JP2006056948A - Method for producing surface-functional member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a surface-functional member which has a functional material-adsorbed layer having a functional material strongly adsorbed thereto and having excellent durability on the surface of a substrate and has excellent functional material retainability and its sustainability, and to provide a surface-functional member obtained by the production method. <P>SOLUTION: This method for producing the surface-functional member is characterized by having a process for directly binding a graft polymer having functional groups capable of interacting with a functional material and cross-linkable functional groups to a substrate, a process for making the functional groups capable of interacting with the functional material adsorb the functional material to form a functional material-adsorbed layer, and a process for imparting energy to the functional material-adsorbed layer to form a cross-linked structure in the functional material-adsorbed layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

Conventionally, various surface functional members have been proposed in which functional fine particles or low molecules (functional materials) are adsorbed on an arbitrary base material to form a surface layer having various functions. Examples of the material in which the functional material is adsorbed on the base material include a material in which fine particles or low molecules are adsorbed on the graft polymer existing on the base material, and such a material is useful for various applications. is there.
For example, Patent Document 1 discloses that silica particles adsorbed as fine particles on a graft polymer chain present on a support are useful as an antireflection member. Patent Document 2 describes that a film in which an infrared absorbing dye is adsorbed on a graft polymer (infrared absorbing layer) is a thin layer and has a higher infrared absorbing ability than a film coated with a conventional dye. Has been. In addition, since the graft polymer as described above is directly bonded to the base material through a covalent bond, adsorbing a functional material to the graft polymer provides strong adhesion to the base material and mechanical abrasion resistance. A surface functional member having high wear resistance and organic solvent resistance and excellent durability has been obtained.

  However, in the surface functional member obtained by the conventional method, since the graft polymer and the functional material that is the adsorbing substance are bonded by ionic bond, even if the functional material is adsorbed to the graft polymer, the saline solution When the electrolyte solution is touched, the functional material is detached from the graft polymer, and the effect of the functional material is not maintained. In particular, in materials used outdoors, the functional material tends to be detached from the graft polymer when exposed to rainwater for a long time.

As described above, the present situation is that further improvement is desired for the improvement of the retention of the functional material in the surface functional member and its sustainability.
JP 2003-112379 A JP 2003-57435 A

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the object of the present invention is to have a functional material adsorbing layer excellent in durability formed by firmly adsorbing the functional material on the surface of the base material, and excellent in retention and sustainability of the functional material. It is providing the manufacturing method of a surface functional member.

  As a result of intensive studies, the present inventor has found that the above problem can be solved by introducing a cross-linked structure into the functional material adsorbing layer containing the graft polymer to which the functional material has been adsorbed. It came to do.

That is, a functional group capable of interacting with the functional material (hereinafter referred to as “interactive group” as appropriate) and a crosslinkable functional group (hereinafter referred to as “crosslinkable group” as appropriate) on the substrate. Directly bonding the graft polymer having,
A step of adsorbing the functional material to the functional group capable of interacting with the functional material of the graft polymer to form a functional material adsorbing layer;
Forming a cross-linked structure in the functional material adsorbing layer by applying energy to the functional material adsorbing layer;
It is a manufacturing method of the surface functional member characterized by having.

  As described above, the present invention provides a crosslinkable group present in the graft polymer after the functional material is adsorbed on the interactive group of the graft polymer directly bonded on the substrate to provide the functional material adsorption layer. To form a cross-linked structure in the functional material adsorbing layer. Although the action of the present invention is not clear, the functional material adsorbed to the interactive group in the graft polymer is included in the cross-linked structure due to the formation of the cross-linked structure in the functional material adsorbing layer. Presumably, the functional material adsorbing layer according to the present invention exhibits high durability and is also significantly improved in the retention and sustainability of the functional material because it is stably immobilized in the material adsorbing layer. Is done.

  According to the present invention, a functional material adsorbing layer excellent in durability formed by firmly adsorbing a functional material on the surface of the substrate, and a surface function excellent in retention and sustainability of the functional material. The manufacturing method of an adhesive member can be provided.

Hereinafter, the present invention will be described in detail.
[Method for producing surface functional member]
A step of directly bonding a graft polymer having a functional group capable of interacting with a functional material (interactive group) and a crosslinkable group on a base material (hereinafter referred to as “graft polymer generation step” as appropriate); A step of adsorbing the functional material to a functional group capable of interacting with the functional material of the graft polymer to form a functional material adsorbing layer (hereinafter referred to as a “functional material adsorbing layer forming step” as appropriate); A step of forming a crosslinked structure in the functional material adsorbing layer by applying energy to the functional material adsorbing layer (hereinafter, appropriately referred to as a “crosslinked structure forming step”). . Hereafter, 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.
As described above, a known method may be applied as a method for forming a state in which the graft polymer is bonded on the substrate. Specifically, for example, Journal of Japan Rubber Association, Vol. 65, 604, 1992 The description of “Surface Modification and Adhesion with Macromonomer” by Shinji Sugii, can be referred to. In addition, a method called a surface graft polymerization method described below can be applied.

(Surface graft polymerization method)
The graft polymer in the present invention is preferably formed by a surface graft polymerization method.
In general, the surface graft polymerization method gives an active species on a polymer compound chain forming a solid surface, and further polymerizes another monomer starting from this active species to synthesize a graft (grafting) polymer. Is the method.

Any known method described in the literature can be used as the surface graft polymerization method for realizing the present invention. For example, New Polymer Experimental Science 10, edited by Polymer Society of Japan, 1994, published by Kyoritsu Shuppan Co., Ltd., p135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams.
As a specific method of the photograft polymerization method, methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.

The plasma irradiation graft polymerization method and the radiation irradiation graft polymerization method can be prepared by the methods described in the above-mentioned literature and Y. Ikada et al, Macromolecules vol. 19, page 1804 (1986). Specifically, a graft polymer can be obtained by treating a polymer surface such as PET with plasma or electron beam to generate radicals on the surface and then reacting the active surface with a monomer.
In addition to the above-mentioned documents, the photograft polymerization method can be applied to the surface of a film substrate as described in JP-A-53-17407 (Kansai Paint) or JP-A-2000-212313 (Dainippon Ink). The graft polymer can also be obtained by applying a photopolymerizable composition to the substrate, and then contacting the radically polymerized compound and irradiating it with light.

  In addition to these, as a means for forming a state in which the graft polymer is bonded on the substrate, reactivity such as trialkoxysilyl group, isocyanate group, amino group, hydroxyl group, carboxyl group at the end of the polymer compound chain It can also be formed by adding a functional group and a coupling reaction between the functional group and the substrate surface functional group.

