KR20070055511A - Process for production of surface-functional members and process for production of conductive membranes - Google Patents

Abstract

A step of directly bonding a graft polymer having a functional group and a crosslinkable functional group capable of interacting with the functional material on the substrate, and adsorbing the functional material to the functional group capable of interacting with the functional material of the graft polymer to form a functional material adsorption layer And a step of forming a crosslinked structure in the functional material adsorption layer by applying energy to the functional material adsorption layer, and the method of producing a surface functional member.

Description

The manufacturing method of a surface functional member, and the manufacturing method of a conductive film {PROCESS FOR PRODUCTION OF SURFACE-FUNCTIONAL MEMBERS AND PROCESS FOR PRODUCTION OF CONDUCTIVE MEMBRANES}

The present invention relates to a method for producing a surface functional member and a method for producing a conductive film, and more particularly, to a method for producing a surface functional member having a functional surface layer formed by adsorbing various functional materials and a method for producing a conductive film. .

Conventionally, various surface functional members which adsorb | suck functional microparticles | fine-particles or low molecular weight (functional material) to arbitrary base materials, and form the surface layer which has various functions are proposed. As a material which made the functional material adsorb | suck on a base material, the material which made the fine particle or low molecule adsorb | suck to the graft polymer which exists on a base material is mentioned, for example, These materials are useful for various uses.

For example, Patent Document 1 discloses that adsorbing silica particles as fine particles to a graft polymer chain present on a support is useful as an antireflection member. Patent Literature 2 describes that a film (infrared absorbing layer) in which an infrared absorbing dye is adsorbed on a graft polymer is thinner and has a higher infrared absorbing ability than a film containing a conventional dye. In addition, since the graft polymer as described above is directly bonded to the substrate by covalent bonding, by adsorbing the functional material to the graft polymer, adhesion to the substrate is strong, mechanical wear resistance and organic solvent resistance are high, and surface durability excellent in durability. Absence was obtained.

However, in the surface functional member obtained by the conventional method, since the graft polymer and the functional material as the adsorbent material are bonded by ionic bonds, even when the functional material is adsorbed to the graft polymer, it is brought into contact with an electrolyte solution such as saline solution. There has been a problem that the functional material is detached from the graft polymer and the like, and the effect of the functional material does not persist. In particular, in materials used outdoors, when exposed to rain or the like for a long time, the tendency of the functional material to detach from the graft polymer was remarkable.

As mentioned above, it is a present situation that further improvement is calculated | required about the retention of the functional material in the surface functional member, and the improvement of the persistence.

Background Art [0002] Recently, image displays (displays) represented by liquid crystal displays (LCDs), plasma displays (PDPs), and electroluminescent (EL) devices have been used in various fields such as televisions, computers, and various mobile devices that have been widely used in recent years. It has become widely used and is making amazing progress. In addition, as part of de-fossil energy in consideration of the global environment, there is a growing demand for dissemination by high functionalization of solar cells.

A transparent conductive film is used for such a display element and a solar cell. It is preferable that this transparent conductive film can achieve high electrical conductivity and high transmittance in the visible light region, specifically, transmittance of 80% or more in the range of wavelength 380 to 780 nm.

Initially, the conductive film was formed by forming a metal such as Au, Ag, Cu, Al into a thin film having a thickness of about 3 to 15 nm, but the metal thin film had a large absorption and also had a problem in film strength. In recent years, a low resistance film called an ITO film formed by forming an indium oxide (In ₂ O ₃ ) containing tin as a dopant on a glass substrate as a transparent conductive film has been widely used as an electrode for display elements such as liquid crystals. However, in the case of ITO, since the starting material is indium, which is a rare metal, there is a limit in reducing the cost of the substrate because it is expensive.

For this reason, the transparent conductive film which has zinc oxide (ZnO) as a main component is gradually spreading from a viewpoint of cost and stable supply. By adding an impurity such as Al, the ZnO film obtains a low resistance film comparable to that of ITO. Such a ZnO-based transparent conductive film is generally produced by sputtering or CVD. The sputtering method has a problem that the manufacturing cost is high because the manufacturing apparatus is expensive, and a large area film is difficult to be formed. In addition, the CVD method is low in manufacturing cost because the device is inexpensive and continuous production is possible, but there is a drawback that if the film having a smooth surface is formed, the resistance value increases and the conductivity becomes low. Moreover, even if any method, such as a sputtering method and a CVD method, was taken, there existed a problem that a metal thin film had insufficient film strength and was low in abrasion resistance.

In view of improving the film strength, a method of immobilizing conductive particles such as metal on a substrate using a binder has also been proposed. However, the conductive film obtained by this method does not have conductivity, and the conductivity may be lowered depending on the fixed state of the fine particles. Thus, the conductive film is insufficient for achieving sufficient film strength and high conductivity.

In order to solve this problem, the conductive film which electrostatically couples electroconductive fine particles to this ionic group using the base material provided with the surface graft polymer which has an ionic group, for example is proposed (for example, refer patent document 3). .). According to this conductive film, the conductive fine particles are ionically adsorbed to the substrate surface and immobilized to form a conductive expression region, whereby a certain result can be achieved in achieving both sufficient film strength and high conductivity. However, like this conductive film, the electroconductive particle immobilized by an ionic bond might detach | desorb from the graft polymer, for example, when it contacted electrolyte solution, such as saline.

From this point of view, the present situation is that further improvement is required for high conductivity and its durability.

In addition, various conductive films are conventionally used for the formation of wiring boards. For example, copper thin films formed on substrate surfaces such as polyimide are preferably used as copper-clad substrates for electrical wiring.

As a typical example of the circuit board forming method, there is a method of adhering a copper foil with an adhesive to the surface of a polyimide substrate, and selectively etching the copper foil to form a predetermined pattern of wiring. However, in this method, since the heat resistance of the adhesive for bonding the metal layer (copper) and the substrate is low, there is a problem that the heat resistance as the circuit board is lowered.

As for the formation of the metal layer on the surface of the substrate, a synchronous plate production method using no adhesive, which forms a copper layer on the polyimide substrate by forming a metal layer on a polyimide substrate by sputtering and then plating, is performed. It is developed (refer patent document 4). However, in this method, since no adhesive is used, there is a problem that the adhesion between the substrate and the copper is bad.

In order to improve the adhesion between the substrate and the metal, the surface of the substrate may be uneven by etching, and the adhesion may be improved by the anchor effect. However, unevenness of the substrate surface is disadvantageous in terms of fine wiring and high frequency adaptability.

In order to improve this point, the graft polymer may be bonded to the surface of the base material, and high adhesion may be expressed by interposing the graft polymer. As such a technique, for example, a surface is subjected to plasma treatment to a polyimide substrate, a polymerization initiator is introduced to the surface of the polyimide substrate, and a monomer is polymerized from the polymerization initiator to introduce a surface graft polymer onto the surface of the polyimide substrate. By performing a process, the method of improving the adhesiveness of a polyimide substrate and a copper layer is proposed (refer nonpatent literature 1). However, this technique has a problem that a large-scale treatment such as plasma treatment is required.

When the graft polymer is bonded to the surface of the base material, sufficient adhesion to the substrate and the metal can be obtained. However, the metal may peel off from the graft polymer under conditions such as high humidity. Therefore, improvement is required.

Patent Document 1: Japanese Patent Publication No. 2003-112379

Patent Document 2: Japanese Patent Publication No. 2003-57435

Patent Document 3: Japanese Patent Publication No. 2003-8040

Patent Document 4: Japanese Patent Publication No. 2003-46223

Non Patent Literature 1: N. Inagaki, S. Tasaka, M. Masumoto, "Macromolecules", 1996, Vol. 29, p.1642

The present invention provides a method for producing a surface functional member having a functional material adsorption layer having excellent durability in which a functional material is strongly adsorbed on the surface of the base material, and having excellent retention and durability of the functional material.

This invention provides the manufacturing method of the electrically conductive film which has high electroconductivity and is excellent in the durability.

This invention provides the manufacturing method of the electrically conductive film which has high electroconductivity and adhesiveness, and is excellent in the retention property of a conductive material, and its durability.

That is, the 1st aspect of this invention is a functional group (henceforth "interacting group" suitably called) which can interact with a functional material on a base material, and a crosslinkable functional group (henceforth "crosslinkable group" suitably). Directly adhering to the graft polymer having a graft polymer; adsorbing a functional material to form a functional material adsorption layer on a functional group capable of interacting with the functional material possessed by the graft polymer; It is a manufacturing method of the surface functional member which has a process of forming a crosslinked structure in the said functional material adsorption layer by providing energy.

According to a second aspect of the present invention, there is provided a step of directly bonding a graft polymer having a functional group (interacting group) and a crosslinkable functional group (crosslinkable group) capable of interacting with conductive particles on a substrate, and the graft polymer has A functional group capable of interacting with the conductive particles has a step of adsorbing the conductive particles to form a conductive particle adsorption layer and a step of forming a crosslinked structure in the conductive particle adsorption layer by applying energy to the conductive particle adsorption layer. It is a manufacturing method of the conductive film characterized by the above-mentioned.

A third aspect of the present invention provides a process for directly bonding a graft polymer having a functional group (interacting group) and a crosslinkable functional group (crosslinkable group) capable of interacting with an electroless plating catalyst or a precursor thereof on a substrate, Forming an electroless plating catalyst-containing layer by applying an electroless plating catalyst or a precursor thereof to the graft polymer, and forming a crosslinked structure in the electroless plating catalyst-containing layer by applying energy to the electroless plating catalyst-containing layer. And it has a process of performing electroless plating, It is a manufacturing method of the conductive film characterized by the above-mentioned.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

1. Manufacturing method of surface functional member

The method for producing a surface functional member of the present invention is a step of directly bonding a graft polymer having a functional group (interacting group) and a crosslinkable group capable of interacting with a functional material on a substrate (hereinafter, appropriately referred to as "graft polymer production process"). A step of adsorbing the functional material to form a functional material adsorption layer (hereinafter referred to as a "functional material adsorption layer formation process" as appropriate), and a functional group capable of interacting with the functional material possessed by the graft polymer; By providing energy to the said functional material adsorption layer, it has a process of forming a crosslinked structure in the said functional material adsorption layer (henceforth "crosslinked structure formation process"), It is characterized by the above-mentioned.

In the method for producing a surface functional member of the present invention, a functional material is adsorbed to an interactive group of a graft polymer bonded directly on a substrate to form a functional material adsorption layer, and then a crosslinkable group present in the graft polymer is reacted. A crosslinked structure is formed in the functional material adsorption layer. Although the action of the present invention is not clear, by forming a crosslinked structure in the functional material adsorption layer, the functional material adsorbed to the interacting group in the graft polymer is contained in the crosslinked structure, so that it is stably immobilized in the functional material adsorption layer. The functional material adsorption layer according to the present invention is not only exhibiting high durability, but also remarkably improved in retainability and durability of the functional material.

Hereinafter, each process in the manufacturing method of the surface functional member of this invention is demonstrated sequentially.

<Graft polymer production process>

In the present invention, first, in the graft polymer production step, the graft polymer is directly bonded onto the substrate.

Thus, as a method of forming the state in which the graft polymer is bonded on the substrate, a known method may be applied. Reference may be made to the description of “Surface Modification and Adhesion by Macromonomers”. In addition, the method called the surface graft polymerization method described below can also be applied.

(Surface Graft Polymerization Method)

It is preferable that the graft polymer in this invention was formed by the surface graft polymerization method.

In general, the surface graft polymerization method is a method for synthesizing a graft (grafting) polymer by providing an active species on a polymer compound chain forming a solid surface, further polymerizing another monomer based on the active species. .

As the surface graft polymerization method for realizing the present invention, any known method described in the literature can be used. For example, Shin Molecular Experimental Science 10, Polymer Society of Japan, 1994, published by Kyoritsu Shotan Co., Ltd., p135, describes the photograft polymerization method and the plasma irradiation graft polymerization method as the surface graft polymerization method. In addition, irradiation graft polymerization methods such as gamma rays and electron beams are described in the adsorption technique manual, NTS Corporation, Takeuchi Supervision, issued Feb. 1999, p203, p695.

As a specific method of the photografting polymerization method, the method described in Unexamined-Japanese-Patent No. 63-92658, Unexamined-Japanese-Patent No. 10-296895, and Unexamined-Japanese-Patent No. 11-119413 can be used.

In the plasma irradiation graft polymerization method and the radiation graft polymerization method, it can be produced by the methods described above, and by the methods described in Y. Ikada et al, Macromolecules vol. 19, page 1804 (1986) and the like. Specifically, a graft polymer can be obtained by treating a surface of a polymer such as PET with a plasma or an electron beam to generate radicals on the surface, and then reacting the active surface with a monomer.

The photograft polymerization method is applied to the surface of a film base material as described in Japanese Patent Application Laid-Open No. 53-17407 (Kansai Paint) and Japanese Patent Application Laid-Open No. 2000-212313 (Dainippon Ink) in addition to the documents described above. A graft polymer can also be obtained by apply | coating a photopolymerizable composition and then irradiating light by making a radical polymerization compound contact.

Moreover, as a means of forming the state in which the graft polymer is couple | bonded on the board | substrate, besides these, reactive functional groups, such as a trialkoxy silyl group, an isocyanate group, an amino group, a hydroxyl group, and a carboxyl group, are provided to the terminal of a high molecular compound chain, and this is described with this. It can also be formed by the coupling reaction of the surface functional group.

In the graft polymer production step in the present invention, a specific method in the case of using the surface graft polymerization method will be described.

In the present invention, an active point is generated on the surface of the substrate by contacting the surface of the substrate with a polymerizable compound having an interactive group and a polymerizable compound having a crosslinkable group and imparting energy, thereby producing the active point and the polymerizable compound. Polymerizable groups react to cause surface graft polymerization.

The contact of the polymerizable compound to the substrate surface may be performed by immersing the substrate in the liquid composition containing the polymerizable compound. It is preferable to carry out by apply | coating to.

Moreover, as a method of providing energy, heating and radiation irradiation can be used, for example. Specifically, light irradiation by UV lamp, visible light, etc., heating by a hot plate, etc. are possible, for example.

In the present invention, the graft polymer to be directly bonded on the substrate is a graft polymer having an interactive group and a crosslinkable group, and has an interactive group and a crosslinkable group in the polymer structure, thereby adsorbing and crosslinking the functional material. Both functions of formation can be exerted.

The graft polymer in this invention is formed by copolymerization of the polymeric compound which has an interactive group, and the polymeric compound which has a crosslinkable group, The graft polymer which is this copolymer on a base material by using the surface graft polymerization method mentioned above. Can be combined directly.

