skilled in the art may be made in the configuration and specifics of the present invention without departing from the scope of the present invention.
As described above, the present invention can provide a surface-treated polymer production method, a metal-plated polymer production method, and an adhesion laminate production method each of which can be performed in a simplified manner and at low cost, and can provide a polymer, a metal-plated polymer, and an adhesion laminate each of which can be produced in a simplified manner and at low cost. The metal-plated polymer according to the present invention is applicable in various fields such as, for example, fields of transportation materials (automobiles, aircraft), electronic devices, building materials, medical devices, and large structures without particular limitations.
The present application claims priority from Japanese Patent Application No. 2018-096676 filed on May 18, 2018 and Japanese Patent Application No. 2018-096677 filed on May 18, 2018, the entire disclosure of which is incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-096676 | May 2018 | JP | national |
| 2018-096677 | May 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/019814 | 5/17/2019 | WO | 00 |