A specific method in the case of using the surface graft polymerization method in the graft polymer production step in the present invention will be described.
In the present invention, an active site is generated on the surface of the substrate by bringing a polymerizable compound having an interactive group and a polymerizable compound having a crosslinkable group shown below into contact with the surface of the substrate and applying energy. Thus, this active site reacts with the polymerizable group of the polymerizable compound to cause a surface graft polymerization reaction.
The contact of the polymerizable compound with the substrate surface may be carried out by immersing the substrate in a liquid composition containing the polymerizable compound. However, from the viewpoint of handleability and production efficiency, the polymerization may be performed. It is preferable to carry out by applying a liquid composition containing a functional compound to the substrate surface.
As a method for applying energy, for example, heating or radiation irradiation can be used. Specifically, for example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible.

  In the present invention, the graft polymer directly bonded to the substrate is a graft polymer having an interactive group and a crosslinkable group, and the polymer structure has an interactive group and a crosslinkable group. Thus, both functions of adsorption of conductive particles and formation of a crosslinked structure can be exhibited.

The graft polymer in the present invention is formed by copolymerization of a polymerizable compound having an interactive group and a polymerizable compound having a crosslinkable group. By using the surface graft polymerization method described above, a base material is obtained. On top of this, the graft polymer which is this copolymer can be directly bonded.
The polymerizable compound having an interactive group and the polymerizable compound having a crosslinkable group may be any of a monomer, a macromer, and a polymer having a polymerizable group. It is particularly preferred.

As the monomer having an interactive group and the monomer having a crosslinkable group used for the formation of the graft polymer, one type each may be used, or a plurality of types of monomers may be used in combination.
In the formation of the graft polymer in the present invention, it is necessary to use at least one monomer having an interactive group and one monomer having a crosslinkable group. You may use other copolymerization monomers other than.

As the content ratio of the monomer component having an interactive group and the monomer component having a crosslinkable group in the graft polymer, from the viewpoint of coexistence of adsorption of the functional material and formation of a crosslinked structure, a molar ratio of 30:70 to 99: 1 is preferable, 50:50 to 95: 5 is more preferable, and 60:40 to 90:10 is more preferable.
Details of matters relating to the adsorption of the functional material and matters relating to the formation of the crosslinked structure will be described in detail in the description of the “functional material adsorbing layer forming step” and the “crosslinked structure forming step” described later.

  Hereinafter, the monomer having an interactive group and the monomer having a crosslinkable group that can be used for forming the graft polymer in the present invention will be described in detail.

-Monomer having an interactive group-
The interactive group possessed by the graft polymer is a functional group having an interactive property corresponding to the functional material adsorbed on the graft polymer.
In the present invention, the interactive group is a functional group capable of adsorbing a functional material. However, when the functional material is not adsorbed, it may function as a functional group having a structure used for a crosslinking reaction. .

  The interactive group in the present invention is preferably a polar group, and more preferably an ionic group. Accordingly, a monomer having an ionic group (ionic monomer) is preferably used as the monomer having an interactive group in the present invention.

  As the ionic monomer, a monomer having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group can be dissociated into a negative charge. And monomers having an acidic group.

  As described above, the ionic monomer that can form an ionic group that can be preferably used in the present invention is a monomer having a positive charge such as ammonium or phosphonium, a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid. And monomers having a negative charge such as a group or an acidic group that can be dissociated into a negative charge.

  Specific examples of the ionic monomer particularly useful in the present invention include the following monomers. For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or their salts, 2-dimethyla Noethyl (meth) acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3- (Methacryloyloxypropyl) ammonium chloride, etc. can be used.

  In the present invention, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxy Polar monomers such as ethylene glycol mono (meth) acrylate are also useful.

  As the monomer having an interactive group in the present invention, a monomer having an anionic functional group such as acrylic acid (anionic monomer) is particularly preferable.

-Monomer having a crosslinkable group-
The crosslinkable group that the graft polymer has is a reactive group that reacts with an interactive group or another functional group contained in the graft polymer to form a covalent bond. For example, a hydroxyl group, a methylol group, a glycidyl group, Functional groups such as isocyanate groups and amino groups can be mentioned.

In the present invention, a monomer having a crosslinkable group (that is, a reactive monomer) that can be used can be appropriately selected from known ones.
Specific examples of the monomer having a crosslinkable group include, for example, 2-hydroxyethyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl methacrylate, Those having a hydroxyl group such as 2-hydroxybutyl methacrylate and 4-hydroxybutyl methacrylate; Those having a methylol group such as N-methylolacrylamide, N-methylolmethacrylamide, and methylol stearamide; Glycidyl groups such as glycidyl acrylate and glycidyl methacrylate Having an isocyanate group such as 2-isocyanate ethyl methacrylate (for example, trade name: Karenz MOI, Showa Denko) Shall; 2-aminoethyl acrylate, such as those having amino group such as 2-aminoethyl methacrylate are mentioned.

(Base material)
The substrate used in the present invention is a dimensionally stable plate-like material, and any material can be used as long as necessary flexibility, strength, durability, etc. are satisfied, and depending on the purpose of use Selected.
When selecting a transparent substrate that requires light transmission, for example, glass, plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate) Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.). In addition to the above, the base material of the surface functional member that does not require transparency includes paper, paper laminated with plastic, metal plate (for example, aluminum, zinc, copper, etc.), and the like as described above. Examples thereof include paper or plastic film on which metal is laminated or vapor-deposited.
The base material is appropriately selected according to the use of the surface functional member and the relationship with the functional material to be adsorbed. From the viewpoint of processability and transparency, the base material having a surface made of a polymer resin is used. Specifically, a resin film, a transparent inorganic base material such as glass whose surface is coated with a resin, and a composite material whose surface layer is a resin layer are all suitable.
Representative examples of the substrate having a resin coated surface include a laminate having a resin film adhered to the surface, a primer-treated substrate, and a hard-coated substrate. Typical examples of the composite material whose surface layer is a resin layer include a resin sealing material having an adhesive layer on the back surface, and a laminated glass that is a laminate of glass and resin.

For example, if the base material of an infrared cut filter to which the present invention is suitably applied is taken as an example, when it is required for a window glass, a display case, a lens, etc., ensure visibility and do not change the color tone of transmitted light. Therefore, it is preferable to select a base material that is also excellent in light transmittance and does not absorb in the visible light region. It may have some absorption in the visible light region, or may be a combination of materials that do not have optical transparency such as pigments and fibers.
As the light transmissive material, resin materials such as polymethyl methacrylate, polycarbonate, polystyrene, polydiethylene glycol bisallyl carbonate are suitable.