The polymerizable compound having an interactive group and the polymerizable compound having a crosslinkable group may be any of monomers, macromers and polymers having a polymerizable group, but are preferably monomers from the viewpoint of polymerizability.

As a monomer which has an interactive group used for formation of a graft polymer, and a monomer which has a crosslinkable group, 1 type may respectively be used and multiple types of monomer may be used together.

In formation of the graft polymer in this invention, although it is necessary to use at least 1 sort (s) of the monomer which has an interactive group, and a crosslinkable group, in another range other than that in the range which does not impair the effect of this invention, You may use a copolymer monomer.

As a content ratio of the monomer component which has an interactive group in a graft polymer, and the monomer component which has a crosslinkable group, 30: 70-99: 1 is preferable at a molar ratio from a viewpoint of compatibility of adsorption of a functional material and formation of a crosslinked structure. 50: 50-95: 5 are more preferable, and 60: 40-90: 10 are still more preferable.

In addition, the detail regarding the matter regarding adsorption | suction of a functional material, and the matter regarding formation of a crosslinked structure is explained in full detail in description of the "functional material adsorption layer formation process" and the "crosslinking structure formation process" mentioned later.

Hereinafter, the monomer which has an interactive group which can be used for formation of the graft polymer in this invention, and the monomer which has a crosslinkable group are demonstrated in detail.

Monomers with Interacting Groups

The interactive group possessed by the graft polymer is a functional group having interactivity according to the functional material adsorbed to the graft polymer.

In the present invention, the interactive group is a functional group capable of adsorbing a functional material, but when the functional material is not adsorbed, it may function as a functional group having a structure used for crosslinking reaction.

As an interactive group in this invention, it is preferable that it is a polar group, and it is more preferable that it is an ionic group. Therefore, as a monomer which has an interactive group in this invention, the monomer (ionic monomer) which has an ionic group is used preferably.

As the ionic monomer, a monomer having a positive charge such as ammonium or phosphonium, or an acid group capable of dissociating with a negative charge or having a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group A monomer etc. are mentioned.

An ionic monomer capable of forming an ionic group which can be preferably used in the present invention is a monomer having a positive charge such as ammonium or phosphonium or a sulfonic acid group, a carboxyl group, a phosphoric acid group, a phosphonic acid group, or the like as described above. And monomers having an acidic group which may have a negative charge of or dissociate into a negative charge.

The following monomers are mentioned as a specific example of the ionic monomer especially useful in this invention. For example, (meth) acrylic acid or its alkali metal salts and amine salts, itaconic acid or its alkali metal salts and amine salts, allylamine or its halogenated hydrochlorides, 3-vinylpropionic acid or its alkali metal salts and amine salts, vinylsulfonic acid or its alkalis Metal salts and amine salts, styrenesulfonic acid or its alkali metal salts and amine salts, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salts and amine salts, 2-acrylamide-2-methyl Propanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylates or salts thereof, 2-dimethylaminoethyl (meth) acrylate or their halogenated hydrochlorides, 3-trimethylammoniumpropyl (Meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxy Ropil) and the like ammonium chloride.

Moreover, in this invention, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monometholol (meth) acrylamide, N-dimetholol (meth) acrylamide, N-vinylpyrrolidone And polar monomers such as N-vinylacetamide and polyoxyethylene glycol mono (meth) acrylate are also useful.

Especially as a monomer which has an interactive group in this invention, the monomer (anionic monomer) which has anionic functional groups, such as acrylic acid, is preferable.

Monomer having a crosslinkable group

The crosslinkable group possessed by the graft polymer is a reactive group which reacts with an interactive group or other functional group contained in the graft polymer to form a covalent bond. For example, a hydroxyl group, a metirol group, a glycidyl group, an isocyanate group, Functional groups, such as an amino group, are mentioned.

In this invention, as a monomer (namely, a reactive monomer) which has a crosslinkable group which can be used, it can select from a well-known thing suitably, and can use.

As a specific example of the monomer which has a crosslinkable group, 2-hydroxyethyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl meth, for example Those having a hydroxyl group such as acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and the like; Those having a metirol group such as N-metholacrylamide, N-metholol methacrylamide, methirol stearoamide, etc .; Those having glycidyl groups such as glycidyl acrylate and glycidyl methacrylate; One having an isocyanate group such as 2-isocyanate ethyl methacrylate (for example, trade name: Carens M0I, Showa Denko); The thing which has amino groups, such as 2-aminoethyl acrylate and 2-aminoethyl methacrylate, etc. are mentioned.

(materials)

As a base material used in this invention, it is a dimensionally stable plate-shaped thing, and if it satisfies required flexibility, strength, durability, etc., it can use any, and it selects suitably according to a purpose of use.

In the case of selecting a transparent substrate requiring light transmittance, for example, glass, plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, butyrate cellulose, butyrate cellulose acetate, cellulose nitrate, polyethylene terephthalate, Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like). As the base material of the surface functional member that does not require transparency, in addition to the above, paper, a paper laminated with plastic, a metal plate (for example, aluminum, zinc, copper, etc.), and a metal laminated or deposited as described above Paper or a plastic film.

Although the base material is suitably selected according to the use of a surface functional member and the relationship with the functional material adsorbed, the base material which has a surface which consists of a polymeric resin from a viewpoint of workability and transparency is preferable, Specifically, a resin film and a surface The transparent inorganic base material, such as glass in which resin is coat | covered, and the composite material in which a surface layer consists of a resin layer are preferable.

As a base material by which resin was coat | covered on the surface, the laminated board which a resin film adhered to the surface, the base material which was treated with a primer, the hard coat process base material, etc. are mentioned as a representative example. As a composite material which a surface layer consists of a resin layer, the resin sealing material with an adhesive bond layer formed in the back surface, laminated glass which is a laminated body of glass and resin, etc. are mentioned as a typical example.

For example, when using the base material of the infrared cut filter to which this invention is preferably applied, for example, when it is required for a window glass, a display case, a lens, etc., it becomes important to ensure visibility and not to change the hue of transmitted light, It is preferable to select one that is excellent in light transmittance and has no absorption in the visible light region, and in the case of ensuring brightness and blocking only heat by infrared rays, the pigment may have absorption in the visible light region to some extent. Or a material having no light transmissivity such as fibers may be used in combination.

As the light transmissive material, resin materials such as polymethyl methacrylate, polycarbonate, polystyrene, and polydiethylene glycol bisallylcarbonate are preferable.

In addition, the base material may be roughened according to the purpose of use.

For example, in the case of the infrared cut filter described above, when applied to a filter for correcting visibility of optical machines such as window glass, video camera, and camera that require visibility, the surface smoothness is transparent to control the surface irregularities to be formed. Although it is preferable to use a substrate, in order to further improve the adsorption amount per unit area of the infrared absorber, it is also possible to roughen the substrate surface in advance in order to increase the surface area and introduce more ionic groups.

As a method of roughening a base material, the well-known method suitable for the material of a base material can be selected. Specifically, for example, when the substrate is a resin film, there may be mentioned glow discharge treatment, sputtering, sandblast polishing, buff polishing, particle adhesion, particle coating, and the like. Moreover, when a base material is inorganic materials, such as a glass plate, the method of roughening mechanically can be applied. As the mechanical method, known methods such as ball polishing, brush polishing, blast polishing, and buff polishing can be used.

Substrate or intermediate layer

The base material in this invention has the surface which the graft polymer in this invention mentioned above can be chemically bonded. In this invention, the surface itself of a base material may have such a characteristic, and the intermediate | middle layer which has such a characteristic may be formed in a base material surface.

Especially as an intermediate | middle layer, when synthesize | combining a graft polymer by the photograft polymerization method, the plasma irradiation graft polymerization method, and the radiation graft polymerization method, it is preferable that it is a layer which has an organic surface, and it is especially preferable that it is a layer of an organic polymer. As organic polymers, synthetic resins such as epoxy resins, acrylic resins, urethane resins, phenol resins, styrene resins, vinyl resins, polyester resins, polyamide resins, melamine resins, formalin resins, gelatin, casein, cellulose, and starch Any of natural resins, such as these, can be used. In the photograft polymerization method, the plasma irradiation graft polymerization method, the radiation graft polymerization method and the like, since the initiation of the graft polymerization proceeds from the drawing of hydrogen of the organic polymer, polymers that are easily drawn out of hydrogen, particularly acrylic resins, urethane resins and styrene resins , Vinyl resins, polyester resins, polyamide resins, epoxy resins and the like are particularly preferable in terms of production suitability.

-Layer expressing polymerization initiator

In the present invention, as a compound which expresses the polymerization initiation ability by applying energy to the base surface, a polymerizable compound and a polymerization initiator are added, and forming a layer expressing the polymerization initiation capacity as an intermediate layer or the base surface is the active point. It is preferable from the standpoint of generating efficiently.

A layer expressing polymerization initiation capability (hereinafter, appropriately referred to as a polymerizable layer) is formed by dissolving the necessary components in a solvent capable of dissolving them, and forming a surface on a substrate surface by a method such as coating and heating or light irradiation. It can be formed by dura mating.

(a) polymerizable compound

The polymerizable compound used for the polymerizable layer is not particularly limited as long as the polymerizable compound has good adhesiveness to the substrate and can add a monomer contained in the upper layer by applying energy such as actinic radiation, but among others, the molecule Preference is given to hydrophobic polymers having polymerizable groups in them.

Specific examples of such hydrophobic polymers include homopolymers of allyl group-containing monomers such as diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, allyl (meth) acrylate, and 2-allyloxyethyl methacrylate;

In addition, binary or multi-component copolymers with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, and the like containing diene-based monomers or allyl group-containing monomers such as polybutadiene, polyisoprene and polypentadiene as structural units ;

Linear polymers or three-dimensional polymers having carbon-carbon double bonds in molecules such as unsaturated polyesters, unsaturated polyepoxides, unsaturated polyamides, unsaturated polyacryl, and high density polyethylene; Etc. can be mentioned.

In addition, in this specification, when both or any one of "acryl and methacryl" is indicated, it may be described as "(meth) acryl".

As for content of a polymeric compound, the range whose solid content is 0-100 mass% in a polymeric layer is preferable, and the range which is 10-80 mass% is especially preferable.

(b) a polymerization initiator

It is preferable that the polymeric layer in this invention contains the polymerization initiator for expressing superposition | polymerization start ability by energy provision. The polymerization initiator used here is suitable according to the objective with the well-known thermal polymerization initiator, photoinitiator, etc. which can express a polymerization initiator by predetermined energy, for example, irradiation of an actinic light, heating, electron beam, etc. Can be used. Among them, it is preferable to use photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization from the viewpoint of production suitability. For this reason, it is preferable to use a photopolymerization initiator.

There is no restriction | limiting in particular if a photoinitiator is active with respect to the actinic light irradiated, and it is possible to superpose | polymerize the polymeric compound contained in a polymeric layer, and the compound which has a polymeric group contained in an upper layer, For example, radical polymerization An initiator, an anionic polymerization initiator, a cationic polymerization initiator, etc. can be used.

As such a photoinitiator, For example, p-tert- butyl trichloro acetophenone, 2,2'- diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Same acetophenones; Ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, and 2-isopropyl thioxanthone; Benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; And benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone.

As for content of a polymerization initiator, the range of 0.1-70 mass% is preferable at solid content in a polymeric layer, and the range of 1-40 mass% is especially preferable.

The solvent used when apply | coating a polymeric compound and a polymerization initiator will not be restrict | limited especially if these components melt | dissolve. From the viewpoint of ease of drying and workability, a solvent in which the boiling point is not too high is preferable, and specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.

Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Acetylacetone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 3-methoxy propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate and the like.

These solvents can be used individually or in mixture. The concentration of solids in the coating solution is preferably 2 to 50% by mass.

The amount of application in the case of forming the polymerizable layer on the substrate is preferably from 0.1 to 20 g / m 2, and preferably from 1 to 20 masses, from the viewpoint of maintaining sufficient expression of polymerization initiation and maintaining film property to prevent film peeling. It is preferable that it is 15 g / m <2>.

As described above, the composition for forming the polymerizable layer is disposed on the surface of the base material by coating or the like, and the film is formed by removing the solvent to form a polymerizable layer. At this time, the film is heated and / or irradiated with light to form a film. It is preferable to make it. Particularly, if the film is dried by heating and then irradiated with light to preliminarily form a certain amount of curing, the curing of the polymerizable compound is performed in advance, so that the situation that the polymerizable layer is dropped after the graft polymer is formed on the substrate can be effectively suppressed. It is preferable because it can. Here, using light irradiation for precure is based on the same reason as described in the term of the said photoinitiator.

The heating temperature and time may be selected under conditions in which the coating solvent can be sufficiently dried. However, from the point of manufacture aptitude, the temperature is preferably 100 ° C. or lower, and the drying time is preferably 30 minutes or less, and the drying temperature is 40 to 80 ° C., and the drying time 10. It is more preferable to select heating conditions within the range.

Light irradiation performed after heating and drying as desired is a light source, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, carbon arc, etc. Examples of the radiation include electron beams, X-rays, ion beams, and far infrared rays. Also g-rays, i-rays, Deep-UV light and high-density energy beams (laser beams) are also used. The polymerizable compound present in the polymerizable layer is partially radically polymerized from the viewpoint that the formation of the graft pattern subsequently carried out and the formation of the bond between the active point and the graft chain of the polymerizable layer carried out by energy application are not inhibited. Even if it is, it is preferable to irradiate light to the extent that it is not radically polymerized completely, and although it changes with the intensity | strength of a light source with respect to light irradiation time, it is preferable that it is generally 30 minutes or less. As a target of such preliminary curing, the film residual ratio after solvent washing becomes 10% or more, and the initiator residual rate after preliminary curing is 1% or more.

Moreover, as one of the preferable forms which produce | generate a graft polymer on the base material in this invention, the compound which combines the compound which has polymerization initiation ability on the surface of a base material, and produces | generates the graft polymer based on the polymerization start site which such compound has as a starting point Can be mentioned.

As a compound having a polymerization initiation ability applicable to the above aspect, for example, a compound having a polymerization initiation site (Y) and a substrate bonding site (Q) capable of initiating radical polymerization by photofragmentation (hereinafter, And "photo cleaving compound (QY)" as appropriate.) Etc. are mentioned.

Hereinafter, the method of bonding a photo cleavage compound (Q-Y) to a base material surface is demonstrated.

In order to bind the photo cleaving compound (QY) to the substrate surface, a photo cleaving compound (QY) is provided on the substrate to be brought into contact with the substrate surface, and the functional group (Z) and the substrate bonding site (Q) present on the substrate surface are bonded. The photo cleavage compound (QY) may be introduced into the substrate surface.

As a functional group (Z) which exists in a base material surface, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned specifically ,. These functional groups may exist originally on the surface of the substrate due to the material of the substrate in the silicon substrate or the glass substrate, or may be present on the surface by subjecting the surface of the substrate to surface treatment such as corona treatment.

The polymerization start site (hereinafter, simply referred to as "polymerization start site (Y)") capable of initiating radical polymerization by photo cleavage is a structure including a single bond that can be cleaved by light.

Examples of the single bond cleaved by the light include α cleavage of carbonyl, β cleavage reaction, light free potential reaction, cleavage of phenacyl ester, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction and N-hydroxysulfonyl The single bond which can be cleavable using ester cleavage reaction, benzylimide cleavage reaction, cleavage reaction of an active halogen compound, etc. is mentioned. By these reactions, the single bond which can be cleaved by light is cut | disconnected. Examples of the cleavable single bond include C-C bonds, C-N bonds, C-O bonds, C-Cl bonds, N-O bonds, and S-N bonds.

In addition, since the polymerization start site (Y) containing the single bond which can be cleaved by these light becomes the starting point of the graft polymerization in the graft polymer production process, when the single bond which can be cleaved by light cleaves, It has a function of generating radicals by the cleavage reaction. Thus, the structure containing the group enumerated below as a structure of the polymerization start site | part (Y) which has a single bond which can be cleaved by light, and can generate a radical is mentioned.

Aromatic ketone group, phenacyl ester group, sulfonimide group, sulfonyl ester group, N-hydroxysulfonyl ester group, benzyl imide group, trichloromethyl group, benzyl chloride group, etc. are mentioned.

Such polymerization initiation site (Y) is cleaved by exposure, and when a radical is generated, when a compound capable of polymerization exists in the vicinity of the radical, the radical functions as a starting point of the graft polymerization reaction to produce a desired graft polymer. Can be.

As the base-bonding site (Q), it is composed of a reactive group capable of reacting with and reacting with the functional group (Z) present on the substrate surface, and specific examples of the reactive group include the groups shown below.

The polymerization start site (Y) and the base bond site (Q) may be bonded directly or may be bonded via a linking group. Examples of the linking group include a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Specifically, for example, a saturated hydrocarbon group, aromatic group, ester group, amide group, A ureido group, an ether group, an amino group, a sulfonamide group, etc. are mentioned. Moreover, this coupling group may have a substituent further, and an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned as a substituent which can be introduce | transduced.

Specific examples of the compound (QY) having the base-bonding site (Q) and the polymerization initiating site (Y) [Example compounds 1 to 16] are shown below together with the cleavage site, but the present invention is limited thereto. It is not.

As a specific method of bonding the photo cleavable compound (QY) to the functional group (Z) present on the substrate surface, the photo cleaved compound (QY) is dissolved or dispersed in an appropriate solvent such as toluene, hexane, acetone, and the solution or dispersion is What is necessary is just to apply the method of apply | coating to the surface of a base material, or the method of immersing a base material in a solution or a dispersion liquid. At this time, as a density | concentration of the photo cleavage compound (Q-Y) of a solution or a dispersion liquid, 0.01-30 mass% is preferable, and it is especially preferable that it is 0.1 mass%-15 mass%. As liquid temperature in the case of making it contact, 0 degreeC-100 degreeC is preferable. As contact time, 1 second-50 hours are preferable, and 10 second-10 hours are more preferable.

As described above, the graft polymer is bonded onto the substrate, and then a functional material adsorption layer forming step is performed.

<Functional material adsorption layer formation process>

In the functional material adsorption layer forming step, the functional material adsorption layer is formed by adsorbing the functional material to the graft polymer bonded on the substrate by the graft polymer production step.

What is necessary is just to select the functional material in this invention suitably according to the objective of a functional surface. Also with respect to the form of the functional material, forms such as fine particles and low molecules are appropriately selected.

When the functional material is fine particles, the particle size of the fine particles can also be selected according to the purpose. Since the fine particles are ionically adsorbed, it goes without saying that the particle size and the adsorption amount are limited depending on the surface charge of the fine particles and the number of ionic groups. In general, the particle diameter is preferably in the range of 0.1 nm to 1 m, more preferably in the range of 1 nm to 300 nm, and particularly preferably in the range of 5 nm to 100 nm.

Particles bound to the graft polymer are described as ionic groups as polar groups. For example, depending on the presence of the ionic groups, the particles are arranged in a substantially monolayer state, or nanoscale fine particles are formed in each ionic group of the long graft chain. It is adsorbed one by one and consequently arranged in a multilayer state.

Next, the example of the functional material which can be used for this invention is demonstrated concretely according to the objective of a surface functional member.

1. Functional material

1-1. Fine particles for antireflection member

When using the surface functional member obtained by this invention as an antireflection member, it is preferable to use at least 1 type of microparticles | fine-particles selected from resin fine particles and metal oxide fine particles as a functional material. By using such fine particles, it is preferable to use the antireflective material which has a uniform and excellent antireflection ability which is preferably used on the surface of an image display body, can obtain a clear image without lowering image contrast, and can achieve excellent durability. The roughening member which can be provided can be provided.

In the resin fine particles, the central part of the fine particles called the core is an organic polymer, and the metal oxide fine particles include silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), and the like. Can be. In addition, so-called transparent pigments such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, pigment fine particles called white pigments, and the like can also be used as long as they have the preferable shapes described below.

As resin microparticles | fine-particles, a thing with high hardness is preferable from a viewpoint of durability, Specifically, the spherical microparticles | fine-particles which consist of resin, such as an acrylic resin, a polystyrene resin, a polyethylene resin, an epoxy resin, a silicone resin, are mentioned, Especially, a crosslinking is carried out. Resin fine particles are preferable.

In this use, the particle diameter of the fine particles is preferably in the range of 100 nm to 300 nm, and more preferably in the range of 100 nm to 200 nm. In this embodiment, the particles which ionically bond with the graft interface are arranged in a substantially monolayer state with regularity. In particular, when the roughening member of the present invention is used as an antireflection material, it is preferable to control the film thickness so as to be λ / 4 with respect to the wavelength λ to prevent reflection, from the viewpoint of the effect, and the particle size of the fine particles Considering that the silver roughening layer is approximately equal to the film thickness of the silver roughening layer, when the particle diameter is smaller than 100 nm, the roughening layer tends to be too thin and the antireflection property is lowered. Since it becomes large and turbidity becomes remarkable, transparency is hard to be obtained, and the contact area which ionically couples with a graft interface becomes too small, and there exists a tendency for the intensity | strength of a roughening layer to fall.

1-2. Conductive fine particles

When using the surface functional member obtained by this invention as a conductive film, as a functional material, at least 1 sort (s) of microparticles selected from electroconductive resin microparticles | fine-particles, electroconductive or semiconductor metal microparticles, metal oxide microparticles, and metal compound microparticles | fine-particles are used. It is preferable to use.

The conductive metal fine particles or the metal oxide fine particles can be widely used as long as they have a resistivity value of 1 × 10 ³ Ω · cm or less of conductive metal compound powder. Specifically, for example, silver (Ag), gold (Au), nickel (Ni ), Copper (Cu), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), iron (Fe), platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd) ), Rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo), and other alloys thereof, as well as tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), and ITO (Indium Tin) Oxide), ruthenium oxide (RuO ₂ ) and the like can be used.

Further, metal oxides and metal compound fine particles having characteristics as semiconductors may be used, for example, In ₂ O ₃ , SnO ₂ , ZnO, Cdo, TiO ₂ , CdIn ₂ O ₄ , Cd ₂ SnO ₂ , Zn ₂ SnO ₄ , Fine particles using oxide semiconductor fine particles such as In ₂ O ₃ -ZnO, and a material doped with impurities suitable for these, fine particles of spinel compounds such as MgInO, CaGaO, conductive nitride fine particles such as TiN, ZrN, HfN, LaB, etc. Electroconductive boride microparticles | fine-particles, etc. are mentioned. These may be used alone or as a mixture of two or more thereof.

1-3.Microparticles for Surface Antimicrobial Materials

When using the surface functional member obtained by this invention as an antimicrobial material, it is preferable to use metal or metal oxide microparticles | fine-particles which have an antibacterial action and a bactericidal action as a functional material.

As a material which can form such metal (compound) microparticles | fine-particles, Specifically, the metal body which has bactericidal properties, such as silver (Ag) and copper (Cu), the alloy containing 1 or more types of these, or these, for example And metal oxides thereof. Further, as a metal compound semiconductor, titanium oxide, iron oxide, tungsten oxide, zinc oxide, strontium titanate, and the like, which exhibit sterilization by irradiation with light in the ultraviolet region such as fluorescent light or sunlight, and these are platinum, gold and palladium. And metal compounds modified with silver, copper, nickel, cobalt, rhodium, niobium, tin and the like.

1-4. Particles for UV Absorption Member

In the case of using the surface functional member obtained by the present invention as an ultraviolet absorbing member, as the functional material, for example, metal oxide fine particles such as iron oxide, titanium oxide, zinc oxide, cobalt oxide, chromium oxide, tin oxide, and antimony oxide are used. It is preferable to use since it has a high shielding function in the ultraviolet-ray A, B area | region (light wavelength of 280-400 nm). In the present invention, by using a polymer compound as the base material and complexing it with this, a high function and workability as an ultraviolet shielding film sheet are expressed, and various applications are expected. It is also expected to improve the light resistance of the polymer material by using the ultraviolet shielding effect of the metal oxide.

1-5. Fine Particles for Optical Materials

As a functional material used for a color filter, a sharp cut filter, a nonlinear optical material, etc. which are used for an optical device, microparticles | fine-particles which consist of semiconductors, such as CdS and CdSe, or metals, such as gold, are mentioned. In the present invention, after using silica glass or alumina glass as the base material, it is not only preferably used for color filters and the like, but also after confirming that the third optical nonlinear susceptibility is large, nonlinear optics such as optical switches and optical memory materials. It is expected as a material. Specific examples of the fine particles used herein include precious metals such as gold, platinum, silver and palladium, alloys thereof, and the like. Substances which are not rapidly dissolved by alkali such as gold and platinum from the viewpoint of stability, etc. These are mentioned preferably.

As the ultrafine particles of a metal (compound), which is preferable as a nonlinear optical material, specifically, for example, gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), and rhodium (Rh) And ultrafine particles having an average particle diameter of 10 to 1000 GPa can be cited as the single-element such as osmium (Os), iron (Fe), nickel (Ni), ruthenium (Ru), and the alloy containing one or more thereof. . The particle diameter may be either primary particles or secondary particles, but it is preferable not to scatter visible light. Among them, precious metal fine particles selected from Au, Pt, Pd, Rh, Ag or less, having a particle size of 10 nm or less dispersed in a solvent such as toluene, or Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd, Metal fine particles selected from Y, W, Sn, Ge, In, and Ga are mentioned preferably.

Using these ultra-fine particles, when producing nonlinear optical materials by conventional methods, i.e., sol-gel method, impregnation method, sputtering method, ion implantation method, melt precipitation method, or the like, the fine particles tend to aggregate very much, so that the fine particle concentration in the composite It has become difficult to increase the temperature, or a problem such as a decrease in productivity has occurred. In particular, the low concentration of the fine particles and the small contribution of the fine particles to physical properties are limited in their use, and are not suitable for image memories, optical integrated circuits, and the like using third-order nonlinear optical effects. According to the constitution of the present invention, the fine particles are ionically bonded to the ionic groups on the surface of the substrate, and since the ionic groups are present at high density by the graft, the fine particle concentration can be easily increased. It is said that it is especially preferable for a nonlinear optical material use.

1-6. Fine particles for gas barrier film

In the case of using the surface functional member obtained by the present invention as a gas barrier film, the functional material may be an inorganic compound such as silicon oxide, zirconium oxide, titanium oxide, alumina, magnesium oxide, tin oxide, or aluminum, tin, It is preferable to use ultrafine powder made of a metal such as zinc, that is, fine particles having an average particle diameter of 100 nm or less, preferably 50 nm or less. The ultra fine powder can be used in the form of a mixture of one or two or more selected from the above inorganic compounds and metals. By using an insulating inorganic compound such as silicon oxide as the ultra fine powder, it is possible to make the whole functional member insulating. The ultrafine powder is particularly preferably silicon oxide which is easy to ultrafine powder.

As the base material, an organic resin film having high gas barrier properties, for example, polyethylene terephthalate, polyamide, polypropylene, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, or the like is preferably used.

1-7. Fine particles for organic light emitting element

The surface functional member obtained by the present invention is an organic light emitting device by forming a layer thereof on the surface of a substrate having electrodes using a fine particle in which organic dye molecules which emit light by excitation by a hot carrier are aggregated as a functional material. Can be formed. Examples of the organic dyes used herein include the following, but of course, the organic dyes are not limited to these and are appropriately selected in consideration of the purpose of use of the solid optical functional element.

blue luminescent dyes such as p-bis [2- (5-phenyloxazole)] benzene (POPOP); Green light-emitting coumarin pigments such as coumarin 2, coumarin 6, coumarin 7, coumarin 24, coumarin 30, coumarin 102, coumarin 540; Rhodamine-based (red) pigments of red luminescence such as rhodamine 6G, rhodamine B, rhodamine 101, rhodamine 110, rhodamine 590 and rhodamine 640; And light emission of near-infrared regions such as oxazine 1, oxazine 4, oxazine 9, and oxazine 118 can be obtained, and particularly preferred are oxazine dyes suitable for optical functional elements suitable for optical communication.

Moreover, cyanine pigment | dyes, such as a phthalocyanine and an iodide cyanine compound, are mentioned. Moreover, when selecting these pigment | dye, it is preferable for the purpose of thin film formation to select the thing which is easy to melt | dissolve in polymers, such as an acrylic resin. As such a pigment | dye, POPOP, coumarin 2, coumarin 6, coumarin 30, rhodamine 6G, rhodamine B, rhodamine 101, etc. are mentioned.

In addition, organic molecules used in organic electroluminescent (EL) membranes, for example, 8-hydroxyquinoline aluminum (AlQ ₃ ), 1,4bis (2,2diphenylvinyl) biphenyl, polyparaphenylenevinyl The fine particles formed by a ethylene (PPV) derivative, a distyryl arylene derivative, a styryl biphenyl derivative, a phenanthroline derivative or the like, or a medium in which an additive is added to the organic molecule may be used.