Further, the base material may be subjected to a surface roughening treatment according to the purpose of use.
For example, in the case of the above-described infrared cut filter, when applied to a filter for correcting the visibility of an optical machine such as a window glass, a video camera, or a camera that requires visibility, the surface irregularity property to be formed is controlled. Therefore, it is preferable to use a transparent substrate with a smooth surface, but in order to improve the amount of adsorption per unit area of the infrared absorber, the purpose is to increase the surface area and introduce more ionic groups. It is also possible to roughen the substrate surface in advance.

  As a method for roughening the substrate, a known method suitable for the material of the substrate can be selected. Specifically, for example, when the substrate is a resin film, glow discharge treatment, sputtering, sandblast polishing method, buff polishing method, particle adhesion method, particle coating method and the like can be mentioned. Further, when the base material is an inorganic material such as a glass plate, a mechanical roughening method 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.

-Base material surface or intermediate layer-
The base material in the present invention has a surface on which the above-described graft polymer in the present invention can be chemically bonded. In the present invention, the surface of the substrate itself may have such characteristics, and an intermediate layer having such characteristics may be provided on the surface of the substrate.

  As the intermediate layer, in particular, when a graft polymer is synthesized by a photograft polymerization method, a plasma irradiation graft polymerization method, or a radiation irradiation graft polymerization method, a layer having an organic surface is preferable. Preferably there is. Organic polymers include epoxy resins, acrylic resins, urethane resins, phenol resins, styrene resins, vinyl resins, polyester resins, polyamide resins, melamine resins, formalin resins and other synthetic resins, gelatin, casein, cellulose, Any natural resin such as starch can be used. In the photograft polymerization method, plasma irradiation graft polymerization method, radiation irradiation graft polymerization method, etc., since the start of graft polymerization proceeds from the extraction of hydrogen of the organic polymer, polymers that can easily extract hydrogen, especially acrylic resins, urethane resins, styrene-based polymers Use of a resin, a vinyl resin, a polyester resin, a polyamide resin, an epoxy resin or the like is particularly preferable from the viewpoint of production suitability.

-Layer that exhibits polymerization initiation ability-
In the present invention, as a compound that exhibits polymerization initiating ability by applying energy to the substrate surface, a polymerizable compound and a polymerization initiator are added, and an intermediate layer or a layer that exhibits polymerization initiating ability as the substrate surface. It is preferable from the viewpoint of efficiently generating active sites.
The layer that expresses the polymerization initiating ability (hereinafter referred to as a polymerizable layer as appropriate) is prepared by dissolving necessary components in a solvent capable of dissolving them, and providing them on the surface of the substrate by a method such as coating. It can be hardened and formed by irradiation.

(A) Polymerizable compound The polymerizable compound used in the polymerizable layer has good adhesion to the substrate and can be added with a monomer contained in the upper layer by applying energy such as actinic ray irradiation. Although there is no particular limitation, a hydrophobic polymer having a polymerizable group in the molecule is preferable.
Specific examples of such hydrophobic polymers include diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and allyl groups such as allyl (meth) acrylates and 2-allyloxyethyl methacrylates. Monomer homopolymer;
Furthermore, binary or multicomponent with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomer such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomer as a constituent unit. Copolymer;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of the polymerizable compound is preferably in the range of 0 to 100% by mass and particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

(B) Polymerization initiator The polymerizable layer in the present invention preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Can be selected and used as appropriate. Among these, use of photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization is preferable from the viewpoint of production suitability, and therefore, a photopolymerization initiator is preferably used.
The photopolymerization initiator is active with respect to irradiated actinic rays, and is capable of polymerizing a polymerizable compound contained in the polymerizable layer and a compound having a polymerizable group contained in the upper layer. For example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and the like can be used.

Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenones such as: benzophenone (4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.
The content of the polymerization initiator in the polymerizable layer is preferably in the range of 0.1 to 70% by mass and particularly preferably in the range of 1 to 40% by mass in terms of solid content.

The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. 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-methoxypropanol, 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, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount when the polymerizable layer is formed on the substrate is 0.1 in terms of the mass after drying from the viewpoint of sufficient polymerization initiation ability and prevention of film peeling while maintaining film properties. -20 g / m ² is preferable, and 1-15 g / m ² is more preferable.

As described above, the polymerizable layer forming composition is disposed on the surface of the substrate by coating or the like, and the solvent is removed to form a polymerizable layer to form a polymerizable layer. It is preferable that the film is hardened by light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that the polymerizable layer falls off after the graft polymer is formed on the substrate. Such a situation can be effectively suppressed. Here, the reason why light irradiation is used for pre-curing is the same as described in the section of the photopolymerization initiator.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried. However, from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

  Light irradiation performed as desired after heat drying includes, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp as a light source. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used. From the viewpoint of not inhibiting the subsequent formation of the graft pattern and the formation of the bond between the active site of the polymerizable layer and the graft chain, which is performed by applying energy, the polymerizable compound present in the polymerizable layer is partially Even after radical polymerization, it is preferable to irradiate with light to such an extent that radical polymerization does not occur completely, and the light irradiation time varies depending on the intensity of the light source, but is generally preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent washing is 10% or more and the initiator remaining rate after pre-curing is 1% or more.

Further, as one of preferred embodiments for generating a graft polymer on a substrate in the present invention, a compound having a polymerization initiating ability is bonded to the surface of the substrate, and a graft polymer is generated from the polymerization initiation site of the compound as a starting point. The aspect to be made is mentioned.
Examples of the compound having a polymerization initiating ability applicable to the above embodiment include a compound having a polymerization initiation site (Q) capable of initiating radical polymerization by photocleavage and a substrate binding site (Y) (hereinafter referred to as “light” as appropriate). Cleaving compound (QY) ").

Hereinafter, a method of bonding the photocleavable compound (QY) to the substrate surface will be described.
In order to bond the photocleavable compound (QY) to the substrate surface, the photocleavable compound (QY) is imparted on the substrate, brought into contact with the substrate surface, and a functional group present on the substrate surface ( Z) and the base material binding site (Q) may be combined to introduce the photocleavable compound (QY) onto the base material surface.

  Specific examples of the functional group (Z) present on the substrate surface include a hydroxyl group, a carboxyl group, and an amino group. These functional groups may be originally present on the surface of the base material due to the material of the base material in the silicon substrate or glass substrate, and may be present on the surface by subjecting the base material surface to a surface treatment such as corona treatment. It may be.

A polymerization initiation site capable of initiating radical polymerization by photocleavage (hereinafter simply referred to as “polymerization initiation site (Y)”) is a structure containing a single bond that can be cleaved by light.
As the single bond that is cleaved by this light, carbonyl α-cleavage, β-cleavage reaction, light-free rearrangement reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, benzyl Examples thereof include a single bond that can be cleaved using an imide cleavage reaction, a cleavage reaction of an active halogen compound, and the like. These reactions break a single bond that can be cleaved by light. Examples of the single bond that can be cleaved include a C—C bond, a C—N bond, a C—O bond, a C—Cl bond, a N—O bond, and a S—N bond.