1-8. Infrared absorbing material (infrared cut filter)

When using the surface functional member obtained by this invention as an infrared cut filter, an infrared absorber can be used as a functional material.

As an infrared absorber, the infrared absorbing dye (infrared absorbing dye) which has an absorption maximum in wavelength 760nm-1200nm is mentioned preferably. As the infrared absorbing dye, a high light fastness is preferable from the viewpoint of stability and durability, and in order to obtain an infrared cut filter excellent in transparency, i.e., visible light transmittance, it is preferable that the maximum absorption is at the long wavelength side.

Representative examples include polymethine dyes containing cyanine dyes, phthalocyanine dyes, naphthoquinone and anthraquinone dyes, dithiol metal complex dyes, triphenylmethane dyes, and aluminum-diimmonium dyes. Can be. Among them, from the viewpoint of stability, polymethine pigments such as pyryllium thiopyryllium series and squarylium series are preferable, and from the viewpoint of transparency, aluminum di having a maximum absorption wavelength in a long wavelength region exceeding 900 nm. Immonium pigment | dye is preferable.

As these infrared absorbers, it is used for various infrared absorbing dyes and spectacle lenses which are described as pigments for recording display in, for example, "Special Function Dye-Technology and Market-" (CMC, 1986) et al. An infrared absorbing dye etc. can also be used suitably. Moreover, the dye etc. which are illustrated as a photothermal conversion agent in Japanese Patent Application No. 2001-4748 specification Paragraph No. 0039-0065 which the applicant of this application submitted first are also applicable.

As mentioned above, although the application example of the surface functional member of this invention and the functional material used preferably in the said field were given the specific example in 1-1 to 1-8, this invention is not limited to this, At least By selecting a type of a functional material having a physical property that can be bonded to the graft polymer and a combination of these, a substrate having a graft polymer bonded to one side thereof and appropriately combining the members having various functional surfaces utilizing the physical properties of the functional material Needless to say.

2. Physical properties of functional materials (charges when ionic bonds with functional groups of graft polymers)

As for the physical properties of the functional material, the functional material is a case in which it has its own charge such as silica fine particles, or in the case of using a state that is normally dissociated with ions in the coating liquid, such as an infrared absorber. The graft polymer having an ionic group opposite to the charged charge can be selected and the functional material can be adsorbed as it is to the graft polymer layer bonded thereto.

Moreover, when a functional member is microparticles | fine-particles, in order to make it adsorb | suck with an ionic group, the particle | grains which have a high density of charge on the surface can be produced by a well-known method, and it can adsorb | suck to the ionic group which a graft polymer has. In such a case, it becomes possible to widen the selection of the fine particles.

The functional material is preferably bonded in terms of durability in the maximum amount that can be adsorbed to the ionic groups of the graft polymer present on the substrate.

For example, when microparticles | fine-particles are used as a functional material, about 0.01-10 mass% of the dispersion concentration of the dispersion liquid containing microparticles | fine-particles is preferable at the efficiency of functional expression on a functional surface. Moreover, when the coating liquid containing the material dissociated with the ions, such as an infrared absorber, is used, about 0.01-10 mass% is preferable for the density | concentration of the functional material in a coating liquid.

3. Form of functional material adsorption

As a method of adsorbing a functional material to the graft polymer layer to form a functional material adsorption layer, a method of dissolving or dispersing a functional material on a substrate directly bonded to the graft polymer, and fine particles having a charge on the surface thereof And a method of immersing the base material to which the graft polymer is directly bonded in the dispersion solution. In either case of application or dipping, in order to supply an excess amount of functional material and to perform sufficient adsorption with the graft polymer layer, the contact time between the dissolution, the dispersion and the substrate having the surface to which the graft polymer is bonded is It is preferable that it is about 10 second-180 minutes, and it is more preferable that it is about 1 minute-about 100 minutes.

Although the following (1) and (2) are mentioned as an example of the specific form of functional material adsorption, this invention is not limited to this.

(1) A graft polymer chain having an ionic group is introduced into the surface of the substrate using an ionic monomer such as ammonium having a positive charge as the interactive group, and then the substrate is immersed in the silica fine particle dispersion for a predetermined time. After that, the extra dispersion liquid is washed and removed with water, whereby fine particles are adsorbed on the surface of the transparent substrate, in which the fine particles of silica are adsorbed densely from almost one layer to a multilayered state depending on the density of ionic groups. (Functional material adsorption layer) is formed.

(2) Dispersion liquid of mercaptonnaphthol metal complex salt (maximum absorption wavelength: 1110 nm) represented by the following formula by introducing an ionic group to the surface of the transparent substrate using an ionic monomer such as ammonium having a positive charge. The substrate is immersed for a predetermined time, after which the excess dispersion is washed and removed with water to form an infrared absorption layer (functional material adsorption layer) in which an infrared absorber is tightly adsorbed on the surface of the transparent substrate.

In this way, the functional material adsorption layer can be formed. Although the film thickness of a functional material adsorption layer can be selected according to the objective, from a viewpoint of scratch resistance, transparency, etc., the range of 0.001 micrometer-10 micrometers is generally preferable, The range of 0.01 micrometer-5 micrometers is more preferable, The range of 0.03 micrometer-2 micrometers is the most preferable.

<Crosslink Structure Forming Process>

In the crosslinking structure forming step, a crosslinked structure is formed in the functional material adsorption layer by applying energy to the functional material adsorption layer formed by the functional material adsorption step.

In the formation of the crosslinked structure, (1) an interactive group in which the functional material is not adsorbed may be used to form the crosslinked structure, and (2) the interactive group only adsorbs the functional material and is not used to form the crosslinked structure. It may be in the form.

Examples of the graft polymer in the crosslinked structure formation of the above (1) and (2) are as follows.

As said (1), the case where the graft polymer is a binary polymer of the monomer which has a carboxyl group, and the monomer which has glycidyl group is mentioned, for example.

As the case of (2) above, for example, when the graft polymer is a ternary polymer of a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having an isocyanate group, the graft polymer has a monomer having a carboxyl group, and N-metholol The case where it is a binary polymer of the monomer which can react by itself, such as acrylamide, and can form a crosslinked structure, etc. are mentioned.

The crosslinking reaction is generated by imparting energy to the functional material adsorption layer under conditions different from the graft polymer production. As an aspect of energy provision, heating, light irradiation, an ultrasonic wave, electron beam irradiation, etc. are mentioned.

In this invention, it is preferable that it is a form which forms a crosslinked structure by heating. As a specific example, reaction of the carboxyl group which is an interaction which a graft polymer has, and the glycidyl group which is a crosslinkable group is mentioned.

When the energy supply is performed by heating, for example, an oven using a heater, a hot plate, heating by photothermal conversion using infrared rays or visible light, or the like can be used as the heating means.

In addition, although heat processing changes also with the kind of graft polymer formed, it heats at 50 degreeC-300 degreeC for about 0.1 second-60 minutes.

If the energy application is performed by light irradiation, as the light irradiation means, for example, light sources from ultraviolet to visible range such as mercury lamps from low pressure to ultra high pressure, metal halide lamps, Xe lamps, and the like can be used.

In addition, the crosslinking rate in the crosslinking structure formed by this invention can be estimated by the weight increase rate of the crosslinked film (functional material adsorption layer) after immersion in a solvent for a fixed time. The solvent is selected from a solvent having the highest affinity with the formed film. When the graft polymer is composed of a polar monomer or an ionic monomer, water or N, N-dimethylacetamide or the like can be selected. The preferred weight increase rate of the crosslinked membrane is 30% or less, more preferably 10% or less, particularly preferably 5% or less.

The surface functional member (surface functional member of this invention) can be manufactured by each process by the manufacturing method of this invention demonstrated above.

The surface functional member obtained by the present invention is a material having a specific function such as an infrared absorber or metal oxide fine particles represented by silica to an interactive group of the graft polymer by directly bonding the graft polymer onto a substrate (functional material). Has a durable functional material adsorption layer which is electrostatically and uniformly adsorbed with high density. In addition, in the present invention, since the surface layer in which the functional material is adsorbed in a monolayer or multilayered state is formed on the interactive group of the graft polymer without using a binder, the surface reflects the physical properties of the functional material as it is. Becomes a functional surface. In addition, since the crosslinked structure is formed in the functional material adsorption layer, the functional material is stably fixed in the functional material adsorption layer, and thus the desorption of the functional material does not occur due to the environment in which the surface functional member is used, and thus the retention of the functional material is maintained. Can continue.

For example, when microparticles | fine-particles for a roughening member are used as a functional material, the roughening layer which has a uniform unevenness | corrugation property, and a uniform and dense unevenness | corrugation is formed. When the roughening member is used as an antireflection material, the layer itself is a thin layer while high antireflection performance is achieved, and in addition to the reflection type in that the transparent substrate is used as the base material, there is no fear of disturbing light transmittance. It can be used suitably also for a transmissive image display body.

In the case of using an infrared absorber as a functional material, an infrared absorbing member (infrared cut filter) having a layer in which the infrared absorber represented by the cyanine dye is uniformly and statically adsorbed on the polar group (ionic group) of the graft polymer. You can do In such an infrared cut filter, since an infrared absorber is localized on the surface of an infrared cut filter, the infrared absorbing layer (functional material adsorption layer) which is uniform and has infrared cut property high compared with the quantity of the absorbed infrared absorber is formed. . In addition, when this infrared cut filter is used for a filter for heat shielding, the layer itself is a thin layer while high infrared absorption ability is achieved, and the visibility is prevented from using a transparent base material as a base material so that there is no fear of impeding the transmission of visible light. It does not disturb and does not change the hue of transmitted light.

As mentioned above, in this invention, the characteristic of a functional material can be reflected by selecting a functional material suitably. In addition, the functional material adsorption layer in which the functional material is adsorbed can be formed by a relatively simple treatment on any substrate surface. Moreover, since the durability of the functional material adsorption layer which can express the outstanding functionality is favorable, it has the advantage that it can be used suitably for a versatile purpose.

Further illustrating the use of the surface functional member obtained by the present invention, by selecting a functional material, by using conductive organic or inorganic fine particles, by using magnetic fine particles such as ferrite particles for electronic and electrical functions on the functional surface By using microparticles that absorb, reflect and scatter light of a specific wavelength, magnetic functions can be expressed on the functional surface, and various functions such as optical products and various industrial products, medicines, catalysts and varistors ( Variable resistor), paint, cosmetics, etc. can be used in a wide range of fields. In addition to these various functions possessed by various fine particle constituent materials, the use of a polymer material as a base material also makes it possible to take advantage of the ease of forming and processing of the polymer material, and development of new materials is also expected.

Specific examples of the application range include, for example, application to shielding films, shielding glasses, shading windows, shading containers, shading plastic bottles, and the like against optical parts, sunglasses, ultraviolet rays, visible light and infrared rays, antimicrobial films, Microbial filter, antibacterial plastic molded product, fishing net, parts for TV, parts for telephone, parts for OA equipment, parts for electric vacuum cleaner, parts for electric fan, parts for air conditioner, parts for refrigerator, parts for washing machine, parts for humidifier, dish dryer Various uses such as various OA devices such as parts for home appliances, home appliances, sanitary articles such as toilet seats and vanity parts, and other building materials, vehicle parts, daily necessities, toys, and sundries.

The manufacturing method of the surface functional member of this invention is applied to a wide range of uses as mentioned above.

One of the preferable aspects of the manufacturing method of the surface functional member of this invention is the manufacturing method of a conductive film. The method for producing a conductive film is a method of forming a crosslinked structure in the conductive particle adsorption layer after adsorbing the conductive particles to form a conductive particle adsorption layer in a functional group capable of interacting with the conductive particles of the graft polymer.

Moreover, as a manufacturing method of the electrically conductive film which applied the manufacturing method of the surface functional member of this invention, an electroless plating catalyst or its precursor is provided to a graft polymer, an electroless plating catalyst containing layer is formed, and an energy is provided to the said electroless plating catalyst containing layer. After providing a crosslinked structure in the said electroless-plating catalyst containing layer, there is also a method of depositing a metal by performing electroless plating.

Below, in the manufacturing method of the said conductive film, the former is made into the manufacturing method (1) of a conductive film, and the latter is demonstrated in detail as the manufacturing method (2) of a conductive film.

2. Manufacturing method of conductive film

2-1.Method of manufacturing conductive film (1)

The manufacturing method (1) of the conductive film of the present invention is a step of directly bonding a graft polymer having a functional group (interacting group) and a crosslinkable group capable of interacting with the conductive particles on the substrate (hereinafter, appropriately referred to as “graft polymer generation”). Step)) and a step of adsorbing the conductive particles to a functional group capable of interacting with the conductive particles of the graft polymer to form the conductive particle adsorption layer (hereinafter, "conductive particle adsorption layer formation step" as appropriate). And a step of forming a crosslinked structure in the conductive particle adsorption layer (hereinafter, referred to as a "crosslinking structure formation process" as appropriate) by applying energy to the conductive particle adsorption layer. do.

The method for producing a conductive film of the present invention (1) adsorbs conductive particles to an interactive group of a graft polymer bonded directly on a substrate to form a conductive particle adsorption layer, and then reacts a crosslinkable group present in the graft polymer. It is characterized by forming a crosslinked structure in an electroconductive particle adsorption layer.

Although the operation of the present invention is not clear, it is assumed as follows.

In the present invention, by forming a crosslinked structure in the conductive particle adsorption layer, the conductive particles adsorbed to the interactive group of the graft polymer are again contained in the crosslinked structure to be physically immobilized. Thereby, the electroconductive particle adsorption layer which concerns on this invention is electroconductive particle by immobilization resulting from the presence of the crosslinked structure in an electroconductive particle adsorption layer in addition to the retention of electroconductive particle resulting from the presence of the interactive group of a graft polymer. It is thought that the sustainability of the remarkably improves.

Hereinafter, each process in the manufacturing method (1) of the electrically conductive film of this invention is demonstrated sequentially.

<Graft polymer production process>

In the present invention, first, in the graft polymer production step, the graft polymer is directly bonded onto the substrate.

In the present invention, first, in the graft polymer production step, the graft polymer is directly bonded onto the substrate.

Thus, as a method of forming a state in which the graft polymer is bonded on the substrate, a known method may be applied, and specifically, for example, Japanese Rubber Association, Vol. 65, No. 604, 1992, by Sugi Seiji, Reference may be made to the description of "Surface Modification and Adhesion by Macromonomer". In addition, the method called the surface graft polymerization method described below can also be applied.

(Surface Graft Polymerization Method)

It is preferable that the graft polymer in the manufacturing method (1) of the electrically conductive film of this invention was produced | generated by the surface graft polymerization method.