  In addition, since the polymerization initiation site (Y) containing a single bond that can be cleaved by light is the starting point of graft polymerization in the graft polymer production step, when the single bond that can be cleaved by light is cleaved, the cleavage reaction causes Has the function of generating radicals. As described above, examples of the structure of the polymerization initiation site (Y) having a single bond that can be cleaved by light and capable of generating radicals include structures containing the following groups.

  Aromatic ketone groups, phenacyl ester groups, sulfonimide groups, sulfonyl ester groups, N-hydroxysulfonyl ester groups, benzylimide groups, trichloromethyl groups, benzyl chloride groups, and the like can be mentioned.

  When such a polymerization initiation site (Y) is cleaved by exposure and a radical is generated, if there is a polymerizable compound in the vicinity of the radical, this radical functions as a starting point for the graft polymerization reaction. The graft polymer can be produced.

  The substrate binding site (Q) is composed of a reactive group capable of reacting with and binding to the functional group (Z) present on the substrate surface. Specific examples of the reactive group are shown below. Such groups are mentioned.

  The polymerization initiation site (Y) and the substrate binding site (Q) may be directly bonded 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 carbon group, an aromatic group, an ester group, an amide group. Ureido group, ether group, amino group, sulfonamide group, and the like. The linking group may further have a substituent, and examples of the substituent that can be introduced include an alkyl group, an alkoxy group, and a halogen atom.

  Specific examples [Exemplary Compound 1 to Exemplified Compound 16] of Compound (QY) having a substrate binding site (Q) and a polymerization initiation site (Y) are shown below together with the cleavage portion. However, it is not limited to these.

  As a specific method for bonding the photocleavable compound (QY) to the functional group (Z) present on the substrate surface, the photocleavable compound (QY) is mixed with an appropriate solvent such as toluene, hexane or acetone. Or a method of applying the solution or dispersion to the surface of the substrate or a method of immersing the substrate in the solution or dispersion. At this time, the concentration of the photocleavable compound (QY) in the solution or in the dispersion is preferably 0.01% by mass to 30% by mass, and particularly preferably 0.1% by mass to 15% by mass. As a liquid temperature in the case of making it contact, 0 to 100 degreeC is preferable. The contact time is preferably 1 second to 50 hours, and more preferably 10 seconds to 10 hours.

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

<Functional material adsorption layer formation process>
In the functional material adsorbing layer forming step, the functional material adsorbing layer is formed by adsorbing the functional material to the graft polymer bonded on the base material in the graft polymer generating step.
What is necessary is just to select the functional raw material in this invention suitably according to the objective of a functional surface. Regarding the form of the functional material, the form of fine particles, small molecules, and the like is 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 adsorbed ionically, it goes without saying that the particle size and the amount of adsorption are limited by the surface charge of the fine particles and the number of ionic groups. The particle size is generally preferably in the range of 0.1 nm to 1 μm, more preferably in the range of 1 nm to 300 nm, and particularly preferably in the range of 5 nm to 100 nm.
Depending on the presence of the ionic group, the particles bonded to the graft polymer are regularly arranged in a substantially single layer state depending on the presence state of the ionic group, or each ionic group of the long graft chain. Nano-scale fine particles are adsorbed one by one, and as a result, they are arranged in multiple layers.

  Next, examples of functional materials that can be used in the present invention will be specifically described in accordance with the purpose of the surface functional member.

1. Functional material 1-1. Fine Particles for Antireflection Member When the functional member of the present invention is used as an antireflection member, it is preferable to use at least one kind of fine particles selected from resin fine particles and metal oxide fine particles as functional fine particles. By using such fine particles, a uniform and excellent antireflection ability that can be suitably used on the surface of an image display body, a clear image can be obtained without reducing image contrast, and excellent durability. It is possible to provide a roughened member that can be suitably used for an antireflection material capable of achieving the above.

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. It is mentioned as a suitable thing. In addition, so-called transparent pigments such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, and talc, and pigment fine particles called white pigments can be used as long as they have preferable shapes described below.
As the resin fine particles, those having high hardness are preferable from the viewpoint of durability, specifically, for example, spherical fine particles made of resin such as acrylic resin, polystyrene resin, polyethylene resin, epoxy resin, silicon resin, among others, Crosslinked resin fine particles are preferred.
In this application, 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 ionically bonded to the graft interface are regularly arranged in a substantially single layer state. In the case of using the roughened member of the present invention as an antireflection material, it is effective from the viewpoint of controlling the film thickness to be λ / 4 with respect to the wavelength (λ) where reflection should be prevented. Preferably, considering that the particle diameter of the fine particles is almost the same as the film thickness of the roughened layer, when the particle diameter is smaller than 100 nm, the roughened layer becomes too thin and the antireflection property tends to decrease. In addition, when the thickness is larger than 300 nm, diffuse reflection is large and white turbidity becomes remarkable. Therefore, it is difficult to obtain a transparent feeling, and the contact area that is ionically bonded to the graft interface becomes too small, resulting in roughening. There is a tendency for the strength of the layer to decrease.

1-2. Fine particles for conductive film When the functional member of the present invention is used as a conductive film, the functional fine particles are selected from conductive resin fine particles, conductive or semiconductor metal fine particles, metal oxide fine particles, and metal compound fine particles. It is preferable to use at least one kind of fine particles.
As the conductive metal fine particles or metal oxide fine particles, any conductive metal compound powder having a specific resistance of 1 × 10 ³ Ω · cm or less can be used widely. 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), etc. and their alloys, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), ruthenium oxide (RuO ₂ ), or the like can be used.
Further, metal oxide or metal compound fine particles having characteristics as a 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 Oxide semiconductor fine particles such as SnO ₄ and In ₂ O ₃ —ZnO, and fine particles using a material doped with impurities compatible with these, and spinel compound fine particles such as MgInO and CaGaO, TiN, ZrN, and HfN And conductive nitride fine particles such as LaB and conductive boride fine particles such as LaB. These can be used alone or as a mixture of two or more.

1-3. Fine particles for surface antibacterial material When the functional member of the present invention is used as an antibacterial material, it is preferable to use metal or metal oxide fine particles having antibacterial action and bactericidal action as functional fine particles.
Specifically, as a material capable of forming such metal (compound) fine particles, for example, a simple metal having bactericidal properties such as silver (Ag), copper (Cu), and the like containing at least one of them. An alloy or a metal oxide thereof can be used. In addition, titanium oxide, iron oxide, tungsten oxide, zinc oxide, strontium titanate, etc., which are metal compound semiconductors that exhibit bactericidal action when irradiated with light including wavelengths in the ultraviolet region such as fluorescent lamps and sunlight, and these And metal compounds modified with platinum, gold, palladium, silver, copper, nickel, cobalt, rhodium, niobium, tin, and the like.

1-4. Fine particles for ultraviolet absorbing member When the functional member of the present invention is used as an ultraviolet absorbing member, examples of the functional fine particles include iron oxide, titanium oxide, zinc oxide, cobalt oxide, chromium oxide, tin oxide, and antimony oxide. Use of metal oxide fine particles is preferable because it has a high shielding function in the ultraviolet A and B regions (light wavelength 280 to 400 nm). In the present invention, a high molecular compound is used as a base material, and by combining it with the polymer compound, a high function and processability as an ultraviolet shielding film and sheet are expressed, and various applications are expected. It is also expected to improve the light resistance of the polymer material by utilizing the ultraviolet shielding effect of the metal oxide.

1-5. Fine particles for optical materials Functional fine particles used for color filters, sharp cut filters, nonlinear optical materials, etc. used in optical equipment include fine particles made of semiconductors such as CdS and CdSe, or metals such as gold, and silica as a substrate. By using glass or alumina glass, it is not only suitable for color filters, but it is expected to be a nonlinear optical material such as optical switches and optical memory materials after the third-order optical nonlinear susceptibility is confirmed to be large. Is done. Specific examples of the fine particles used here include noble metals such as gold, platinum, silver and palladium or alloys thereof, and from the viewpoint of stability, they can be rapidly dissolved by an alkali such as gold or platinum. Non-substances are preferred.

  Further, as the ultrafine particles of metal (compound) suitable as a nonlinear optical material, specifically, for example, gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), A simple substance such as rhodium (Rh), osmium (Os), iron (Fe), nickel (Ni), ruthenium (Ru), and an alloy containing one or more of these, and an average particle diameter of 10 to 1000 angstroms Ultrafine particles having The particle diameter may be either primary particles or secondary particles, but those that do not scatter visible light are preferred. Among them, fine particles of noble metals selected from Au, Pt, Pd, Rh, Ag having a particle size of 10 nm or less, dispersed independently in a solvent such as toluene, or Ti, V, Cr, Mn, Fe, Ni, Cu, Zn Preferred examples include metal fine particles selected from Cd, Y, W, Sn, Ge, In, and Ga.

  Using these ultrafine particles, when forming a nonlinear optical material by a usual method, that is, a sol-gel method, an impregnation method, a sputtering method, an ion implantation method, a melt precipitation method, etc., the fine particles are very likely to aggregate. For this reason, problems such as difficulty in increasing the concentration of fine particles in the composite and reduction in productivity have occurred. In particular, those having a low concentration of fine particles and a small contribution ratio of the fine particles to physical properties are limited in application and unsuitable for image memories, optical integrated circuits and the like using a third-order nonlinear optical effect. According to the configuration of the present invention, the fine particles are directly ionically bonded to the ionic group on the surface of the substrate, and the ionic groups are present at a high density by grafting, so that the fine particle concentration can be easily increased, Among optical materials, it can be said to be particularly suitable for such nonlinear optical material applications.

1-6. Fine particles for gas barrier film When the surface functional member of the present invention is used as a gas barrier film, as the functional fine particles, inorganic compounds such as silicon oxide, zirconium oxide, titanium oxide, alumina, magnesium oxide, tin oxide, or aluminum, Ultrafine powder made of a metal such as tin or zinc, that is, fine particles having an average particle diameter of 100 nm or less, preferably 50 nm or less is preferred. The ultrafine powder can be used in the form of one or a mixture of two or more selected from the above inorganic compounds and metals. By using an insulating inorganic compound such as silicon oxide as the ultrafine powder, the entire functional member can be made insulating. The ultrafine powder is particularly preferably silicon oxide that can be easily made into ultrafine powder.
As the substrate, it is preferable to use an organic resin film having a high gas barrier property, such as polyethylene terephthalate, polyamide, polypropylene, an ethylene-vinyl alcohol copolymer, polyvinyl alcohol, or the like.

1-7. Fine particles for organic light-emitting elements Organic fine-particle elements can be formed by forming fine particles obtained by agglomeration of organic dye molecules that emit light when excited by hot carriers and forming a layer of these on the surface of a substrate having electrodes. it can. Examples of the organic dye used here are as follows, but of course not limited thereto, and are appropriately selected in consideration of the purpose of use of the solid-state optical functional element.

Blue luminescent oxazole dyes such as p-bis [2- (5-phenyloxazole)] benzene (POPOP); green luminescent such as coumarin 2, coumarin 6, coumarin 7, coumarin 24, coumarin 30, coumarin 102, coumarin 540, etc. Coumarin-based dyes: Rhodamine 6G, rhodamine B, rhodamine 101, rhodamine 110, rhodamine 590, rhodamine 640 and other red-emitting rhodamine-based (red) dyes; and oxazine 1, oxazine 4, oxazine 9, and oxazine 118 Oxazine dyes suitable for optical functional elements that can emit light in the outer region and are particularly suitable for optical communication can be mentioned.
Further examples include cyanine dyes such as phthalocyanine and cyanide iodide compounds. In addition, when selecting these pigment | dyes, it is preferable on the objective of thin film formation to select what is soluble in polymers, such as an acrylic resin. Examples of such a dye include POPOP, coumarin 2, coumarin 6, coumarin 30, rhodamine 6G, rhodamine B, rhodamine 101 and the like.

In addition, organic molecules used in organic electroluminescence (EL) films, such as 8-hydroxyquinoline aluminum (AlQ ₃ ), 1,4 bis (2,2 diphenylvinyl) biphenyl, polyparaphenylene vinylene (PPV) derivatives, di Fine particles formed of a styryl arylene derivative, a styryl biphenyl derivative, a phenanthroline derivative, or the like, or a medium obtained by adding an additive to the organic molecule may be used.