The surface graft polymerization method in the manufacturing method (1) of a conductive film is the same as the surface graft polymerization method in the manufacturing method of a surface functional member.

Monomers with Interacting Groups

The interactive group possessed by the graft polymer is a functional group having interactivity according to the conductive particles adsorbed onto the graft polymer.

In the present invention, the interactive group is a functional group capable of adsorbing the conductive particles, but when the conductive particles are not adsorbed, they may function as a functional group having a structure used for crosslinking reaction.

As an interactive group in the manufacturing method (1) of a conductive film, it is preferable that it is a polar group, and it is more preferable that it is an ionic group. Therefore, as a monomer which has an interactive group in this invention, the monomer (ionic monomer) which has an ionic group is used preferably.

As the ionic monomer, a monomer having a positive charge such as ammonium or phosphonium, or an acid group capable of dissociating with a negative charge or having a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group A monomer etc. are mentioned.

An ionic monomer capable of forming an ionic group which can be preferably used in the method for producing a conductive film is, as described above, a monomer having a positive charge such as ammonium or phosphonium, or a sulfonic acid group, a carboxyl group, or a phosphoric acid group. And monomers having an acidic group capable of dissociating with a negative charge such as a phosphonic acid group or the like.

The following monomers are mentioned as a specific example of the ionic monomer especially useful in the manufacturing method (1) of a conductive film. For example, (meth) acrylic acid or its alkali metal salts and amine salts, itaconic acid or its alkali metal salts and amine salts, allylamine or its halogenated hydrochlorides, 3-vinylpropionic acid or its alkali metal salts and amine salts, vinylsulfonic acid or its alkalis Metal salts and amine salts, styrenesulfonic acid or its alkali metal salts and amine salts, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salts and amine salts, 2-acrylamide-2-methyl Propanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylates or salts thereof, 2-dimethylaminoethyl (meth) acrylate or their halogenated hydrochlorides, 3-trimethylammoniumpropyl (Meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxy Ropil) and the like ammonium chloride.

Moreover, in the manufacturing method (1) of a conductive film, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monometholol (meth) acrylamide, N-dimetholol (meth) acrylamide, N Polar monomers such as vinylpyrrolidone, N-vinylacetamide, and polyoxyethylene glycol mono (meth) acrylate are also useful.

Especially as a monomer which has an interactive group in the manufacturing method (1) of a conductive film, the monomer (anionic monomer) which has anionic functional groups, such as acrylic acid, is preferable.

Monomer having a crosslinkable group

The crosslinkable group possessed by the graft polymer is a reactive group which reacts with an interactive group or other functional group contained in the graft polymer to form a covalent bond. For example, a hydroxyl group, a metyrol group, a glycidyl group, an isocyanate group, an amino group Functional groups, such as these, are mentioned.

In the manufacturing method (1) of a conductive film, it can select suitably from a well-known thing as a monomer (namely, a reactive monomer) which has a crosslinkable group which can be used.

As a specific example of the monomer which has a crosslinkable group, 2-hydroxyethyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl meth, for example Those having a hydroxyl group such as acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and the like; Those having a metirol group such as N-metholacrylamide, N-metholol methacrylamide, methirol stearoamide, etc .; Those having glycidyl groups such as glycidyl acrylate and glycidyl methacrylate; Those having isocyanate groups such as 2-isocyanate ethyl methacrylate (for example, trade name: Karenz M0I, Showa Denko); The thing which has amino groups, such as 2-aminoethyl acrylate and 2-aminoethyl methacrylate, etc. are mentioned.

(materials)

As a base material used for the manufacturing method (1) of a conductive film, it is a dimensionally stable plate-shaped thing, and if it satisfies required flexibility, strength, durability, etc., it can use any, and it is suitably selected according to a purpose of use.

In the case of selecting a transparent substrate requiring light transmittance, for example, glass, plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, butyrate cellulose, butyrate cellulose acetate, cellulose nitrate, polyethylene terephthalate, Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like).

Moreover, as a base material of the electrically conductive film which does not require transparency, in addition to the above-mentioned thing, paper, a paper in which plastic was laminated, a metal plate (for example, aluminum, zinc, copper, etc.), the paper in which metal was laminated or deposited as mentioned above, or Plastic films; and the like.

In the manufacturing method (1) of a conductive film, although a base material is suitably selected according to the use of a conductive film and the relationship with the electroconductive particle adsorbed, the base material which has a surface which consists of a polymeric resin from a viewpoint of workability and transparency is preferable, As a resin, transparent inorganic base materials, such as glass in which resin is coat | covered on the surface, and the composite material which a surface layer consists of a resin layer are all preferable.

As a base material by which resin was coat | covered on the surface, the laminated board which a resin film adhered to the surface, the base material which was treated by primer, the hard coat process base material, etc. are mentioned as a representative example. Moreover, as a representative example, the composite material whose surface layer consists of a resin layer is a resin sealing material in which the adhesive bond layer was formed in the back surface, laminated glass which is a laminated body of glass and resin, etc. are mentioned.

In addition, the base material may be roughened according to the purpose of use.

For example, in order to improve the adsorption amount per unit area of electroconductive particle, it is possible to roughen a base material surface previously, for the purpose of increasing the surface area and introducing more ionic groups.

As a method of roughening a base material, the well-known method suitable for the material of a base material can be selected. Specifically, for example, when the substrate is a resin film, a glow discharge treatment, sputtering, sandblast polishing, buff polishing, particle adhesion, particle coating, or the like can be given. Moreover, when a base material is inorganic materials, such as a glass plate, the method of roughening mechanically can be applied. As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method or a buff polishing method can be used.

Substrate or intermediate layer

The base material in the manufacturing method (1) of an electrically conductive film has a surface which can chemically bond a graft polymer directly. In the manufacturing method (1) of a conductive film, the surface itself of a base material may have such a characteristic, and the intermediate | middle layer which has such a characteristic may be formed in a base material surface. The intermediate | middle layer in the manufacturing method (1) of a conductive film is the same as the intermediate | middle layer in the manufacturing method of a surface functional member.

-Layer expressing polymerization initiator

In the manufacturing method (1) of a conductive film, a compound which expresses a polymerization initiator function by applying energy to a base material surface is added, The polymeric compound and a polymerization initiator are added, and the layer which expresses a polymerization initiator activity as an intermediate | middle layer or a base material surface is formed. It is preferable from the viewpoint of generating the active point efficiently during the graft polymerization. The layer expressing the polymerization initiation ability in the manufacturing method (1) of a conductive film is the same as the layer which expresses the polymerization initiation ability in the manufacturing method of a surface functional member.

As described above, the graft polymer is bonded onto the substrate, and then the conductive particle adsorption layer forming step is performed.

<Conductive particle adsorption layer forming process>

In the conductive particle adsorption layer forming step, the conductive particle adsorption layer is formed by adsorbing the conductive particles to the interactive group of the graft polymer bonded on the substrate by the graft polymer generating step.

The conductive particles adsorbed to the interacting groups of the graft polymer are described as examples of the ionic group as the interacting group, and are arranged in a substantially monolayer state according to the presence of the ionic group, or each of the long graft polymer chains. The nanoscale fine particles are adsorbed one by one to the ionic group of, and consequently, are arranged in a multilayer state.

Next, the electroconductive particle which can be used for this invention is demonstrated concretely.

As the conductive particles, it is preferable to use at least one kind of fine particles selected from conductive metal particles and metal oxide particles, metal oxide particles and metal compound fine particles having semiconductor characteristics, and conductive resin fine particles.

As said electroconductive metal particle and metal oxide particle, if the resistivity value is a powder of the conductive metal or metal oxide of 1x10 <^3> ohm * cm or less, it can be used widely, For example, silver (Ag), Gold (Au) ), Nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), iron (Fe), platinum (Pt), iridium (Ir), osmium (Os) ), Palladium (Pd), rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo) and other alloys and tin alloys (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), ruthenium oxide (RuO ₂ ), and the like can be used.

Further, metal oxide particles and metal compound particles having the characteristics as the semiconductor may be used, for example, In ₂ O ₃ , SnO ₂ , ZnO, Cdo, TiO ₂ , CdIn ₂ O ₄ , Cd ₂ SnO ₂ , Zn ₂ SnO ₄ , oxide semiconductor particles such as In ₂ O ₃ -ZnO, particles using a material doped with impurities suitable for these, and phenyl type compound particles such as MgInO and CaGaO, and conductive nitride particles such as TiN, ZrN, and HfN. And conductive boride particles such as LaB.

These electroconductive particles may be used independently and may use 2 or more types together. Moreover, in order to acquire desired electroconductivity, you may mix and use a some material previously.

Moreover, it is a matter of course that a particle size and an adsorption amount are restrict | limited according to the surface charge of electroconductive particle and the number of ionic groups, in order for an electroconductive particle to adsorb ionically with respect to an interactive group as a preferable aspect.

Although the particle diameter of electroconductive particle can be selected according to the objective and a use, it is preferable that it is generally the range of 0.1 nm-1 micrometer, and, more preferably, it is the range of 1 nm-300 nm from the point of electroconductive expression and the adsorptivity. And particularly preferably in the range of 5 nm to 100 nm.

Relationship between the Interaction Group (ionic Group) of the Graft Polymer and the Conductive Particles-

When the graft polymer obtained in the graft polymer production step has an anionic group (anionic group) having an anionic such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group, the interactive group has a negative charge. The electroconductive particle adsorption layer is formed by making the cationic electroconductive particle which has a positive charge here adsorb | suck here.

Examples of such cationic conductive particles include metal (oxide) fine particles having a positive charge. Fine particles having a high density and positive charge on the surface are, for example, by methods such as Yonezawa Toru, ie, T. Yonezawa, Chemistry Letters., 1999 page 1061, T. Yonezawa, Langumuir 2000, vol. 16, 5218 and Yonezawa Toru, Polymer preprints, Japan vol. 49. It may be produced by the method described in 2911 (2000). Yonezawa et al. Show that by using a metal-sulfur bond, the surface of a metal particle densely chemically modified by a functional group having a positive charge can be formed.

On the other hand, when the graft polymer obtained has an interactive group (ionic group) of a cationic group such as an ammonium group described in Japanese Patent Application Laid-Open No. 10-296895, since the interactive group has a positive charge, The electroconductive particle adsorption layer is formed by adsorb | sucking electroconductive particle which has a negative electric charge to it.

As electroconductive particle negatively charged, the gold or silver particle obtained by citric acid reduction is mentioned.

As a method of adsorbing electroconductive particle to the interactive group (ionic group) of a graft polymer, the method of apply | coating the liquid which melt | dissolved or disperse | distributed electroconductive particle to the base surface to which the graft polymer was directly bonded, and melt | dissolved electroconductive particle Or a method of immersing a substrate to which the graft polymer is directly bonded in the dispersed liquid.

In either case of coating or dipping, an excessive amount of conductive particles are supplied to form a solution or dispersion and a graft polymer so as to be introduced by sufficient ionic bonding between the graft polymer and the interactive group (ionic group). The contact time of the surface is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

Moreover, it is preferable that the maximum amount which an electroconductive particle can adsorb | suck to the hydrophilic group of a graft polymer is couple | bonded, and from the viewpoint of ensuring electroconductivity, the dispersion concentration of the dispersion liquid containing electroconductive particle is about 0.001-20 mass% is preferable.

In this way, electroconductive particle is adsorbed by the interactive group of the graft polymer directly bonded to the base material, and an electroconductive particle adsorption layer can be obtained.

Although the film thickness of an electroconductive particle adsorption layer can be selected according to the objective, from a viewpoint of scratch resistance (film strength), transparency, etc., generally, the range of 0.001 micrometer-10 micrometers is preferable, and the range of 0.01 micrometer-5 micrometers More preferably, the range of 0.1 micrometer-2 micrometers is the most preferable.

<Crosslink Structure Forming Process>

In the crosslinked structure formation step, a crosslinked structure is formed in the conductive particle adsorption layer by applying energy to the conductive particle adsorption layer formed by the conductive particle adsorption step.

In the formation of the crosslinked structure, (1) the form in which the interactive group to which the conductive particles are not adsorbed may be used for forming the crosslinked structure, and (2) the interactive group is used only for adsorbing the conductive particles. It may be a form that is not used for.

Examples of the graft polymer in the crosslinked structure formation of (1) and (2), a method for generating a crosslinking reaction, and a preferable embodiment thereof are as described in the crosslinked structure formation step in the method for producing a surface functional member. same.

In this way, a crosslinked structure is formed in the electroconductive particle adsorption layer. The crosslinking rate in this crosslinked structure can be estimated by the mass increase rate after immersing the electroconductive particle adsorption layer in which the crosslinked structure was formed in the solvent for a fixed time. The solvent used here is selected from a solvent having the highest affinity for the conductive particle adsorption layer having a crosslinked structure, and the graft polymer constituting the conductive particle adsorption layer is formed of an ionic monomer or a monomer having a polar group. In this case, water or N, N-dimethylacetamide can be selected.

It is preferable that the mass increase rate of the electroconductive particle adsorption layer in which the crosslinked structure was formed is 30% or less, It is more preferable that it is 10% or less, It is especially preferable that it is 5% or less.

Moreover, when the base material in which such electroconductive particle adsorption layer was formed does not have affinity with respect to the solvent used at the time of approximating a crosslinking rate, even if it is immersed in the base material solvent, the mass increase rate of the electroconductive particle adsorption layer in which the crosslinked structure was formed is computed. can do.

A conductive film can be manufactured by each process according to the manufacturing method (1) of the conductive film of this invention demonstrated above.

The electrically conductive film obtained by the manufacturing method (1) of an electrically conductive film has an electroconductive particle adsorption layer by which electroconductive particle was electrostatically and uniformly adsorbed to the interactive group which the said graft polymer has by making the graft polymer directly bond | attach on a base material. Moreover, in this invention, since the layer which electroconductive particle adsorb | sucked in the monolayer state or the multilayer state is formed in the interactive group which a graft polymer has, without using a binder, high electroconductivity can be expressed. In addition, since the crosslinked structure is formed in the conductive particle adsorption layer, the conductive particles are firmly immobilized in the conductive particle adsorption layer, so that the conductive particles are not detached due to the environment in which the conductive film is used, and the durability of the conductivity is excellent. .

Moreover, the electroconductive particle adsorption layer which electroconductive particle adsorb | sucks can be formed by the comparatively simple process on the arbitrary substrate surface, and the retention of the electroconductive particle of the electroconductive particle adsorption layer which can express the outstanding electroconductivity is favorable. Therefore, the present invention can be applied to a variety of uses other than the display element and the solar cell described above, and is used for producing an infrared cut material, an electromagnetic wave preventing material, and an electrical wiring, for example.

3. Manufacturing method of conductive film (2)

The method (2) for producing a conductive film of the present invention is a step of directly bonding a graft polymer having a functional group (interacting group) and a crosslinkable group capable of interacting with an electroless plating catalyst or a precursor thereof on a substrate (hereinafter, appropriately). (Hereinafter referred to as a "graft polymer production process"), and an electroless plating catalyst which is provided with an electroless plating catalyst or a precursor thereof to the graft polymer to interact with the electroless plating catalyst or precursor thereof possessed by the graft polymer. Or a step of adsorbing the precursor to form an electroless plating catalyst-containing layer (hereinafter, referred to as an "electroless plating catalyst-containing layer forming step" as appropriate) and the electroless plating catalyst-containing layer by applying energy to the electroless plating catalyst-containing layer. A step of forming a crosslinked structure in the plating catalyst-containing layer (hereinafter referred to as "crosslinked structure formation step" as appropriate) ) And electroless plating (hereinafter referred to as "electroless plating process" as appropriate).

In this invention, it is a preferable aspect to have the process of electroplating again after the said process of electroless plating is complete | finished.

In addition, the conductive film of the present invention includes a base material and a layer having a metal deposited by electroless plating on the graft polymer bonded directly on the base material, and the metal precipitated on the graft polymer by electroless plating. The attached layer is crosslinked, which is a conductive film.

As described above, the present invention, after adsorbing an electroless plating catalyst or a precursor thereof to an interactive group of the graft polymer bonded directly on the substrate to form an electroless plating catalyst-containing layer, the crosslinkability present in the graft polymer The group is reacted to form a crosslinked structure in the electroless plating catalyst-containing layer.

Although the operation of the present invention is not clear, it is assumed as follows.

In the present invention, by forming a crosslinked structure in the electroless plating catalyst-containing layer, the electroless plating catalyst or precursor thereof adsorbed or impregnated with the interactive group of the graft polymer is again contained in the crosslinked structure to be physically immobilized. The conductive film obtained by the present invention (the conductive film of the present invention) is obtained by performing electroless plating on an electroless plating catalyst-containing layer as described above, exhibits high conductivity and adhesion, and precipitates metal Since the conductive material is firmly held in the crosslinked structure, even when placed under conditions such as high humidity, the conductive material is not detached from the graft polymer, and it is assumed that the retainability is not impaired.

Hereinafter, each process in this invention is demonstrated sequentially.

<Graft polymer production process>

In the present invention, first, in the graft polymer production step, the graft polymer is directly bonded onto the substrate.

(Surface Graft Polymerization Method)

It is preferable that the graft polymer in the manufacturing method (2) of the electrically conductive film of this invention was produced | generated by the surface graft polymerization method.

The surface graft polymerization method in the manufacturing method (2) of a conductive film is the same as the surface graft polymerization method in the manufacturing method of a surface functional member.

Monomers with Interacting Groups

The interactive group possessed by the graft polymer is a functional group having an interaction according to an electroless plating catalyst or a precursor thereof adsorbed to the graft polymer.

In the present invention, the interactive group is a functional group capable of adsorbing an electroless plating catalyst or a precursor thereof, but when the electroless plating catalyst or a precursor thereof is not adsorbed, it functions as a functional group having a structure used for crosslinking reaction. You may also

As an interactive group in the manufacturing method (2) of a conductive film, it is preferable that it is a polar group, and it is more preferable that it is an ionic group. Therefore, as a monomer which has an interactive group in this invention, the monomer (ionic monomer) which has an ionic group is used preferably.

As the ionic monomer, a monomer having a positive charge such as ammonium or phosphonium, or an acid group capable of dissociating with a negative charge or having a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group A monomer etc. are mentioned.

The ionic monomer which can form the ionic group which can be used preferably in the manufacturing method (2) of a conductive film is a monomer or sulfonic acid group which has a positive charge, such as ammonium and a phosphonium group, a carboxyl group, a phosphoric acid group, as mentioned above. And monomers having an acidic group capable of dissociating with a negative charge such as a phosphonic acid group or the like.

The following monomers are mentioned as a specific example of the ionic monomer especially useful in the manufacturing method (2) of a conductive film. For example, (meth) acrylic acid or its alkali metal salts and amine salts, itaconic acid or its alkali metal salts and amine salts, allylamine or its halogenated hydrochlorides, 3-vinylpropionic acid or its alkali metal salts and amine salts, vinylsulfonic acid or its alkalis Metal salts and amine salts, styrenesulfonic acid or its alkali metal salts and amine salts, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salts and amine salts, 2-acrylamide-2-methyl Propanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylates or salts thereof, 2-dimethylaminoethyl (meth) acrylate or their halogenated hydrochlorides, 3-trimethylammoniumpropyl (Meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxy Propyl) ammonium chloride and the like.

Moreover, in the manufacturing method (2) of a conductive film, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monometholol (meth) acrylamide, N-dimetholol (meth) acrylamide, N Polar monomers such as vinylpyrrolidone, N-vinylacetamide, and polyoxyethylene glycol mono (meth) acrylate are also useful.

Especially as a monomer which has an interactive group in the manufacturing method (2) of an electrically conductive film, the monomer (anionic monomer) which has anionic functional groups, such as acrylic acid, is preferable.

Monomer having a crosslinkable group

The crosslinkable group possessed by the graft polymer is a reactive group that reacts with the functional group or other functional group contained in the graft polymer to form a covalent bond. For example, a hydroxyl group, a metyrol group, a glycidyl group, an isocyanate group, an amino group, etc. The functional group is mentioned.

In the manufacturing method (2) of a conductive film, it can select suitably from a well-known thing as a monomer (namely, a reactive monomer) which has a crosslinkable group which can be used.

As a specific example of the monomer which has a crosslinkable group, 2-hydroxyethyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl meth, for example. Those having a hydroxyl group such as acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and the like; Those having a metirol group such as N-metholacrylamide, N-metholol methacrylamide, methirol stearoamide, etc .; Those having glycidyl groups such as glycidyl acrylate and glycidyl methacrylate; Those having isocyanate groups such as 2-isocyanate ethyl methacrylate (for example, trade name: Karenz M0I, Showa Denko); The thing which has amino groups, such as 2-aminoethyl acrylate and 2-aminoethyl methacrylate, etc. are mentioned.

(materials)

As a base material used for the manufacturing method (2) of a conductive film, the content demonstrated by the manufacturing method (1) of a conductive film is similarly applied.

Substrate or intermediate layer

The base material in the manufacturing method (2) of an electrically conductive film has a surface to which a graft polymer can be chemically bonded directly. In the manufacturing method (2) of a conductive film, the surface itself of a base material may have such a characteristic, and the intermediate | middle layer which has such a characteristic may be formed in a base material surface. As an intermediate | middle layer, the content demonstrated by the manufacturing method of a surface functional member is similarly applied.

-Layer expressing polymerization initiator

In the manufacturing method (2) of a conductive film, as a compound which expresses a polymerization initiation ability by applying energy to a base surface, a polymeric compound and a polymerization initiator are added, and the layer which expresses a polymerization initiation ability as an intermediate | middle layer or a base surface is formed. It is preferable from the viewpoint of generating the active point efficiently during the graft polymerization. As the layer expressing the polymerization initiation capacity, the content described in the method for producing the surface functional member is similarly applied.

As described above, the graft polymer is bonded onto the substrate, and then, an electroless plating catalyst-containing layer forming step is performed.

<Electroless Plating Catalyst Containing Layer Forming Process>

In the electroless plating catalyst-containing layer forming step, an electroless plating catalyst or a precursor thereof is provided to the interactive group of the graft polymer bonded on the substrate to form the electroless plating catalyst-containing layer by the graft polymer producing step.

Electroless Plating Catalyst

The electroless plating catalyst used in this process is mainly a 0-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, Co and the like. In the present invention, in particular, Pd and Ag are preferred from the advantages of the handleability and the height of the catalytic ability. As a method of fixing a zero-valent metal to a graft polymer, the method of giving the graft polymer the metal colloid which adjusted the charge so that it interacts with the interactive group in a graft polymer, for example is used. Generally, metal colloids can be produced by reducing metal ions in a solution in which a charged surfactant or a protective agent with a charge is present. The charge of the metal colloid can be controlled by the surfactant or protecting agent used herein, and the metal colloid (electroless plating) is applied to the graft polymer by interacting the charged metal colloid with the interactive group of the graft polymer. Catalyst) can be adsorbed.

Electroless Plating Catalyst Precursor

The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can be an electroless plating catalyst by chemical reaction. The metal ion of the 0-valent metal used for the said electroless plating catalyst is mainly used. The metal ion which is an electroless plating catalyst precursor becomes a zero-valent metal which is an electroless plating catalyst by a reduction reaction. The metal ion, which is an electroless plating catalyst precursor, may be converted into a zero-valent metal by a separate reduction reaction after being applied to a substrate and then immersed in the electroless plating bath, to be an electroless plating catalyst, or as an electroless plating catalyst precursor. It may be immersed in an electroless plating bath and changed into a metal (electroless plating catalyst) by the reducing agent in an electroless plating bath.

In fact, the metal ion which is an electroless plating precursor is given to the graft polymer in the state of a metal salt. The metal salt to be used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion). M (NO ₃ ) n, MCln, M _{2 / n} (S0 ₄ ), M _{3 / n} (P0 ₄ ) (M represents an n-valent metal atom). As the metal ion, one in which the metal salt is dissociated can be preferably used. Specific examples include Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferred in terms of catalytic ability.

As a method of imparting a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor on a graft pattern, the metal colloid is dispersed in a suitable dispersion medium, or a metal salt is dissolved in a suitable solvent to decompose a metal ion. A solution to be prepared may be prepared, and the solution may be applied to the surface of the graft polymer-bonded substrate, or the base material to which the graft polymer is bonded may be immersed in the solution. Adsorbing metal ions to an interactive group of the graft polymer by contacting a solution containing the metal ion, or by using a dipole-ion interaction, or adsorbing the metal ion to the layer containing the graft polymer Ions can be impregnated. From the viewpoint of sufficiently performing such adsorption or impregnation, the metal ion concentration or the metal salt concentration in the solution to be contacted is preferably in the range of 0.01 to 50 mass%, more preferably in the range of 0.1 to 30 mass%. Moreover, as contact time, it is preferable that it is about 1 minute-about 24 hours, and it is more preferable that it is about 5 minutes-about 1 hour.

In this way, the electroless plating catalyst or its precursor can be adsorbed or impregnated on the interactive group of the graft polymer directly bonded to the substrate, thereby obtaining an electroless plating catalyst-containing layer.

Although the film thickness of an electroless-plating catalyst containing layer can be selected according to the objective, from a viewpoint of scratch resistance (film strength), transparency, etc., the range of 0.001 micrometer-10 micrometers is generally preferable, and 0.01 micrometer-5 micrometers are preferable. The range of is more preferable, and the range of 0.1 micrometer-2 micrometers is the most preferable.

<Crosslink Structure Forming Process>

In the crosslinked structure formation step, a crosslinked structure is formed in the electroless plating catalyst-containing layer by applying energy to the electroless plating catalyst-containing layer formed by the electroless plating catalyst-containing layer forming step.

In addition, from a viewpoint of an effect, although a crosslinked structure formation process is normally performed after completion | finish of an electroless-plating catalyst containing layer formation process before an electroless plating process mentioned later, it can also be performed after an electroless plating process.

In the formation of the crosslinked structure, (1) an electroless plating catalyst or an interactive group to which the precursor is not adsorbed may be used in the formation of the crosslinked structure, and (2) the interactive group may be used to form the electroless plating catalyst or the precursor thereof. It may be in the form of adsorption only and not used to form a crosslinked structure.

Examples of the graft polymer in the crosslinked structure formation of (1) and (2), a method for generating a crosslinking reaction, and a preferable embodiment thereof are as described in the crosslinked structure formation step in the method for producing a surface functional member. same.

The crosslinking structure formed by this process is determined by the crosslinking rate between graft polymers (how many crosslinks have occurred between graft polymers / graft polymers) and the distance between crosslinking points. The degree of crosslinking also affects the ease of electroless plating and the size of adhesion.

In the manufacturing method (2) of an electrically conductive film, the grade of bridge | crosslinking can make it bridge | crosslink by heating etc. without providing an electroless plating catalyst etc., and can estimate the grade of swelling with respect to the solvent of this crosslinked film. In that case, the solvent which has the most affinity with respect to a crosslinked film is selected as a solvent. For example, in the case of a graft polymer produced from monomers having high affinity for water such as acrylic acid and acrylamide, water, methanol, acetonitrile and the like are selected as the solvent. As a swelling degree which is preferable for the effect of this invention to be exhibited, it is 0.1-100% as a mass fraction, Preferably it is the range of 1.0-10%.

<Electroless Plating Process>

In this step, by electroless plating to the electroless plating catalyst containing layer (layer containing the electroless plating catalyst or a precursor thereof), the metal can be precipitated with high density in the electroless plating catalyst containing layer, and the deposited metal is grafted. It is maintained firmly by the crosslinked structure of the polymer.

Electroless Plating

Electroless plating refers to an operation of depositing a metal by chemical reaction using a solution in which metal ions desired to be deposited as plating are dissolved.

In the electroless plating in this step, for example, in the case where the electroless plating catalyst-containing layer contains an electroless plating catalyst, after washing the substrate on which the layer is formed, the excess electroless plating catalyst (metal) is removed, It is performed by immersing in an electroless plating bath. As the electroless plating bath to be used, generally known electroless plating baths can be used.

In addition, when the electroless plating catalyst-containing layer contains an electroless plating catalyst precursor and the electroless plating catalyst precursor is immersed in the electroless plating bath in the state of being adsorbed or impregnated with the graft polymer, the substrate is washed with water and an extra precursor (metal salt) And the like) are then immersed in the electroless plating bath. In this case, electroless plating is performed following reduction of a precursor and this in an electroless plating bath. As the electroless plating bath used here, generally known electroless plating bath can be used similarly to the above.

As a composition of a general electroless plating bath, the additive (stabilizer) which improves the stability of 1. metal plating for metal plating, 2. reducing agent, and 3. metal ion is mainly contained. In addition to these, this plating bath may contain well-known additives, such as a stabilizer of a plating bath.

As a kind of metal used for an electroless plating bath, copper, tin, lead, nickel, gold, palladium, rhodium is known, and copper and gold are especially preferable from a conductive viewpoint.