1-8. Infrared absorbing member (infrared cut filter) material When the functional member of the present invention is used as an infrared cut filter, an infrared absorbent can be used as the functional material.
As the infrared absorber, an infrared absorbing dye (infrared absorbing pigment) having an absorption maximum at a wavelength of 760 nm to 1200 nm is preferably exemplified. As the infrared absorbing dye, those having high light fastness are preferable from the viewpoint of stability and durability. In addition, when an infrared cut filter excellent in transparency, that is, visible light transmission, is to be obtained, it is maximum. Those having absorption on the long wavelength side are preferred.
Typical examples include polymethine dyes containing cyanine dyes, phthalocyanine dyes, naphthoquinone / anthraquinone dyes, dithiol metal complex dyes, triphenylmethane dyes, aminium / diimonium dyes, and the like. Among these, from the viewpoint of stability, polymethine dyes such as pyrylium / thiopyrylium-based and squarylium-based dyes are preferable, and from the viewpoint of transparency, aminium / diimmonium-based dyes having a maximum absorption wavelength in a long wavelength region exceeding 900 nm are preferable. preferable.
Examples of these infrared absorbers include various infrared absorbing dyes and spectacle lenses described as dyes for recording and display in “Special Function Dyes—Technology and Market—” edited by Tadaburo Ikeda et al. (CMC, 1986). An infrared absorbing dye to be used can also be preferably used. In addition, dyes exemplified as photothermal conversion agents in paragraphs [0039] to [0065] of Japanese Patent Application No. 2001-4748 filed earlier by the applicant of the present application are also applicable.

  As described above, in 1-1 to 1-8, the application example of the surface functional member of the present invention and the functional material suitably used in the field have been described with specific examples, but the present invention is limited to this. It is not a thing, but the functional material has by selecting the base material which the graft polymer is bonded to at least one side and the kind of the functional material having the physical property that can be bonded to the graft polymer, and combining them appropriately. It goes without saying that various members having functional surfaces that make use of physical properties can be constructed.

2. Regarding the physical properties of the functional material (charge when ionically bound to the functional group of the graft polymer) With regard to the physical properties of the functional material, for example, when it has its own charge such as silica fine particles, When using an absorbent that is normally dissociated into ions in the coating solution, select a graft polymer having an ionic group opposite to the charge of the functional material. The functional material can be adsorbed as it is to the graft polymer layer to which is bonded.
In addition, when the functional member is a fine particle, for the purpose of adsorbing with the ionic group, fine particles having a high density on the surface are prepared by a known method and adsorbed to the ionic group of the graft polymer. It can also be made. In such a case, it is possible to widen the selection range of the fine particles.

From the viewpoint of durability, the functional material is preferably bonded in the maximum amount that can be adsorbed to the ionic group of the graft polymer present on the base material.
For example, in the case where fine particles are used as the functional material, the dispersion concentration of the dispersion liquid containing fine particles is preferably about 0.01 to 10% by mass from the efficiency of the functional expression on the functional surface. Moreover, if the coating liquid containing the raw material dissociated into ions, such as an infrared absorber, is used, the concentration of the functional material in the coating liquid is preferably about 0.01 to 10% by mass.

3. Functional material adsorption mode The functional material is adsorbed on the graft polymer layer, and the functional material adsorption layer is provided by applying a solution in which the functional material is dissolved or dispersed on the base material to which the graft polymer is directly bonded. And a method of immersing a base material to which a graft polymer is directly bonded in a dispersion of charged fine particles on the surface. In both cases of application and immersion, an excessive amount of functional material is supplied, and in order to achieve sufficient adsorption between the graft polymer layer, the surface where the dissolution, dispersion, and graft polymer are bonded is used. The contact time with the substrate is preferably about 10 seconds to 180 minutes, more preferably about 1 to 100 minutes.
Although the following (1) and (2) are mentioned as an example of the specific aspect of functional material adsorption | suction, this invention is not limited to this.

(1) A graft polymer chain having an ionic group is introduced on the surface of the substrate using an ionic monomer such as ammonium having a positive charge as an interactive group, and then the substrate is added to the silica fine particle dispersion. By immersing for a predetermined time and then washing and removing excess dispersion with water, silica fine particles are formed on the surface of the transparent substrate from a state of almost one layer according to the density of ionic groups. A fine particle adsorbing layer (functional material adsorbing layer) formed by dense adsorption is formed up to the state.

(2) An ionic group such as ammonium having a positive charge is introduced into the surface of the transparent substrate, and then a mercaptonaphthol metal complex salt (maximum absorption wavelength: 1110 nm) represented by the following formula: This base material is immersed in the dispersion for a predetermined time, and then the excess dispersion liquid is washed and removed with water. A functional material adsorbing layer) is formed.

  Thus, a functional material adsorption layer can be provided. The film thickness of the functional material adsorbing layer can be selected depending on the purpose, but generally from the viewpoint of scratch resistance and transparency, a range of 0.001 μm to 10 μm is preferable, and a range of 0.01 μm to 5 μm is preferable. More preferably, the range of 0.03 μm to 2 μm is most preferable.

<Crosslinked structure forming step>
In the cross-linked structure forming step, energy is imparted to the functional material adsorbing layer formed in the functional material adsorbing step to form a cross-linked structure in the functional material adsorbing layer.

  In the formation of the crosslinked structure, (1) an interactive group to which the functional material is not adsorbed may be used for forming the crosslinked structure, and (2) the interactive group adsorbs the functional material. However, it may be an embodiment that is not used for forming a crosslinked structure.

Examples of the graft polymer in the formation of the crosslinked structure (1) and (2) are as follows.
Examples of the case (1) include a case where the graft polymer is a binary polymer of a monomer having a carboxyl group and a monomer having a glycidyl group.
In the case of the above (2), for example, when the graft polymer is a terpolymer of a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having an isocyanate group, or the graft polymer is a carboxyl group And a case where the monomer is a binary polymer of N-methylolacrylamide or the like which can react with itself to form a crosslinked structure.

The cross-linking reaction is caused by applying energy under conditions different from the graphene polymer generation to the functional material adsorption layer. Examples of the energy application include heating, light irradiation, ultrasonic waves, electron beam irradiation, and the like.
In the present invention, it is preferable that the crosslinked structure is formed by heating. As a specific example, there can be mentioned a reaction between a carboxyl group which is an interactive group of the graft polymer and a glycidyl group which is a crosslinkable group.

In the case where the energy application is performed by heating, as the heating means, 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.
Moreover, although heat processing changes with kinds of graft polymer formed, it is performed by heating at 50 to 300 degreeC for about 0.1 second to 60 minutes.
In the case where the energy application is performed by light irradiation, as the light irradiation means, for example, light sources from ultraviolet to visible regions such as mercury lamps, metal halide lamps, and Xe lamps from low pressure to ultrahigh pressure can be used. .

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

  The surface functional member (surface functional member of the present invention) can be produced by the steps described above according to the production method of the present invention.

  In the surface functional member obtained by the present invention, the graft polymer is directly bonded to the substrate, so that the graft polymer has an interactive group such as an infrared absorber or metal oxide fine particles represented by silica. A material having a specific function (functional material) has a functional material adsorbing layer excellent in durability, adsorbed electrostatically at a high density and uniformly. Further, in the present invention, the surface layer is functional because the functional material is adsorbed in a single layer state or a multilayer state on the interactive group of the graft polymer without using a binder. A functional surface that directly reflects the physical properties of the material. Furthermore, since the functional material is stably immobilized in the functional material adsorption layer by forming a cross-linked structure in the functional material adsorption layer, it is suitable for environments where surface functional members are used. The retainability of the functional material can be maintained without causing separation of the functional material.