There are also reducing agents and additives that are optimal for the metal. For example, copper electroless plating baths contain chelating agents such as Cu (SO ₄ ) ₂ as copper salt, HCOH as reducing agent, and stabilizer of copper ions as additive. The plating bath used for the electroless plating of CoNiP contains cobalt sulfate, nickel sulfate, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as a complexing agent. In addition, the electroless plating bath of palladium, the EDTA is included as NH _3, H ₂ NNH _2, the stabilizing agent as metal ions _{(Pd (NH 3) 4)} Cl 2, as a reducing agent. These plating baths may contain components other than the said component.

The film thickness of the conductive film thus formed can be controlled by the metal salt or metal ion concentration of the plating bath, the immersion time in the plating bath, the temperature of the plating bath, or the like, but from the viewpoint of conductivity, the film thickness is preferably 0.5 µm or more. It is more preferable that it is 3 micrometers or more. Moreover, as immersion time in a plating bath, it is preferable that it is about 1 minute-about 3 hours, and it is more preferable that it is about 1 minute-about 1 hour.

As for the electrically conductive film obtained as mentioned above, it was confirmed by the cross-sectional observation by SEM that the electroless-plating catalyst and the microparticles | fine-particles of plated metal were densely dispersed in the surface graft film, and the comparatively large particle precipitated on it. Since the interface is a hybrid state of the graft polymer and the fine particles, the adhesion was good even when the uneven difference between the base material (organic component) and the inorganic material (electroless plating catalyst or plating metal) was 100 nm or less.

Electroplating Process

In this invention, after performing the said electroless plating process, you may have the process of electroplating (electroplating process).

In this process, after the said electroless plating, electroplating can be performed again using the electrically conductive film formed by this process as an electrode. Thereby, based on the electrically conductive film excellent in adhesiveness with a base material, the electrically conductive film which has arbitrary thickness can be easily formed in it. By adding this process, a metal film can be formed in the thickness according to the objective, and it is suitable for applying the electrically conductive film of this invention to various uses for which high electroconductivity is calculated | required.

As a method of electroplating, a conventionally well-known method can be used. Moreover, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned, From a viewpoint of electroconductivity, copper, gold, silver is preferable, and copper is more bar. It is good.

The film thickness of the conductive film obtained by electroplating varies depending on the use, and can be controlled by adjusting the metal concentration, immersion time, current density, and the like contained in the plating bath. Moreover, it is preferable that it is 0.3 micrometer or more from a viewpoint of electroconductivity, and, as for the film thickness when using for general electrical wiring etc., it is more preferable that it is 3 micrometers or more.

A conductive film can be manufactured by each process according to the manufacturing method of this invention demonstrated above.

The electrically conductive film of this invention is obtained by the manufacturing method (2) of the electrically conductive film of this invention, Comprising: The base material and the layer which the metal deposited by electroless-plating to the graft polymer bonded directly on the said base material adhered are provided, And a layer having a metal deposited on the graft polymer deposited by electroless plating is crosslinked.

In the conductive film of the present invention, by bonding the graft polymer directly on the substrate, the metal precipitated by the electroless plating on the graft polymer is electrostatically and uniformly adsorbed. In the conductive film, no binder is used, and a layer in which the metal deposited by the electroless plating on the graft polymer is deposited in a single layer state or in a multi-layer state is formed. For this reason, the electrically conductive film obtained by this invention can express high electroconductivity and adhesiveness.

In addition, since the electroless plating catalyst or the like contained in the layer is firmly immobilized in the electroless plating catalyst-containing layer by forming a crosslinked structure in the electroless plating catalyst-containing layer, the metal precipitated by the electroless plating performed thereafter is The crosslinked structure is firmly maintained, and even if the substrate is placed under high humidity or the like, the sustainability of the metal part is not impaired.

The conductive film of the present invention can be formed on an arbitrary substrate surface by a relatively simple treatment, and because the holding property of the conductive material (metal) contained in the conductive film is good, the FPC substrate, TAB tape, semiconductor package, rigid It is characterized by being applicable to various uses, such as a board | substrate circuit, an electromagnetic shield, a conductive plastic, and a conductive mat.

Example

Although an Example is given to the following and this invention is concretely demonstrated to it, this invention is not limited to this.

Example 1

In the present Example, the infrared cut filter which is the surface functional member of this invention was produced as follows.

1. Graft Polymer Production Process

As a base material, a flat plate magnetron sputtering apparatus (CFS-10-EP70 made by Shibaura Electronics) was used as a glow treatment using a biaxially stretched polyethylene terephthalate film (A4100, manufactured by Toyou Bow Co., Ltd.) having a film thickness of 188 µm. It used and the oxygen glow process was performed on condition of the following.

Oxygen glow treatment conditions

Initial vacuum: 1.2 × 10 ^-3 Pa

Oxygen pressure: 0.9 Pa

RF Glow: 1.5kW, Processing Time: 60sec

Production of Graft Polymers

Next, the glow-treated film was immersed in a 5 wt% aqueous solution of acrylic acid / glycidyl methacrylate (80/20 molar ratio) and heated at 70 ° C. for 7 hours under a nitrogen atmosphere. After heating, the substrate was taken out and immersed in distilled water overnight. The excess polymer was then washed off with running water again. As described above, a copolymer in which a copolymer of acrylic acid and glycidyl methacrylate was graft polymerized on the substrate surface was obtained. The obtained base material is used as the base material A.

2. Functional material adsorption layer formation process

In this embodiment, an infrared absorber was used as the functional material. As an infrared absorber, the cyanine dye (maximum absorption wavelength in methanol 813 nm) of the following structure which has a positive charge in the solution was used.

Application of Infrared Absorber Solution to Substrate A

The base material A obtained above was immersed for 20 minutes in the solution which consists of 0.05 g of cyanine dyes and 5 g of methanol. Thereafter, the surface was sufficiently washed with running water to remove the excess infrared absorber solution to form an infrared absorbing layer (functional material adsorption layer) on the surface of the substrate A.

3. Bridge structure formation process

Substrate A having an infrared absorbing layer was heated at 140 ° C. for 5 minutes using a hot plate (model: T2B, manufactured by Banstead) to crosslink the carboxyl group and the glycidyl group of the graft polymer.

As mentioned above, the infrared cut filter which is a surface functional member of Example 1 was obtained. This was made into the infrared cut filter 1-1.

Comparative Example 1

In the graft polymer production of the kraft polymer production step of Example 1, instead of bonding the graft polymer composed of acrylic acid and glycidyl methacrylate (80/20 molar ratio) to the substrate surface, the following method consists of acrylic acid. The infrared cut filter which is a surface functional member of the comparative example 1 was obtained like Example 1 except having bonded the graft polymer to the base surface, and carrying out the crosslinked structure formation process again. This was made into the infrared cut filter 1-2.

Production of Graft Polymers

The glow treated film obtained in the same manner as in Example 1 was immersed in a nitrogen bubbled acrylic acid aqueous solution (10 wt%) at 70 ° C. for 7 hours. The immersed film was washed with water for 8 hours to obtain a substrate on which acrylic acid was graft polymerized on the substrate surface.

<Evaluation 1-1>

Evaluation of the retention of a functional material was performed as follows.

The obtained infrared cut filter (1-1) and (1-2) were immersed in saturated saline for 10 minutes, and the retention of a functional material was evaluated by comparing the infrared rays transmittance (%) before and after immersion. The results are shown in Table 1 below.

<Evaluation 1-2>

The friction test was done as an evaluation of durability.

The surface of the obtained infrared cut filter (1-1) and (1-2) was rubbed 100 times by hand using the cotton | cloth wetted with water (BEMCOT, Asahi Kasei Co., Ltd. make). Evaluation was performed by comparing the infrared ray transmittance (%) before and after friction. The results are shown in Table 1 below.

<Evaluation 1-3>

It evaluated by approximating by the weight increase rate (%) of the formation property of a crosslinked structure.

Evaluation was performed by immersing the obtained infrared cut filter (1-1) and (1-2) in water for 1 hour, and comparing the weight increase rate (%) before and behind immersion.

Table 1

As shown in Table 1, the infrared cut filter 1-1 of the Example which formed the crosslinked structure in the infrared absorber layer (functional material adsorption layer) does not change the infrared transmittance before and after saturated saline immersion, and maintains the infrared absorber retention property. You can see that this is high. On the other hand, the infrared cut filter (1-2) of the comparative example which did not form a crosslinked structure in the infrared absorber layer had the same infrared ray transmittance as in Example before immersion in saturated saline, but the infrared ray transmittance increased significantly after immersion in saturated saline. It can be seen that the retention of the infrared absorber in the layer and its persistence are low.

In addition, the infrared cut filter 1-1 of the Example has a low weight increase rate, and it can confirm that sufficient crosslinked structure is formed in an infrared absorber layer.

Examples 2-1 to 2-3

In this example, the surface functional member which adsorb | sucked the pigment | dye on the glass base material was produced.

1. Graft Polymer Production Process

Preparation of Substrate with Compound Having Polymerization Initiation

The glass substrate (Nihon Itagara Co., Ltd.) was immersed in the piranha solution (sulfuric acid / 30% hydrogen peroxide = 1/1 volume ratio mixed liquid) overnight, and then it wash | cleaned with pure water. The substrate was placed in a nitrogen-substituted separable flask and immersed in 0.5 wt% of a dehydrated toluene solution of the compound A described below and heated to reflux for 1 hour. After taking out, it wash | cleaned sequentially with toluene, acetone, and pure water. The obtained base material is referred to as base material A1.

Production of Graft Polymers

On the substrate A1 obtained above, 5 ml of a 5 wt% monomer aqueous solution of acrylic acid / glycidyl methacrylate (molar ratio is 90/10) was dropped, and a 5 wt% monomer aqueous solution was uniformly covered between the substrate A1 and the quartz plate. Put on. Next, it exposed for 5 minutes using the exposure machine (UVX-02516S1LPO1, the product made by Ushio Denki Co., Ltd.). Thereafter, the quartz plate was removed and washed with water to obtain a substrate copolymerized with acrylic acid and glycidyl methacrylate. This is referred to as description B.

2. Functional material adsorption process

The obtained base material B was immersed for 5 minutes in 5 wt% of sodium bicarbonate water. After taking out, it was immersed in 0.5 wt% aqueous solution of methylene blue for 1 minute, and it washed with water and obtained the glass plate (base material C) which adsorb | sucked methylene blue.

3. Crosslinked Structure Forming Process

The obtained base material C was heated at 120 ° C in Example 2-1 (140 ° C in Example 2-2 and 160 ° C in Example 2-3) using a hot plate (model: T2B, manufactured by Banstead) for 5 minutes. The carboxyl group and the glycidyl group which the graft polymer has were crosslinked.

As described above, each surface functional member of Examples 2-1 to 2-3 was obtained. Let these be surface functional members 2-1-(2-3).

Comparative Example 2

In the preparation of Example 2-1, the surface functional member of Comparative Example 1 was obtained in the same manner as in Example 2-1 except that the crosslinked structure forming step (heating) was not performed. Let this be the surface functional member 2-4.

Examples 3-1 to 3-3

In the graft polymer production step of Examples 2-1 to 2-3, except that the molar ratio of acrylic acid / glycidyl methacrylate was changed from 90/10 to 80/20, Examples 2-1 to 2-3 In the same manner as in the above, each surface functional member of Examples 3-1 to 3-3 was obtained. Let these be surface functional members 3-1-(3-3).

Comparative Example 3

In the preparation of Example 3-1, the surface functional member of Comparative Example 3 was obtained in the same manner as in Example 3-1 except that the crosslinked structure forming step (heating) was not performed. Let this be the surface functional member 3-5.

Examples 4-1 to 4-3

In the graft polymer production process of Examples 2-1 to 2-3, except that the molar ratio of acrylic acid / glycidyl methacrylate was changed from 90/10 to 70/30, Examples 2-1 to 2-3 In the same manner as in the above, each surface functional member of Examples 4-1 to 4-3 was obtained. Let these be surface functional members 4-1-(4-3).

Comparative Example 4

In the preparation of Example 4-1, the surface functional member of Comparative Example 4 was obtained in the same manner as in Example 4-1 except that the crosslinked structure forming step (heating) was not performed. Let this be the surface functional member 4-4.

<Evaluation 2-1>

The change (discoloration) of the retention of the functional material by the heating conditions in the crosslinked structure forming step was evaluated. The results are shown in Table 2.

Evaluation was performed by immersing the surface functional members (2-1) to (2-4), (3-1) to (3-4), and (4-1) to (4-4) in saturated saline for 5 minutes, respectively. Thereafter, the absorbance at 570 nm, which is the absorption wavelength of the dye (methylene blue), was measured by UV-Vis absorption spectrum, and the pigment residual ratio (%) before and after saturated saline immersion was calculated by the following formula. .

Dye retention rate (%) = absorbance after saturated saline immersion / absorbance before saturated saline immersion x 100

<Evaluation 2-2>

The formation property of the crosslinked structure was evaluated by approximating the weight increase rate (%). Evaluation was performed by immersing the obtained functional member in water for 1 hour, and comparing the weight increase rate (%) before and behind immersion. Moreover, this evaluation was performed only about surface functional members 2-1-(2-4). The results are shown in Table 2.

Table 2

As shown in Table 2, each of the surface functional members of the Example has a high pigment residual ratio when compared with each of the surface functional members of the Comparative Example, and performs a crosslinked structure forming step to obtain a functional material (pigment). It can be seen that the retention and its durability are improved.

In addition, heating operation for 5 minutes at 160 ° C. for acrylic acid / glycidyl methacrylate (90/10) and at 140 ° C. for acrylic acid / glycidyl methacrylate (80/20) or (70/30) is performed. When it was carried out, the pigment | dye persistence of 80% or more was confirmed. In this regard, it is understood that the sufficient crosslinked structure is formed in the functional material adsorption layer, whereby the retention of the functional material (pigment) and its sustainability are further improved.

Moreover, as for each surface functional member of an Example, all have low weight increase rate, and it can confirm that sufficient crosslinked structure is formed in a functional material adsorption layer.

Example 5

In the graft polymer production step of Example 2-1, acrylic acid / glycidyl methacrylate (molar ratio 90/10) is changed to acrylic acid / N-metholacrylamide (molar ratio 80/20), and acrylic acid and N The surface functional member of Example 5 in the same manner as in Example 2-1, except that the graft polymer of methirolacrylamide was produced and the heating conditions in the crosslinked structure forming step were changed from 130 ° C. to 10 minutes. Got. This is referred to as surface functional member 5.

As a result of evaluating the obtained surface functional member 5 in the same manner as in <Evaluation 2-1>, it was confirmed that the pigment | dye persistence was 80% or more.