  For example, if fine particles for a roughening member are used as the functional material, a roughening layer having uniform and fine irregularities in the shape of the fine particles is formed. If this roughened member is used as an antireflection material, the layer itself is a thin layer while achieving high antireflection performance, and there is a concern that light transparency may be hindered by using a transparent base material as the base material. Therefore, it can be suitably used not only for the reflection type but also for the transmission type image display.

  If an infrared absorber is used as a functional material, a layer in which an infrared absorber typified by a cyanine dye is adsorbed electrostatically at a high density and uniformly on the polar group (ionic group) of the graft polymer It can be set as the infrared rays absorption member (infrared cut filter) in which was formed. In such an infrared cut filter, since the infrared absorbent is localized on the surface of the infrared cut filter, the infrared absorbent layer is uniform and has a high infrared cut property compared to the amount of the absorbed infrared absorbent ( A functional material adsorption layer) is formed. Furthermore, when this infrared cut filter is used as a heat blocking filter, the layer itself is a thin layer while achieving high infrared absorption ability, and the transparency of visible light can be improved by using a transparent substrate as the substrate. Since there is no concern about hindrance, visibility is not hindered and the color tone of transmitted light is not changed.

  As described above, in the present invention, the characteristics of the functional material can be reflected by appropriately selecting the functional material. Moreover, the functional material adsorption layer formed by adsorbing the functional material can be formed on a surface of an arbitrary base material by a relatively simple process. Furthermore, since the durability of the functional material adsorbing layer capable of expressing excellent functionality is good, it has an advantage that it can be suitably used for various purposes.

  For further examples of 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, an electronic / electrical function can be imparted to the functional surface with ferrite. Various functions are expressed on the functional surface by using magnetic fine particles such as particles, optical functions using fine particles that absorb, reflect, and scatter light of a specific wavelength. It can be used in various fields such as various industrial products, pharmaceuticals, catalysts, varistors (variable resistors), paints and cosmetics. In addition to these various functions of various fine particle constituent materials, by using a polymer material as a base material, the ease of molding processing possessed by the polymer material can be utilized, and a novel material Development is also expected.

  Specific examples of the scope of application include, for example, optical parts, sunglasses, application to shielding films, shielding glass, shielding windows, shielding containers, shielding plastic bottles, etc. against light such as ultraviolet rays, visible light, and infrared rays, antibacterial films , Microbicidal filter, Antibacterial plastic molding, Fishing net, TV parts, Telephone parts, OA equipment parts, Vacuum cleaner parts, Fan parts, Air conditioner parts, Refrigerator parts, Washing machine parts Wide range of uses such as various office automation equipment such as humidifier parts and dish dryer parts, household appliances, sanitary goods such as toilet seats and washstand parts, other building materials, vehicle parts, daily necessities, toys and sundries It is done.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[Example 1]
In this example, an infrared cut filter which is a surface functional member of the present invention was produced as follows.

1. Graft polymer production process A biaxially stretched polyethylene terephthalate film (A4100, manufactured by Toyobo Co., Ltd.) with a film thickness of 188 μm is used as a base material, and a lithographic magnetron sputtering apparatus (CFS-10-EP70 manufactured by Shibaura Eletech) is used as a glow treatment. Then, oxygen glow treatment was performed under the following conditions.
-Oxygen glow treatment conditions-
Initial vacuum: 1.2 × 10 ⁻³ Pa
Oxygen pressure: 0.9 Pa
RF glow: 1.5 kW, processing time: 60 sec

-Formation of graft polymer-
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 in a nitrogen atmosphere. After heating, the substrate was taken out and immersed in distilled water overnight. Thereafter, excess polymer was washed away with running water. As described above, a base material in which a copolymer of acrylic acid and glycidyl methacrylate was grafted onto the base material surface was obtained. The obtained material is designated as a base material A.

2. Functional material adsorption layer forming step In this example, an infrared absorber was used as the functional material. As an infrared absorber, a cyanine dye having the following structure having a positive charge in a solution (maximum absorption wavelength in methanol of 813 nm) was used.

-Application of infrared absorbent solution to substrate A-
The substrate A obtained as described above was immersed in a solution composed of 0.05 g of the following cyanine dye and 5 g of methanol for 20 minutes. Thereafter, the surface was sufficiently washed with running water to remove excess infrared absorbent solution, and an infrared absorbing layer (functional material adsorbing layer) was formed on the surface of the substrate A.

3. Crosslinking structure forming step The base material A on which the infrared absorption layer is formed is heated at 140 ° C. for 5 minutes using a hot plate (model: T2B, manufactured by Banstead), and the carboxyl group and glycidyl group of the graft polymer are thereby obtained. Cross-linked.
As described above, an infrared cut filter that 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 in the kraft polymer production process of Example 1, instead of bonding a graft polymer comprising acrylic acid and glycidyl methacrylate (80/20 molar ratio) to the substrate surface, a graft comprising acrylic acid was produced by the following method. An infrared cut filter which is a surface functional member of Comparative Example 1 was obtained in the same manner as in Example 1 except that the polymer was bonded to the substrate surface and the cross-linked structure forming step was not performed. This was made into the infrared cut filter (1-2).

-Formation of graft polymer-
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 soaked film was washed with water for 8 hours to obtain a base material in which acrylic acid was graft-polymerized on the surface of the base material.

<Evaluation 1-1>
Evaluation of the retention of the functional material was performed as follows.
The obtained infrared cut filters (1-1) and (1-2) are immersed in saturated saline for 10 minutes, and the infrared transmittance (%) before and after immersion is compared to evaluate the retention of the functional material. did. The results are shown in Table 1 below.

<Evaluation 1-2>
A rubbing test was conducted as an evaluation of durability.
The surfaces of the obtained infrared cut filters (1-1) and (1-2) were rubbed 100 times by hand using cotton (BEMCOT, manufactured by Asahi Kasei Kogyo Co., Ltd.) wetted with water. Evaluation was performed by comparing the infrared transmittance (%) before and after rubbing. The results are shown in Table 1 below.

<Evaluation 1-3>
Evaluation was made by estimating the weight increase rate (%) of the formability of the crosslinked structure.
The evaluation was performed by immersing the obtained infrared cut filters (1-1) and (1-2) in water for 1 hour and comparing the weight increase rate (%) before and after the immersion.