According to the present invention, as shown in Examples 1, 2-1 to 2-3, 3-1 to 3-3, 4-1 to 4-3, and 5, the functional material is firmly adsorbed on the substrate surface. The manufacturing method of the surface functional member which has the durable functional material adsorption layer made excellent, and is excellent in the retention of a functional material, and its durability can be provided.

Example 6

1. Graft polymer production process

PET (188 µm, manufactured by Toray Industries, Inc.) was used as the substrate, and the following photopolymerizable composition was applied to the surface thereof using a rod bar 18, dried at 80 ° C for 2 minutes to form an intermediate layer having a thickness of 6 µm.

<Photopolymerizable composition>

Allyl methacrylate / methacrylic acid copolymer 2 g

  (Copolymerization molar ratio 80/20, average molecular weight 100,000)

· Ethylene oxide modified bisphenol A diacrylate... 4 g

1-hydroxycyclohexylphenyl ketone... 1.6 g

1-methoxy-2-propanol... 16 g

Production of Graft Polymers

Next, 5 ml of 5 mass% monomer aqueous solution of acrylic acid / glycidyl methacrylate (molar ratio: 80/20) is dripped on the intermediate | middle layer, the quartz plate is covered on it, and this monomer aqueous solution is uniformly mixed with an intermediate | middle layer and a quartz plate. Put on. Next, it exposed for 5 minutes using the exposure machine (UVX-02516S1LP01, the Ushio Denki company make). As described above, a substrate having a graft polymer composed of a copolymer of acrylic acid and glycidyl methacrylate bonded to the substrate surface was obtained. The obtained base material is used as the base material A.

2. Electroconductive particle adsorption layer formation process

The base material A is immersed in the Ag particle dispersion which has the positive charge obtained as follows, the surface is wash | cleaned sufficiently with the flowing water after that, the excess particle dispersion is removed, and the electroconductive particle adsorption layer which electroconductive particle adsorb | sucks is formed. Got it.

(Preparation of Ag particle dispersion)

To 50 ml of silver perchlorate ethanol solution (5 mmol / L), 3 g of bis (1,1-trimethylammoniumdecanoylaminoethyl) disulfide was added, and 30 ml of sodium borohydride solution (0.4 mol / L) was slowly added with vigorous stirring. It dripped and the ion was reduced, and the dispersion liquid of the silver particle coat | covered with quaternary ammonium was obtained. As a result of measuring the size of this silver particle with the electron microscope, the average particle diameter was 5 nm.

3. Crosslinked Structure Forming Process

The substrate A on which the conductive particle adsorption layer was formed was heated at 140 ° C. for 5 minutes using a hot plate (model: T2Z. Bamstead Co., Ltd.) to crosslink the carboxyl group and the glycidyl group of the graft polymer to form a conductive particle adsorption layer. A crosslinked structure was formed.

As described above, the conductive film of Example 6 was obtained.

Comparative Example 5

In the graft polymer formation of the kraft polymer production process of Example 6, instead of producing a graft polymer composed of acrylic acid and glycidyl methacrylate (80/20 molar ratio), a graft polymer composed only of acrylic acid was produced, A conductive film of Comparative Example 5 was obtained in the same manner as in Example 6 except that the crosslinked structure forming step was not performed.

<Evaluation>

(Evaluation of conductivity)

The surface conductivity of the conductive particle adsorption layer having a crosslinked structure in the conductive film of Example 6 was measured by four probe method using LORESTA-FP (manufactured by Mitsubishi Kagaku Co., Ltd.). Indicated.

Moreover, 1.5 ohms / square which measured the surface conductivity of the electroconductive particle adsorption surface in the electroconductive film of the comparative example 5 by the method similar to Example 1 was shown.

In this respect, it was found that also in Example 6 and Comparative Example 5, a conductive film having excellent conductivity was formed.

(Evaluation of the durability)

The holding | maintenance durability of electroconductive particle was evaluated by immersing the electrically conductive films of Example 6 and the comparative example 5 for 10 minutes, respectively, and comparing the surface conductivity before and behind immersion. Here, the measuring method of surface conductivity is the same as the measuring method of surface conductivity in the said evaluation of electroconductivity. In addition, the surface conductivity before immersion is a result of evaluation of the said electroconductivity. The measurement results are shown in Table 3 below.

Table 3

From the above evaluation results, it can be seen that the conductive film of Example 6 in which the crosslinked structure was formed in the conductive particle adsorption layer was maintained in a state where the surface conductivity before and after saturated saline immersion was high and its durability was excellent.

On the other hand, the conductive film of Comparative Example 5, in which a graft polymer composed only of acrylic acid was formed to form a conductive particle adsorption layer, and a crosslinked structure was not formed in the conductive particle adsorption layer, had the same surface conductivity as that of Example 6 before saturated saline immersion. Although it is shown, after saturated saline immersion, surface electroconductivity fell remarkably and it is guessed that the detachment | disassembly of electroconductive particle might have arisen.

As shown in Example 6 above, according to the manufacturing method (1) of the conductive film of this invention, the manufacturing method of the conductive film which has high electroconductivity and is excellent in the durability can be provided.

Example 7

1. Graft polymer production process

Using a polyimide film (product name: Kapton, manufactured by Toray DuPont) as a substrate, the following photopolymerizable composition was applied to the surface thereof using a rod No. 18 coating bar, dried at 80 ° C. for 2 minutes, and an intermediate layer having a film thickness of 6 μm. Formed.

<Photopolymerizable composition>

Allyl methacrylate / methacrylic acid copolymer 2 g

  (Copolymerization molar ratio 80/20, average molecular weight 100,000)

· Ethylene oxide modified bisphenol A diacrylate... 4 g

1-hydroxycyclohexylphenyl ketone... 1.6 g

1-methoxy-2-propanol... 16 g

Production of Graft Polymers

Next, 5 ml of 5 mass% monomer aqueous solution of acrylic acid / glycidyl methacrylate (molar ratio is 80/20) was dropped on a middle layer, and a quartz plate was covered, and a 5 mass% monomer aqueous solution was uniformly sandwiched between the middle layer and the quartz plate. Put in. Next, it exposed for 5 minutes using the exposure machine (UVX-02516S1LP01, the Ushio Denki company make). After that, the quartz plate was removed and washed with water. As described above, a substrate having a graft polymer composed of a copolymer of acrylic acid and glycidyl methacrylate bonded to the substrate surface was obtained.

2. Electroless Plating Catalyst Containing Layer Forming Process

After immersing this base material A in the aqueous solution of 1 mass% of silver nitrates (made by Wako Pure Chemical Industries, Ltd.) for 1 hour, it wash | cleaned with distilled water. Then, it immersed in 1 mass% aqueous solution of sodium borohydride for 1 hour, the fine particle of silver was formed in the graft film, and the electroless plating catalyst containing layer was formed.

3. Crosslinked Structure Forming Process

A substrate on which a layer containing an electroless plating catalyst is formed is heated at 140 ° C. for 5 minutes using a hot plate (model T2B, manufactured by Banstead) to crosslink the carboxyl group and the glycidyl group of the graft polymer to form an electroless plating catalyst-containing layer. A crosslinked structure was formed in the middle.

4. Electroless Plating Process

The base material which completed the bridge | crosslinking structure formation process was immersed for 20 minutes in the electroless plating bath of the following composition, and the metal (copper) was deposited, and the electrically conductive film A of Example 7 was produced.

<Electroless Plating Bath Components>

· OPC Cupper-H T1 (manufactured by Okuno Seiyaku Co., Ltd.) 6 mL

· OPC Cupper-H T2 (manufactured by Okuno Seiyaku Co., Ltd.) 1.2 mL

· OPC Cupper-H T3 (manufactured by Okuno Seiyaku Co., Ltd.) 10 mL

·water… 83 mL

Example 8

The electroconductive film A produced in Example 7 was electroplated again for 15 minutes to prepare the conductive film B of Example 8.

<Composition of Electroplating Bath>

· Sulfuric acid copper… 38 g

Sulfuric acid 95 g

·Hydrochloric acid… 1 mL

· Caper Grimm PCM (made by Marutex Co., Ltd.) 3 mL

·water… 500 mL

Comparative Example 6

In the production of the graft polymer of the kraft polymer production step of Example 7, except that glycidyl methacrylate was not used and a graft polymer composed only of acrylic acid was produced, the conductive film of Comparative Example 6 was prepared in the same manner as in Example 7. C was obtained.

Comparative Example 7

The conductive film C produced in Comparative Example 6 was subjected to electroplating in the same manner as in Example 8 to obtain a conductive film D of Comparative Example 7.

<Evaluation>

1. Evaluation of conductivity

The surface conductivity of the conductive films A to D obtained above was measured by a four probe method using LORESTA-FP (manufactured by Mitsubishi Kagaku Co., Ltd.). The results are shown in Table 4 below.

2. Evaluation of adhesion

An aluminum plate (thickness of 0.1 mm) was bonded to the surfaces of the obtained conductive films A to D with an epoxy adhesive (Aldite, manufactured by Chiba Co., Ltd.), dried at 140 ° C. for 4 hours, and then peeled at 90 ° based on JISC6481. The experiment was conducted. The results are shown in Table 4 below.

3. Humidity test

After leaving obtained electrically conductive films A-D for 7 days on 100 degreeC and 85 RH% conditions, it evaluated by performing peeling test using a mylar tape. Evaluation criteria are as follows. The results are shown in Table 4 below.

-Evaluation standard-

○: there is no peeling of the metal part

X: There is peeling of the metal part

Table 4

As shown in Table 4, the conductive films A and B of the examples in which the crosslinked structure was formed in the electroless plating catalyst-containing layer were conductive films having high conductivity and excellent adhesion, and the metal parts were not peeled off even when placed for a long time under high humidity. The sustainability was excellent. In this respect, it is assumed that the metal precipitated by electroless plating is firmly held by the crosslinked structure of the graft polymer.

On the other hand, the conductive films C and D of Comparative Example 6 in which a graft polymer composed only of acrylic acid were formed to form an electroless plating catalyst-containing layer, and no crosslinked structure was formed in the electroless plating catalyst-containing layer were compared with the conductive films of the examples. It was found that all of the conductivity, the adhesion, and the adhesion were inferior, and in particular, the sustainability of the metal part was remarkably decreased. In this respect, it is estimated that the metal precipitated by electroless plating peels off the graft polymer by high humidity.

As shown in Examples 7 and 8, according to the manufacturing method (2) of the conductive film of the present invention, the conductive film has a high conductivity and adhesion, and is excellent in the retention of the conductive material and its durability, and the conductive film manufacturing method. The conductive film obtained by can be provided.

Claims (20)

Directly bonding a graft polymer having a functional group and a crosslinkable functional group capable of interacting with the functional material on the substrate; Adsorbing the functional material to a functional group capable of interacting with the functional material of the graft polymer to form a functional material adsorption layer; And A method for producing a surface functional member comprising the step of forming a crosslinked structure in the functional material adsorption layer by applying energy to the functional material adsorption layer. The method of manufacturing a surface functional member according to claim 1, wherein the functional group capable of interacting with the functional material is a polar group. The method of manufacturing a surface functional member according to claim 1, wherein the functional group capable of interacting with the functional material is an ionic group. The method for producing a surface functional member according to claim 1, wherein the crosslinkable functional group is selected from the group consisting of a hydroxyl group, a metyrol group, a glycidyl group, an isocyanate group, and an amino group. The fine functional material according to claim 1, wherein the functional material is an antireflection member fine particle, conductive fine particle, surface antibacterial material fine particle, ultraviolet absorbing fine particle, optical material fine particle, gas barrier film fine particle, organic light emitting element fine particle, and infrared ray. Method for producing a surface functional member, characterized in that selected from the group consisting of absorbent material. The method of manufacturing a surface functional member according to claim 5, wherein the functional material is a material for an infrared absorbing member. Directly bonding a graft polymer having a functional group and a crosslinkable functional group capable of interacting with the conductive particles on the substrate; Adsorbing the conductive particles to a functional group capable of interacting with the conductive particles of the graft polymer to form a conductive particle adsorption layer; And A method for producing a conductive film, comprising the step of forming a crosslinked structure in the conductive particle adsorption layer by applying energy to the conductive particle adsorption layer. The method for producing a conductive film according to claim 7, wherein the functional group capable of interacting with the conductive particles is a polar group. The method for producing a conductive film according to claim 7, wherein the functional group that can interact with the conductive particles is an ionic group. The method for producing a conductive film according to claim 7, wherein the crosslinkable functional group is selected from the group consisting of a hydroxyl group, a methirol group, a glycidyl group, an isocyanate group, and an amino group. The conductive film according to claim 7, wherein the conductive fine particles are one or more fine particles selected from conductive metal particles and metal oxide particles, metal oxide particles and metal compound particles having semiconductor characteristics, and conductive resin particles. Manufacturing method. 12. The method for producing a conductive film according to claim 11, wherein a particle diameter of the conductive fine particles is in a range of 0.1 nm to 1 m. Directly bonding a graft polymer having a functional group and a crosslinkable functional group capable of interacting with an electroless plating catalyst or a precursor thereof on the substrate; Providing an electroless plating catalyst or a precursor thereof to the graft polymer to form an electroless plating catalyst-containing layer; Forming a crosslinked structure in the electroless plating catalyst-containing layer by applying energy to the electroless plating catalyst-containing layer; And It has a process of electroless plating, The manufacturing method of the electrically conductive film characterized by the above-mentioned. The method for producing a conductive film according to claim 13, wherein the functional group capable of interacting with the electroless plating catalyst or its precursor is a polar group. The method for producing a conductive film according to claim 13, wherein the functional group capable of interacting with the electroless plating catalyst or its precursor is an ionic group. The method for producing a conductive film according to claim 13, wherein the crosslinkable functional group is selected from the group consisting of a hydroxyl group, a methrol group, a glycidyl group, an isocyanate group, and an amino group. The method for manufacturing a conductive film according to claim 13, wherein the metal precipitated by electroless plating is selected from the group consisting of copper, tin, lead, nickel, gold, and palladium and rhodium. The manufacturing method of the conductive film of Claim 13 which has the process of electroplating again after the process of electroless plating is complete | finished. 19. The method of manufacturing a conductive film according to claim 18, wherein the metal used for the electroplating is selected from the group consisting of copper, chromium, lead, nickel, gold, silver, tin, and zinc. A conductive film obtained by the method for producing a conductive film according to claim 13, comprising: a base material and a layer having a metal deposited by electroless plating on a graft polymer bonded directly on the base material; A conductive film characterized by crosslinking a layer with a metal deposited by sea plating.