As shown in Table 1, the infrared cut filter (1-1) of the example in which a crosslinked structure was formed in the infrared absorbent layer (functional material adsorbing layer) had an infrared transmittance before and after immersion in saturated saline. It can be seen that there is no change and the retention of the infrared absorber 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 transmittance as that of the example before being immersed in saturated saline, but saturated sodium chloride. It can be seen that the infrared transmittance has increased remarkably after immersion in water, and the retention and sustainability of the infrared absorbent in the infrared absorbent layer is low.
Moreover, the infrared cut filter (1-1) of an Example has a low weight increase rate, and it can be guessed that sufficient crosslinked structure is formed in the infrared absorber layer.

[Examples 2-1 to 2-3]
In this example, a surface functional member having a pigment adsorbed on a glass substrate was produced.
1. Graft polymer production process-Fabrication of a substrate bonded with a compound capable of initiating polymerization-
A glass substrate (Nippon Sheet Glass Co., Ltd.) was immersed in a Piranha solution (sulfuric acid / 30% hydrogen peroxide = 1/1 volume ratio mixed solution) overnight, and then washed with pure water. The substrate was placed in a separable flask purged with nitrogen, immersed in a dehydrated toluene solution of 0.5 wt% of the following compound A, and heated to reflux for 1 hour. After taking out, it wash | cleaned in order with toluene, acetone, and a pure water. Let the obtained base material be base material A1.

-Formation of graft polymer-
On the substrate A1 obtained above, 5 ml of a 5 wt% monomer aqueous solution of acrylic acid / glycidyl methacrylate (molar ratio 90/10) is dropped and covered with a quartz plate to uniformly apply the 5 wt% monomer aqueous solution to the base material A1. And sandwiched between quartz plates. Next, it exposed for 5 minutes using exposure machine (UVX-02516S1LP01, Ushio Electric Co., Ltd. product). Thereafter, the quartz plate was removed and washed with water to obtain a base material in which acrylic acid and glycidyl methacrylate were copolymerized. This is called a base material B.

2. Functional material adsorption | suction process The obtained base material B was immersed in 5 wt% sodium bicarbonate water for 5 minutes. After taking out, it was immersed in a 0.5 wt% aqueous solution of methylene blue for 1 minute and then washed with water to obtain a glass plate (base material C) on which methylene blue was adsorbed.

3. Crosslinking structure formation process The obtained base material C is 120 degreeC in Example 2-1 (140 degreeC in Example 2-2, Example 2-3) using a hotplate (model: T2B, the Banstead company make). Then, heating was performed at 160 ° C. for 5 minutes to crosslink the carboxyl group and glycidyl group of the graft polymer.
As described above, the surface functional members of Examples 2-1 to 2-3 were obtained. These are designated as surface functional members (2-1) to (2-3).

[Comparative Example 2]
In the production of Example 2-1, a 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. This is designated as a surface functional member (2-4).

[Examples 3-1 to 3-3]
In the graft polymer production process of Examples 2-1 to 2-3, the same procedure as in Examples 2-1 to 2-3 was performed except that the molar ratio of acrylic acid / glycidyl methacrylate was changed from 90/10 to 80/20. Thus, each surface functional member of Examples 3-1 to 3-3 was obtained. These are designated as surface functional members (3-1) to (3-3).

[Comparative Example 3]
In the production of Example 3-1, a surface functional member of Comparative Example 1 was obtained in the same manner as in Example 3-1, except that the crosslinked structure forming step (heating) was not performed. This is designated as a surface functional member (3-5).

[Examples 4-1 to 4-3]
In the graft polymer production process of Examples 2-1 to 2-3, the same procedure as in Examples 2-1 to 2-3 was performed except that the molar ratio of acrylic acid / glycidyl methacrylate was changed from 90/10 to 70/30. Thus, each surface functional member of Examples 4-1 to 4-3 was obtained. These are designated as surface functional members (4-1) to (4-3).

[Comparative Example 4]
In the production of Example 4-1, a surface functional member of Comparative Example 4 was obtained in the same manner as in Example 4-1, except that the crosslinking structure formation step (heating) was not performed. . This is designated as a surface functional member (4-4).

<Evaluation 2-1>
The change (decolorization) of the retention of the functional material due to the heating conditions in the crosslinked structure forming step was evaluated. The results are shown in Table 2.
Evaluation is carried out by using the surface functional members (2-1) to (2-4), (3-1) to (3-4), and (4-1) to (4-4) in saturated saline, respectively. After the immersion for 5 hours, the absorbance at 570 nm, which is the absorption wavelength of the dye (methylene blue), is measured by UV-Vis absorption spectrum, and the dye residual ratio (%) before and after immersion in saturated saline is calculated by the following formula. Was done.
Dye remaining rate (%) = absorbance after immersion in saturated saline / absorbance before immersion in saturated saline × 100

<Evaluation 2-2>
The formability of the crosslinked structure was evaluated by estimating 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 after immersion. In addition, this evaluation was performed only about the surface functional members (2-1) to (2-4). The results are shown in Table 2.

As shown in Table 2, each of the surface functional members of the examples had a high dye residual ratio when compared with each of the surface functional members of the comparative examples, and the crosslinked structure forming step was performed. It can be seen that the retention of the functional material (pigment) and its sustainability have been improved.
When acrylic acid / glycidyl methacrylate (90/10) is heated at 160 ° C. for 5 minutes, and acrylic acid / glycidyl methacrylate (80/20) or (70/30) is heated at 140 ° C. for 5 minutes or longer. A dye residual ratio of 80% or more was observed. From this, it can be seen that the sufficient retention structure and the sustainability of the functional material (pigment) are further improved by forming a sufficient cross-linked structure in the functional material adsorbing layer.
Moreover, each surface functional member of an Example has low weight increase rate, and it can be guessed that sufficient crosslinked structure is formed in the functional material adsorption layer.

[Example 5]
In the graft polymer production step of Example 2-1, acrylic acid / glycidyl methacrylate (molar ratio 90/10) was changed to acrylic acid / N-methylolacrylamide (molar ratio 80/20), and acrylic acid and N- A surface functional member of Example 5 was obtained in the same manner as in Example 2-1, except that a graft polymer of methylolacrylamide was produced and the heating condition in the crosslinked structure forming step was changed to 130 ° C. for 10 minutes. It was. This is the surface functional member 5.
When evaluation of the obtained surface functional member 5 was performed in the same manner as in the above <Evaluation 2>,
It was confirmed that the dye residual ratio was 80% or more.

Claims (1)

Directly bonding a graft polymer having a functional group capable of interacting with a functional material and a crosslinkable functional group on a substrate;
A step of adsorbing the functional material to the functional group capable of interacting with the functional material of the graft polymer to form a functional material adsorbing layer;
Forming a cross-linked structure in the functional material adsorbing layer by applying energy to the functional material adsorbing layer;
A method for producing a surface functional member, comprising: