JP2024101271A - Surface-modified article - Google Patents

Abstract

To provide surface modification of an improved material.SOLUTION: In one aspect, the present disclosure provides a method for surface modification of a material, the method comprising (1) oxidizing the material so that the oxidation level of the surface of the material is in a specific numerical range when measured by X-ray photoelectron spectroscopy (XPS), and (2) A. grafting the oxidized material, and/or B. treating the oxidized material with a hydrophilic polymer. In one aspect, the present disclosure provides a method for producing a fiber composite material in which the fiber material is included in the second material, the method comprising (1) oxidizing at least one of the fiber material and the second material, (2) after the oxidizing step, interfacing or bonding the fiber material and the second material, and (3) melting the second material to obtain a fiber composite material.SELECTED DRAWING: None

Description

The present disclosure relates to surface modification of articles. In particular, the present disclosure provides methods for making articles by surface modification and surface-modified articles, as well as articles including composite materials using surface-modified materials.

Adhesive materials or composite materials formed by integrating different materials are used in various products such as automobile parts, aircraft parts, medical devices, and electronic devices (e.g., International Publication No. 2005/075190). The strength of the adhesive material or composite material may be insufficient, especially at the interface between the different materials, which may limit the use of the adhesive material or composite material. Therefore, it is desirable to improve the bond strength between the different materials.

International Publication No. WO 2005/075190

The inventors have found that the surface modification of the present disclosure and composite materials using the same are suitable for various articles. Based on this finding, the present disclosure provides a method for producing an article by surface modification, a surface-modified article, and an article including a composite material using the surface-modified material.

Thus, the present disclosure provides:
(Item 1)
1. A method of making an article comprising a surface-modified material, comprising:
Surface modifying the material, comprising:
(1) subjecting the material to an oxidation treatment;
(2) surface-coating the oxidized material;
and forming an article from the surface-modified material.
Method.
(Item 2)
The method of any of the preceding items, wherein the article is selected from the group consisting of battery separators, masks, plastic members, aircraft materials, base materials and coating layers of wind power blades, sporting goods, medical, sanitary and cosmetic products, transplant devices, makeup brushes, sponges, writing implement members, various equipment members, building members, civil engineering members, articles having a coating layer on their surface, wrapping materials for motor sliding parts, plastics for printing, cell culture-related products, permeable membranes, adhesive tapes, paper, toys, anisotropic conductive films, mounted chips using conductive adhesives, lighting equipment, displays or films on their surfaces, screens, soundproofing and sound absorbing articles, vibration-proofing articles, conductive articles, and thermally conductive articles.
(Item 3)
The plastic member includes a plate, a film, a cloth, or a thread; the airframe material includes a ship, an airplane, an automobile, a rocket, a railway, a robot, an agricultural machine, a wheelchair, a nursing equipment, or a drone component, an automobile bonnet, or an automobile seat component; the sporting goods include a golf club shaft, a fishing rod, a tennis racket, a skiboard, or a skateboard; the medical, sanitary, or cosmetic product includes a diaper, a sanitary product, a bandage, a gauze, a tape, a disinfectant patch, various cleaning and face packs, napkins, agricultural and dry land greening materials, synthetic paper, a filter material, a wiping and cleaning material, an orthodontic bracket, a connection device for infusion or drip, a syringe, a drain tube, a cannula, or a joint; and the transplant device includes an artificial organ, an artificial joint, a spinal treatment implant, or a dental treatment implant. the writing implement member includes an ink collector, an ink regulator, an ink tank, an ink guide core, a pen core, a pen shaft, a batting, an ink absorbing sponge or a pen head; the cell culture-related product includes a cell adhesiveness control material or a cell fixation functional material; the building member includes an interior component for application such as wallpaper, a wall material, a floor material, a decking, a bridge pier or a tunnel inner wall; the article having a coating layer on its surface includes an article having an antibacterial/antiviral coating, a photocatalytic coating, an anti-rust coating, a plated surface or a vapor deposition surface; the paper includes synthetic paper composed of a plurality of materials selected from the group consisting of natural fibers, semi-synthetic fibers, chemical fibers and polymers; and the mounted chip using the conductive adhesive includes a silver-epoxy conductive adhesive/tin plating interface.
(Item 4)
The method of any of the preceding items, wherein the article is a battery separator comprising a surface-modified plastic nonwoven fabric.
(Item 5)
The method of any of the preceding items, wherein the article is a mask comprising a surface-modified plastic nonwoven fabric.
(Item 6)
The method of any of the preceding items, wherein the material comprises a material selected from metal materials such as steel/iron alloys, stainless steel, copper/copper alloys, titanium/titanium alloys, aluminum/aluminum alloys, tin, zinc, and tungsten carbide, and oxides thereof, silicon carbide, carbon fiber, cellulose fiber, foam, polymer materials, polyethylene, polypropylene, polytetrafluoroethylene, polyoxymethylene (POM) resin, polyamide (nylon), MC Nylon (registered trademark), silicone resin, and fluororesin.
(Item 7)
The method of any of the preceding items, wherein the article has the shape of a powder, a fiber, a woven fabric, a nonwoven fabric, a cloth, a plate, a film, a sheet, a tube, a rod, a hollow container, a box, a foam, a laminate, a plate, a timber, a round timber, a round steel, a round tube, a pipe joint, or a coupling joint.
(Item 8)
The oxidation treatment is
(i) the oxidation is carried out so that the percentage of C-O bonds/total carbon bonds within a depth of 10 nm of the surface of the material is increased by about 1 to 20% compared to before the oxidation treatment, as measured by X-ray photoelectron spectroscopy (XPS);
(ii) the C-O bond/total carbon bond ratio within a depth of 10 nm of the surface of the material is about 5-15% as measured by X-ray photoelectron spectroscopy (XPS);
(iii) The method of any of the preceding items, characterized in that the method is carried out so that the O/C atomic ratio within a depth of 10 nm of the surface of the material is about 0.03 to 0.2 as measured by X-ray photoelectron spectroscopy (XPS).
(Item 9)
surface modifying the material;
and interfacially bonding or adhering the material to a second material to produce an adhesive material. And forming an article from the adhesive material.
2. The method of any of the preceding items.
(Item 10)
The method of any of the preceding items, wherein the article is selected from the group consisting of implantable devices, automotive seating materials, various machinery components, building components, civil engineering components, and sporting goods mandrels.
(Item 11)
The method of any of the preceding items, wherein the implant device comprises an artificial joint, a spinal implant, or a dental implant, and the sporting goods stem comprises a golf shaft, a fishing rod, or a racquet grip.
(Item 12)
The method of any of the preceding items, wherein the article is an implant device comprising a titanium and plastic composite material.
(Item 13)
The method of any of the preceding items, wherein the article is a golf shaft or fishing rod comprising a composite of surface modified fiber and resin.
(Item 14)
20. The method of any of the preceding claims, wherein the interfacial bonding or adhering step is performed in the presence of an adhesive between the material and a second material.
(Item 15)
2. The method of any of the preceding claims, further comprising performing a step of interfacially bonding or adhering the material to a second material about one hour after the step of surface modifying the material.
(Item 16)
1. A method of manufacturing an article comprising a fiber composite material, the fiber material being contained within a second material, comprising the steps of:
(1) subjecting at least one of the fiber material and the second material to an oxidation treatment;
(2) a step of interfacially adhering or bonding the fiber material and the second material after the step of performing the oxidation treatment;
(3) melting the second material to obtain the fiber composite material;
(4) molding an article from the fiber composite material;
A method comprising:
(Item 17)
The method of any of the preceding items, wherein the article is a sports equipment axle.
(Item 18)
2. The method of any of the preceding items, wherein the second material is a resin material.
(Item 19)
The oxidation treatment is
(i) the oxidation is carried out so that the percentage of C-O bonds/total carbon bonds within a depth of 10 nm of the surface of the material is increased by about 1 to 20% compared to before the oxidation treatment, as measured by X-ray photoelectron spectroscopy (XPS);
(ii) the C-O bond/total carbon bond ratio within a depth of 10 nm of the surface of the material is about 5-15% as measured by X-ray photoelectron spectroscopy (XPS);
(iii) The method of any of the preceding items, characterized in that the method is carried out so that the O/C atomic ratio within a depth of 10 nm of the surface of the material is about 0.03 to 0.2 as measured by X-ray photoelectron spectroscopy (XPS).
(Item 20)
2. The method of any of the preceding items, wherein the weight percentage of fibrous material in the fibrous composite material is about 30% or less.
(Item 21)
2. The method of any of the preceding items, comprising a step of washing the material to be oxidized prior to the step of oxidizing.
(Item 22)
The method according to any of the preceding items, wherein the step of oxidizing comprises oxidizing by a treatment selected from the group consisting of plasma treatment, ozone treatment, ultraviolet radiation treatment, corona discharge treatment, high voltage discharge treatment and chemical oxidation.
(Item 23)
The surface coating step includes: (a) grafting a hydrophilic vinyl monomer onto the oxidized material;
The method of any of the preceding items, comprising (a) grafting a hydrophilic monomer and applying a hydrophilic polymer, or (c) grafting a vinyl ester monomer and subjecting to hydrolysis.
(Item 24)
An article manufactured by any of the methods described above.
(Item 25)
1. An article comprising an adhesive material in interfacial contact or adhesion between a first material and a second material,
An article, wherein a cut surface of at least one of the first material side half material and the second material side half material obtained by cutting the adhesive material along the interface between the first material and the second material has a (C-O bond)/(total carbon bond)% of about 5 to 15% within a depth of 10 nm of the material surface when measured by X-ray photoelectron spectroscopy (XPS).
(Item 26)
An article comprising a fibre composite material which, when assessed by a three-point bending test using a test piece 80 mm long, 10 mm wide and 2 mm thick, with a speed of 2 mm/min and a support distance of 40 mm, does not break at the breaking point.

In the present disclosure, it is contemplated that one or more of the above features may be provided in combinations in addition to those combinations explicitly stated. Still further embodiments and advantages of the present disclosure will be recognized by those skilled in the art upon reading and understanding the following detailed description, if necessary.

The present disclosure provides articles with excellent properties, such as high strength articles and articles with high hydrophilicity.

FTIR-ATR spectra of polypropylene samples with different oxidation times are shown. 1 shows the relationship between the absorbance ratio in the FTIR-ATR spectrum of an oxidized polypropylene sample and the oxidation treatment time. 1 shows the FTIR-ATR spectrum of a highly oxidized ultra-high molecular weight polyethylene sample. 1 shows the relationship between the oxidation time of a polypropylene sample and (A) the C1s narrow spectrum and (B) the O1s narrow spectrum in XPS measurement. 1 shows the relationship between the ratio of O1s/C1s orbitals determined from the XPS narrow spectrum of a polypropylene sample and the oxidation treatment time. The relationship between the type and percentage (%) of carbon bonds determined from the XPS narrow spectrum of a polypropylene sample and the oxidation treatment time is shown. The relationship between the oxidation treatment time of a polypropylene sample and the proportion (%) of the number of C—O—H bonds is shown. The figure shows the relative ratio of the atmospheric pressure plasma discharge treatment time of polypropylene fabric and the tensile shear strength of the sample. 1 shows the relationship between the ozone treatment time of polypropylene fabric and the relative tensile shear strength of the treated samples. 1 shows the relationship between the oxidation treatment time and the tensile shear strength for a sample in which a DHM-treated polypropylene plate and an aluminum plate are bonded together. (A) shows the load-displacement curves in a three-point bending test for a fiber composite material of polypropylene (PP) fiber/epoxy resin, and (B) shows the load-displacement curves in a three-point bending test for a fiber composite material of ultra-high molecular weight polyethylene (UHMWPE) fiber/epoxy resin. The improvement of water wettability due to the surface modification of the present disclosure is shown. A is a photograph of the polypropylene cloth before treatment when water is added. B is a photograph of the polypropylene cloth after the surface modification of the present disclosure when water is added. C is a photograph of the silicone rubber with the surface modification of the present disclosure applied only to the center when water is added. This shows the improvement in adhesion due to the surface modification of the present disclosure. By applying the surface modification of the present disclosure, paper and an aluminum plate were able to adhere to foamed polyethylene, which would not normally adhere to the surface. The improvement in adhesion due to the surface modification of the present disclosure is shown in the photographs of two polytetrafluoroethylene (PTFE) plates (top: untreated, middle: plasma-treated, bottom: surface modification of the present disclosure) attached with adhesive and then peeled off. When the surface modification of the present disclosure was applied, a strong force was required to peel off the PTFE plate, and the PTFE plate was distorted. FIG. 1 shows the improvement in water-based paintability due to the surface modification of the present disclosure. Photographs of water-based paints on TPX® resin (polymethylpentene) film. The left shows the results of the film with the surface modification of the present disclosure, and the right shows the results of the untreated film. The improvement of water-based paintability by the surface modification of the present disclosure is shown. The photographs show the case where water-based paint is applied to a silicone resin. The upper part shows the result over time of the plasma-treated silicone resin, and the lower part shows the result over time of the silicone resin that has been surface-modified according to the present disclosure.

Hereinafter, the present disclosure will be described with reference to the best mode. Throughout this specification, singular expressions should be understood to include the concept of the plural form, unless otherwise specified. Thus, singular articles (e.g., in the case of English, "a", "an", "the", etc.) should be understood to include the concept of the plural form, unless otherwise specified. In addition, it should be understood that the terms used in this specification are used in the sense commonly used in the field, unless otherwise specified. Therefore, unless otherwise defined, all technical terms and scientific and technical terms used in this specification have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. In the case of conflict, the present specification (including definitions) will take precedence.

The present disclosure will now be described by way of illustrative examples, with reference to the accompanying drawings, where necessary. Throughout this specification, the singular form should be understood to include the concept of the plural form, unless otherwise specified. In addition, it should be understood that the terms used in this specification are used in the same sense as commonly used in the art, unless otherwise specified. Therefore, unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. In the case of conflict, the present specification (including definitions) will take precedence.

The following provides definitions of terms used specifically in this specification and/or provides basic technical information as appropriate.

(Definitions, etc.)
As used herein, an "article" refers to a substance formed from one or more materials (including composite materials) and contemplated for use in a particular application. The article need not be the entire substance in its commercial form, but may be a component that constitutes a portion thereof. Unless otherwise specified, any reference to any material in this specification is intended to be a reference to any article.

In this specification, the term "composite material" refers to a material formed by integrating multiple different materials (which may be the same material). For example, a composite material may be a molded product in which materials are bonded or adhered to each other at an interface, or a molded product in which at least some of the materials are melted or fused, and the melted or fused parts are mixed together and solidified. In particular, a composite material in which one of the materials is fiber may be called a fiber composite material. In addition, in this specification, the term "adhesive material" refers to a composite material made by bonding materials.

In this specification, "X-ray photoelectron spectroscopy" (which may be abbreviated as XPS) refers to an analytical method that utilizes the emission of photoelectrons when the surface of a sample to be measured is irradiated with X-rays, and is a method that is widely used as a method for analyzing the surface layer of a sample to be measured. XPS allows qualitative and quantitative analysis to be performed using the X-ray photoelectron spectroscopy spectrum obtained by analyzing the surface of the sample to be measured. The relationship between the depth from the sample surface to the analysis position (hereinafter also referred to as "detection depth") and the photoelectron take-off angle is generally expressed by the following formula:
Detection depth ≒ electron mean free path × 3 × sin θ
(In the formula, the detection depth is the depth at which 95% of the photoelectrons constituting the X-ray photoelectron spectroscopy spectrum are generated, and θ is the photoelectron take-off angle.)
can be established. From the above formula, it can be understood that the smaller the photoelectron take-off angle, the shallower the depth from the sample surface can be analyzed, and the larger the photoelectron take-off angle, the deeper the depth can be analyzed. For example, in an analysis performed by XPS with a photoelectron take-off angle of 10 degrees, the analysis position is usually a very superficial layer about a few nm deep from the sample surface. Among the X-ray photoelectron spectroscopy spectra (horizontal axis: binding energy (eV), vertical axis: intensity) obtained by the analysis performed by XPS, for example, the C1s spectrum contains information on the energy peak of the 1s orbit of the carbon atom C. The elemental composition of the material within the measurement range can be determined, for example, by wide scan measurement (scan range: 0 to 1000 eV, energy resolution: 1 eV/step, etc.), and the ratio of each element can be calculated, for example, from the peak area of the 1s spectrum corresponding to each element. The bonding state of a certain element can be analyzed by narrow scan measurement (scan range: 1s spectrum range of that element, energy resolution: 0.1 eV, etc.). For example, in the C1s spectrum, the C-H and C-C peaks are located at about 284.6 eV, the C-N peak is located at about 285.7 eV, the C-O peak is located at about 286.1 eV, the C=O peak is located at about 288 eV, and the O-C-O peak is located at about 289 eV. Other eV peak positions for carbon or other elemental bonds are known or can be readily determined by one of ordinary skill in the art. XPS analysis can be performed, for example, on a surface of a 0.1 ^mm2 area of the material.

In this specification, the term "resin" refers to a polymer of the same polymerizable compound or a polymer of two or more polymerizable compounds with different structures, and includes a homopolymer and a copolymer.

As used herein, the term "about" refers to the indicated value plus or minus 10%, unless otherwise specified. When used with respect to ratios, "about" refers to a ratio of plus or minus 10% of the value (X) to the left of the indicated ratio (e.g., X:Y). When used with respect to temperature, "about" refers to the indicated temperature plus or minus 5°C.

Preferred Embodiments
In one aspect, the present disclosure provides methods of producing various articles by surface modification and various surface modified articles. In one embodiment, the present disclosure provides methods of producing articles, including composite materials made using surface modified materials, and the articles so produced.

The surface modification of the present disclosure can be applied to any material, such as petrochemical materials, wood, stone, metal materials, and glass materials. Suitable articles include, for example, battery separators (e.g., those containing a surface-modified (improved hydrophilicity) plastic nonwoven fabric), masks (e.g., those containing a surface-modified (improved hydrophilicity) plastic nonwoven fabric), plastic members (e.g., plates, films, cloth, threads, etc.), aircraft materials (e.g., members for ships, railways, robots, aircraft, automobiles, rockets, drones, etc., such as automobile bonnets (e.g., PP interior covers), automobile seat members), and motor parts. materials (e.g., wrapping materials for sliding parts), base materials and coating layers for wind power generation blades, sporting goods (e.g., golf club shafts, fishing rods, tennis rackets, skiboards, skateboards), medical, sanitary and cosmetic products (e.g., diapers, sanitary products, bandages, gauze, tapes, disinfectant patches, various sanitary and facial packs, napkins, agricultural and arid land greening materials, synthetic paper, filtration materials, wiping and cleaning materials, orthodontic brackets, medical equipment materials (infusion and drip connection devices, syringes, drainage tubes, cannulas, joints, tubes, threads, plates), transplant devices (e.g., artificial organs, artificial joints, spinal treatment implants), dental implants), cosmetic brushes, sponges, writing implement parts (e.g., ink collectors, ink regulators, ink tanks, ink guide cores, pen cores, pen shafts, batting, ink absorbing sponges, brush heads), various equipment parts, building parts (wallpaper and other interior parts for application, wall materials, floor materials, decking, bridge piers, tunnel inner walls, etc.), civil engineering parts, articles with a coating layer on the surface (antibacterial/antiviral coatings, photocatalytic coatings, articles with plated or vapor-deposited surfaces), printing plastics (e.g., for aqueous printing), cell culture related products (cell adhesion control materials, cell fixation functional materials, etc.), permeation membranes ( Examples of such materials include seawater desalination osmosis membranes, adhesive tapes, paper (such as synthetic paper composed of multiple materials selected from natural fibers, semi-synthetic fibers, chemical fibers, and polymers), toys, anisotropic conductive films, chips mounted using conductive adhesives (such as silver-epoxy conductive adhesive/tin-plated interfaces), lighting fixtures, displays or films on their surfaces, screens, sound-insulating and sound-absorbing articles, vibration-proof articles, conductive articles, and thermally conductive articles. Examples of plastics include polyolefins (such as polypropylene), nylon, and polyester, which are also described elsewhere in this specification as materials to which the surface modification of the present disclosure can be applied.

In one embodiment, articles containing composite materials made using the surface-modified materials of the present disclosure include implant devices (e.g., artificial joints, spinal implants, dental implants; composite materials of titanium and plastic, etc.), automobile seat materials (composite materials of urethane sponge and fiber, etc.), various equipment components, building components, civil engineering components (e.g., those containing composite materials containing metal (metal-reinforced plastic, metal-reinforced wood, etc.)), and axles for sporting goods (e.g., golf shafts, fishing rods, racket grips; composite materials of surface-modified fibers such as carbon fiber and resin, etc.).

In a specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a material for shipbuilding and marine vessels (commercial ships, work boats, naval vessels, fishing boats, motorboats, yachts, cruisers, etc.), and is a structural component of a vessel that uses a composite material made of fibers and plastics with improved adhesiveness. A type of vessel known as an FRP vessel is well known, and by using high-strength FRP produced by the surface modification of the present disclosure in the vessel, it is possible to strengthen the hull, reduce its weight, and reduce costs.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is an agricultural or dry land greening material (agricultural greenhouses, greenhouse covering materials, irrigation materials, mist equipment, agricultural polypropylene, mulch, fruit mulch, windbreak, insect and animal pest netting, etc.), in which nonwoven fabric of polymers such as polypropylene or polyethylene is made water absorbent and the absorbed material is placed to enable water retention.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a wall or floor material with soundproofing and heat insulation properties, which is made by bonding polymer foam to a metal plate. Polyethylene, polypropylene, urethane resin sponge, etc. cannot normally be bonded, but by carrying out the surface modification of the present disclosure, it becomes possible to strongly bond a thin metal plate such as an aluminum plate to the non-adhesive foam material, providing a lightweight composite material.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a flooring material that has been surface modified to increase the adhesiveness of an adhesive or pressure-sensitive adhesive tape. A flooring is a plate-shaped material that is laid on the floor of a farm, a construction site, or a building for protection purposes. A sheet of plastic, rubber, FRP, wood, metal, or a mixture of these can be laminated (using a pressure-sensitive adhesive tape as necessary) with a sheet of plastic, rubber, FRP, wood, metal, or a mixture of these that has been treated separately to form an enlarged sheet. Currently, it is common to transport polyethylene flooring to the site, connect it with a PE adhesive tape, and lay it down in a large size, but the adhesive strength between the PE flooring and the pressure-sensitive adhesive tape is weak, so it often separates. Therefore, the edge portion of the PE flooring can be surface modified to improve its adhesiveness, and then adhered with a PE adhesive tape (or a tape of PE or other polymers whose adhesiveness has been improved by surface modification) to make the flooring large.

In another specific embodiment, the article produced by the surface modification of the present disclosure is a polymer film, foam, molded body, or hook that has been surface modified to increase the adhesion of an adhesive, pressure sensitive adhesive tape, or double-sided tape adhesive. Commercially available adhesive hooks have limited load capacity due to low adhesion between the plastic body and the adhesive, but if the adhesive is peeled off and the surface modification treatment of the present disclosure is applied to the portion of the plastic body that is to be attached, the load capacity of the commercially available double-sided tape can be greatly increased.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a tape substrate made of a surface-modified polymer, a silicone resin, a fluororesin tape, a sheet, or a molded article that has increased adhesive properties for the adhesive. The surface modification of the present disclosure makes it possible to manufacture a pressure-sensitive adhesive tape made of a poorly adhesive polymer material coated with an adhesive, which has never been done before.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a plastic toy or molded object that can be painted with a water-based paint. Water-based or oil-based paint applied to polyethylene or polypropylene will peel off due to friction, but the surface modification of the present disclosure makes it possible to paint toys made of PE, PP, or silicone resin with a water-based (oil-based) paint. Materials often used in toys, such as polyvinyl chloride, have the problem of residual monomers, so the present disclosure provides an alternative material for use in children's toys.

In another specific embodiment, the article produced by the surface modification of the present disclosure is a plastic film, sheet or molding that can be printed with water-based inks.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a wind power generation blade, and the surface modification of the present disclosure makes the paint less likely to peel off, thereby providing stable protection for the blade, which is prone to damage and requires frequent repairs.

In another specific embodiment, the article produced using the surface modification of the present disclosure is an aircraft, helicopter, automobile, or other airframe, and the composite material that has been surface modified using the present disclosure can be water-based painted.

In another specific embodiment, the article produced by carrying out the surface modification of the present disclosure is ski equipment that is an adhesion product between wood and a board made of ultra-high molecular weight PE whose adhesive properties have been improved by the present treatment. Ultra-high molecular weight PE (UHMWPE) is used for ice skating rinks and the like because of its high strength and excellent abrasion resistance, but it has no adhesive properties and cannot normally be made into a composite material with other materials. However, ultra-high molecular weight PE that has been subjected to the surface modification treatment of the present disclosure can strongly adhere to other materials. The adhesive properties of the uneven surface of ultra-high molecular weight PE with an uneven surface can be improved to provide even stronger adhesion to wood. Metal or fiber composite materials can also be used instead of wood.

In a specific embodiment, examples of articles that can be produced by carrying out the surface modification of the present disclosure include a large-sized single sheet made by lining up plastic plates and bonding film to both sides (when film is bonded to one side, the film surface is elastic and acts as a hinge, allowing it to be folded to make it more compact), and a composite round pipe frame for a bicycle bonded to a pipe tube.

In a specific embodiment, articles produced by carrying out the surface modification of the present disclosure include robots, space equipment (rockets), aircraft, agricultural machinery (cultivators, tractors, etc.), wheelchairs, nursing care equipment, etc., and high-strength, lightweight components can be produced by using the fiber composite material (fiber-reinforced plastic, etc.) of the present disclosure.

In a specific embodiment, the article produced by carrying out the surface modification of the present disclosure may be an article such as a metal material, a wind power generation blade, or an article made of a material that is difficult to paint (plastic, polyolefin (e.g., polyethylene, polypropylene, polymethylpentene), etc.), and by carrying out the surface modification of the present disclosure on such an article, the surface of the article can be made hydrophilic or adhesive. For example, by carrying out the surface modification of the present disclosure on only a specific surface of the article, an article having different properties depending on the surface can be prepared, which may be useful, for example, for ship hull members. In addition, by carrying out the surface modification of the present disclosure before applying a coating to the surface of the article, such as a rust-preventive coating for a metal material or a coating for a wind power generation blade, the coating can be firmly bonded.

In a specific embodiment, the article produced by carrying out the surface modification of the present disclosure is an article made of resin (e.g., fluororesin), such as a lighting fixture, film, monitor, mobile phone screen, or various screens, and carrying out the surface modification of the present disclosure improves the coating (including water-based paint) on the article surface, making it possible to apply anti-reflective agents, antioxidants, water repellents, insect repellents, fluorescent agents, etc.

In a specific embodiment, the article produced by carrying out the surface modification of the present disclosure is a paper, film or molding, and may be produced from a mixture of a material in which the surface modification of the present disclosure has been carried out on a fiber (which may be a natural fiber, a semi-synthetic fiber, or a chemical fiber) and a paper pulp material, a polymer (polyolefin, polyester, polylactic acid, cellulose acetate, nitrocellulose, or a protein material (silk, animal hair fiber, etc.). Natural fiber waste (sugar cane, pineapple, hemp, cotton, etc.) can be used.

In one aspect, a method for manufacturing an article by surface-modifying a material of the present disclosure includes (1) oxidizing the material so that the oxidation level of the surface of the material (e.g., within 10 nm) is within a specific range as measured by X-ray photoelectron spectroscopy (XPS), and (2) surface-coating the oxidized material. In a preferred embodiment, the oxidizing step can be performed to achieve an oxidation level of the surface of the material below a level detectable by infrared absorption spectroscopy. The present disclosure also provides a method for manufacturing an article including an adhesive material, comprising a step of interfacially adhering or bonding the surface-modified material and a second material. In this specification, "interfacially adhering" means directly bonding the materials. In this specification, "adhering" means bonding the materials via an adhesive. Since the material produced by the surface modification of the present disclosure can replace conventional materials, a conventional process can be used for manufacturing an article using the material. Modifications may be made to conventional processes for manufacturing articles in consideration of changes in the properties of the material surface due to the surface modification.

In one aspect, the present disclosure provides a method for manufacturing an article including a fiber composite material in which a fiber material is contained within a second material, the method including the steps of (1) oxidizing at least one of the fiber material and the second material, (2) interfacially bonding or adhering the fiber material to the second material after the oxidizing step, and (3) melting the second material to obtain a fiber composite material. In a preferred embodiment, the second material is a resin material (including rubber). Since the fiber composite material made by the method of the present disclosure can replace conventional materials, the process for manufacturing an article using the material can be a conventional process. Modifications may be made to the conventional process for manufacturing an article to take into account changes in the properties of the composite material.

In one aspect, the present disclosure provides articles with a level of high strength not previously achievable.

(material)
In the present disclosure, materials to be surface-modified, interfacially bonded or adhered to the surface of an article include, but are not limited to, polymer materials, metals, glass, ceramics, aluminum nitride, silicon, silicon nitride, gallium nitride, carbon materials, wood, composite materials thereof, and the like, and it is contemplated that interfacially bonded or adhered between any of these materials can be achieved.

In one embodiment, the polymer material (e.g., resin (including rubber)) is selected from the group consisting of: (1) addition polymer: a homopolymer or copolymer of a monomer selected from the group consisting of olefins, vinyl compounds, vinylidene compounds, and other compounds having a carbon-carbon double bond; (2) fluororesin: polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethyne, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyvinyl fluoride; (3) polycondensate: polyester (including polyethylene terephthalate, aliphatic and wholly aromatic polyesters), polycarbonate, polybenzoate, polyimide, polyamide (including aliphatic polyesters such as nylon), (including polyamides and aromatic polyamides), (4) addition condensates: phenolic resins, urea resins, melamine resins, xylene resins, or polymers thereof, (5) polyaddition products: polyurethanes, polyureas, or polymers thereof, (6) ring-opening polymers: homopolymers or copolymers of cyclopropane, ethylene oxide, propylene oxide, lactones, lactams, or the like, (7) cyclized polymers: homopolymers or copolymers of divinyl compounds (e.g., 1,4-pentadiene), diyne compounds (e.g., 1,6-heptadiyne), or the like, (8) isomerized polymers: alternating copolymers of ethylene and isobutene, or the like, (9) electrolytic polymers: homopolymers or copolymers of pyrrole, aniline, acetylene, or the like, (10) silicon resins, silicone resins, (11) aldehyde or ketone polymers, (12) polyethersulfones, and (13) natural polymers: cellulose, proteins, polysaccharides, or the like. Other polymer materials (e.g., resins) include polyacetal, polyphenol, polyphenylene ether, polyalkyl paraoxybenzoate, polyimide, polybenzimidazole, poly-p-phenylene benzobisthiazole, poly-p-phenylene benzobisoxazole, polybenzothiazole, polybenzoxazole, and fibers such as acetate, carbon fiber, cellulose fiber, regenerated cellulose fiber (rayon, cupra, polynosic, etc.), vinylon, and fibers made from copolymers of vinyl alcohol and vinyl chloride.

Vinyl compounds, vinylidene compounds and other compounds having carbon-carbon double bonds as monomers that form polymer materials (e.g., resins (including rubber)) include ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, vinyl chloride, styrene, acrylic acid, methacrylic acid, esters of acrylic acid or methacrylic acid, vinyl acetate, vinyl ethers, vinylcarbazole, acrylonitrile, vinylidene chloride, vinylidene fluoride, isobutylene, maleic anhydride, pyromellitic anhydride, 1-butenoic acid, tetrafluoroethylene, trifluorochloroethylene, butadiene, isoprene, chloroprene, etc. Specific examples of polymer materials (e.g., resins, plastics) include polyester, polypropylene, polyethylene, polyolefin, acrylic, polyvinyl acetate, AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), polytetrafluoroethylene, polyoxymethylene (POM), polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyallyl diglycol carbonate, copolymers containing butadiene, synthetic rubber, polyether ether ketone (PEEK), rayon, cupra, polystyrene (PS), polyphenylene sulfide (PPS), polyaramid, polyimide, polyamide (nylon), MC nylon (registered trademark), polymethylpentene (Mitsui Chemicals' TPX (registered trademark)), vinylon, cotton, linen, silk, wool, etc.

In one embodiment, the polymeric material (e.g., resin) may be formed from a single type of polymer or a mixture of multiple types of polymers. In one embodiment, the polymeric material (e.g., resin) may be thermoplastic or thermosetting.

In one embodiment, the metal material may be steel, iron alloy, stainless steel, copper, copper alloy, titanium, titanium alloy, aluminum, aluminum alloy, tin, zinc, tungsten carbide, or oxides thereof.

In one embodiment, the article (or material) may have a shape such as, but is not limited to, a powder, fiber, woven fabric, nonwoven fabric, cloth, plate, film, sheet, tube, rod, hollow container, box, foam, laminate, etc. In one embodiment, for example, the metal article (or material) has a shape of a plate, square timber, round timber, round steel, round tube, pipe joint, or coupling joint.

In one embodiment, the material (e.g., a polymeric material) may include additives such as antioxidants, stabilizers, nucleating agents, flame retardants, fillers, foaming agents, and antistatic agents.

(process)
In one embodiment, the surface of the material may be washed to remove impurities prior to the surface modification treatment. In one embodiment, the material may be washed with a solvent or mixture of solvents having an SP value that differs from the solubility parameter of the material by about 0.5 to 10, for example, about 0.5, about 1, about 1.5, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, or a range between any two of these values. For example, polyolefins, silicone resins, fluororesins, polyvinyl chloride, polyvinylidene chloride, etc. are preferably washed with alcohol or toluene. Acetate, nylon, polyester, polystyrene, acrylic resins, polyvinyl acetate, polycarbonate, polyurethane, etc. are preferably washed with alcohol. Cellulosic materials such as rayon and cupra are preferably washed with detergent and then with alcohol. In one embodiment, silicone oil is preferably removed because it may inhibit oxidation of the material surface in the oxidation treatment step described herein. To remove silicone oil, the surface of the material may be washed with a cleaning agent such as, for example, a solvent with a solubility parameter of about 7-10 (e.g., about 7, about 8, about 9, about 10, or a range between any two of these values), isopropyl alcohol, nax Silicon Off SP (Nippon Paint), etc. In one embodiment, the material may be washed with a volume of cleaning agent of about 0.05 to 1 times the volume of the material, for example, about 0.05, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.7, about 1, or a range between any two of these values. In one embodiment, the material may be washed with the cleaning agent 2-5 times. In one embodiment, the washing may be performed with a combination of solvent and temperature that does not dissolve the surface of the material.

In one embodiment, before the surface modification treatment, the surface of the material may be roughened by scratching (such as by scraping with a file), which increases the area of interfacial adhesion or bonding, and may improve the strength of the composite material formed. In one embodiment, before the surface modification treatment, the material (particularly the polymer material) may be impregnated. The impregnation treatment is a process in which a compound (impregnant) that has affinity for the material is brought into contact with the material at a temperature below the softening point of the material to introduce the impregnant into the material surface. It is preferable that the material is not substantially deformed by the impregnation treatment. The impregnant may penetrate into the amorphous region of the material to form gaps inside the material. The impregnation treatment may facilitate the oxidation step, grafting step, etc. in the surface modification treatment. Any compound that has affinity for the material may be used as the impregnant. In one embodiment, the impregnant may be a solvent or mixture of solvents having a solubility parameter (SP value) that differs from the solubility parameter (SP value) of the material by about 0.5, about 1, about 2, about 3, about 4, or about 5. Even if the solvent dissolves the material at room temperature, it can be used as an impregnating agent if it is used at a low temperature and/or for a short time. The impregnating agent can be selected according to the type of material. For example, for polypropylene materials, a mixture of toluene, xylene, decalin, tetralin, cyclohexane, 1 volume of dichloroethane, and 4 volumes of ethanol can be used as an impregnating agent; for polyethylene materials, a mixture of toluene, xylene, α-chloronaphthalene, 1 volume of dichlorobenzene, and 1 volume of methanol can be used as an impregnating agent; for polystyrene materials, a mixture of 1 volume of toluene and 10 volumes of methanol can be used as an impregnating agent; and for polyethylene terephthalate materials, a mixture of 1 volume of phenol and 10 volumes of hexane can be used as an impregnating agent.

In one embodiment, the surface modification of the present disclosure includes a step of oxidizing the surface of the material. In one embodiment, the oxidation treatment of the material can be performed so that the percentage of bonds between major elements and oxygen (e.g., C-O bonds, Si-O bonds, etc.)/total bonds of the same element (e.g., carbon, silicon) within a depth of 10 nm of the surface of the material is increased by about 1-20%, about 1.5-15%, or about 2-10% from before the oxidation treatment, as measured by XPS. In one embodiment, the oxidation treatment of the material can be performed so that the percentage of bonds between major elements and oxygen (e.g., C-O bonds, Si-O bonds, etc.)/total bonds of the same element (e.g., carbon, silicon) within a depth of 10 nm of the surface of the material is increased by about 3-25%, about 4-20%, or about 5-15%.

In one embodiment, the oxidation treatment of the material can be performed so that the percentage of oxygen atoms among all atoms excluding hydrogen within a depth of 10 nm from the surface of the material increases by about 1-20%, about 1.5-15%, or about 2-10% from before the oxidation treatment when measured by XPS. In one embodiment, the oxidation treatment of the material can be performed so that the percentage of oxygen atoms among all atoms excluding hydrogen within a depth of 10 nm from the surface of the material increases by about 3-25%, about 4-20%, or about 5-15% when measured by XPS.

In one embodiment, the oxidation treatment of the material can be carried out under conditions such that the percentage of (C-O bonds)/(total carbon bonds) within a depth of 10 nm of the surface of the block-shaped polypropylene material increases by about 1-20%, about 1.5-15%, or about 2-10% from before the oxidation treatment when measured by XPS. In one embodiment, the oxidation treatment of the material can be carried out under conditions such that the percentage of (C-O bonds)/(total carbon bonds) within a depth of 10 nm of the surface of the block-shaped polypropylene material increases by about 3-25%, about 4-20%, or about 5-15% when measured by XPS.

In one embodiment, the oxidation treatment of the material can be carried out under conditions such that, when measured by XPS, the ratio of oxygen atoms among all atoms excluding hydrogen within a depth of 10 nm from the surface of the block-shaped polypropylene material increases by about 1-20%, about 1.5-15%, or about 2-10% from before the oxidation treatment. In one embodiment, the oxidation treatment of the material can be carried out under conditions such that, when measured by XPS, the ratio of oxygen atoms among all atoms excluding hydrogen within a depth of 10 nm from the surface of the block-shaped polypropylene material increases by about 3-25%, about 4-20%, or about 5-15%.

In one embodiment, the oxidation treatment of the material can be carried out under conditions such that the oxygen atom/carbon atom ratio within 10 nm of the surface of the block-shaped polypropylene material is increased by about 1-20%, about 1.5-15%, or about 2-10% from before the oxidation treatment when measured by XPS. In one embodiment, the oxidation treatment of the material can be carried out under conditions such that the oxygen atom/carbon atom ratio within 10 nm of the surface of the block-shaped polypropylene material is increased by about 3-25%, about 4-20%, or about 5-15% when measured by XPS.

The radiation source in the above XPS measurement may be, for example, Cr Kα radiation, Al Kα radiation, etc. The incident angle in the above XPS measurement may be, for example, about 10°, about 20°, about 30°, about 40°, about 50°, about 60°, about 70°, about 80°, or about 90°. The take-off angle in the above XPS measurement may be, for example, about 10°, about 20°, about 30°, about 40°, about 50°, about 60°, about 70°, about 80°, or about 90°. The number of atoms or the number of bonds in the above XPS measurement may be a value obtained only from the measurement result of 1s. The above XPS measurement may be performed by cleaning the material after the oxidation treatment.

The degree of oxygen introduction by oxidation treatment can also be measured by infrared absorption spectroscopy, and can be evaluated, for example, by the ratio of the absorbance of the absorption based on the carbonyl group introduced in the oxidation-treated material to the absorbance of the absorption based on the structure of the unchanged crystalline portion. For example, in the case of a polypropylene material, the ratio of the absorbance at about 1710 cm ⁻¹ based on the introduced carbonyl group to the absorbance at 973 cm ⁻¹ based on the absorption based on the methyl group of the unchanged crystalline portion can be an indicator of the introduction of oxygen. However, the inventors have found that oxidation treatment to a degree detectable by infrared absorption spectroscopy is generally excessive and can rather reduce the strength of the adhesive material or composite material, and have found that the degree of oxidation treatment that is within the above-mentioned specific numerical range when measured by X-ray photoelectron spectroscopy (XPS) is preferable. In particular, excessive oxidation treatment can cause a decrease in strength in adhesive materials or composite materials using materials in the form of fibers or films. The degree of oxidation treatment can be easily set by those skilled in the art by adjusting the treatment time, etc.

In one embodiment, the method described herein includes a step of oxidizing the surface of a fiber material (which may include a film-shaped material in addition to a fiber-shaped material). The fiber material may be any material, such as a polymer material (e.g., resin), metal, glass, carbon material, or a composite material thereof, as described herein. In one embodiment, the material of the fiber material may be polyester, polypropylene, polyethylene, nylon, acrylic, polyvinyl acetate, rayon, cupra, vinylon, polystyrene (PS), polyphenylene sulfide (PPS), polyaramid, polyimide, or polyamide. In one embodiment, the fiber material may be a mixed fiber material in which a plurality of fiber materials are mixed. In particular, both high strength and high toughness can be achieved by using a mixed fiber of high strength fibers (such as carbon fibers and glass fibers) and high toughness fibers (such as polypropylene fibers) to create a fiber resin composite material. In one embodiment, the fiber material may have a diameter of, but is not limited to, about 10 nm to about 1000 μm, for example, about 10 nm to about 1000 μm, about 100 nm to about 1000 μm, about 1 μm to about 1000 μm, about 10 μm to about 1000 μm, about 10 nm to about 100 μm, about 1 μm to about 100 μm, about 10 μm to about 100 μm, about 10 nm to about 10 μm, about 100 nm to about 10 μm, about 1 μm to about 10 μm, about 10 nm to about 1 μm, about 100 nm to about 1 μm, about 100 nm to about 1 μm, or about 10 nm to about 100 nm. Smaller diameters may be preferred with lower degrees of oxidation. In one embodiment, the fiber material may be made up of fine diameter (e.g., about 1 μm to about 100 μm) filaments twisted together to form a thicker diameter (e.g., about 100 μm to about 1000 μm) fiber.

The oxidation step can be carried out by plasma treatment, ozone treatment, ultraviolet irradiation treatment, high-voltage discharge treatment, chemical oxidation, etc.

Ozone treatment is a treatment in which the surface of a material is exposed to ozone. The exposure method can be any method, such as a method in which the material is held in an atmosphere in which ozone is present for a predetermined time, or a method in which the material is exposed to an ozone stream for a predetermined time. Ozone can be generated by supplying an oxygen-containing gas, such as air, oxygen gas, or oxygen-added air, to an ozone generator, and the ozone-containing gas can be introduced into a container or the like that holds the material to perform ozone treatment. Conditions such as the ozone concentration in the ozone-containing gas, exposure time, and exposure temperature can be determined according to the material so as to achieve the degree of oxidation of the material described in this specification.

In plasma treatment, a material is placed in a vessel containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen, or air, and exposed to plasma generated by glow discharge. When an inert gas such as argon or neon is present at low pressure, the surface of the material is attacked by the generated plasma, and radicals may be generated on the surface. When the material is then exposed to air, the radicals combine with oxygen, and carboxylic acid groups, carbonyl groups, amino groups, and the like may be introduced onto the surface of the material. The conditions of the glow discharge, such as intensity, time, and type of gas, can be determined according to the material so as to achieve the degree of oxidation of the material described in this specification.

The ultraviolet irradiation process is a process in which ultraviolet light is irradiated onto the surface of a material. Light sources for irradiating ultraviolet light include low-pressure mercury lamps, high-pressure mercury lamps, extra-high-pressure mercury lamps, xenon lamps, and metal halide lamps. In one embodiment, the surface of the material may be treated with an ultraviolet absorbing solvent before irradiation. Conditions such as the wavelength, intensity, and irradiation time of the ultraviolet light can be determined according to the material so as to achieve the degree of oxidation of the material described in this specification. In one embodiment, the wavelength of the ultraviolet light may be 360 nm or less.

High-voltage discharge treatment is a process in which a high voltage of hundreds of thousands of volts is applied between numerous electrodes installed on the inner walls of a tunnel-shaped treatment device while the material is moved through the device, causing discharge in the air. The discharge strength, time, and other conditions can be determined according to the material so as to achieve the degree of oxidation of the material described in this specification.

Corona discharge treatment is a process in which a high voltage of several thousand volts is applied between a grounded metal roll and a wire-shaped electrode placed a few mm apart to generate a corona discharge, and the material is passed between the electrode and the roll during this discharge. The discharge strength, time, and other conditions can be determined according to the material so as to achieve the degree of oxidation of the material described in this specification.

Chemical oxidation is an oxidation treatment in which a compound with oxidizing properties (oxidizing agent) is applied to the surface of a material. The oxidizing agent can be selected by a person skilled in the art from any suitable oxidizing agent in the relevant technical field.

In one embodiment, a treatment other than ozone treatment for oxidizing the surface of a material oxidizes the surface by irradiating the material, so ozone treatment is preferred when there are shadowed areas due to the shape of the material, such as a fiber aggregate like a nonwoven fabric.

In one embodiment, the surface coating step includes (a) grafting a hydrophilic vinyl monomer onto the oxidized material, (b) grafting a hydrophilic monomer and applying a hydrophilic polymer, (c) applying a hydrophilic polymer, (d) applying a hydrophilic polymer and grafting a hydrophilic monomer, or (e) grafting a vinyl ester monomer and subjecting to hydrolysis. Whether a monomer or polymer is hydrophilic is generally understood by those skilled in the art based on the presence of a hydroxyl group, a carboxyl group, a phosphate group, or a sulfo group, or on its solubility in water. Specific examples of these monomers and polymers are described elsewhere in this specification.

In one embodiment, the surface coating step does not substantially increase the weight of the oxidized material. Conventional grafting processes can increase the weight of a sample by 10-20%, which can result in detachment of the grafted portion. On the other hand, the surface coating of the present disclosure is less susceptible to such problems and may be preferred. In one embodiment, the surface coating step increases the weight of the oxidized material by less than about 5%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.2%, or less than about 0.1%.

In one embodiment, the surface modification of the present disclosure may include a step of grafting a monomer onto the surface of a material. The grafting step may be performed after a step of oxidizing the surface, or after a step of treating (coating) the material with a polymer. The monomer to be grafted is not limited as long as it is graftable, and a compound having a carbon-carbon double bond may be used. Examples of hydrophilic monomers include (meth)acrylamide, hydroxyalkyl (meth)acrylates such as 1-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, (alkyl)aminoalkyl (meth)acrylates such as 1-dimethylaminoethyl (meth)acrylate and 1-butylaminoethyl (meth)acrylate, alkylene glycol mono(meth)acrylates such as ethylene glycol mono(meth)acrylate and propylene glycol mono(meth)acrylate, and polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate. , ethylene glycol allyl ether, ethylene glycol vinyl ether, (meth)acrylic acid, aminostyrene, hydroxystyrene, vinyl acetate, glycidyl (meth)acrylate, allyl glycidyl ether, vinyl propionate, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N-(1-hydroxyethyl) methacrylamide, N-isopropyl methacrylamide, methacryloylmorpholine, N-vinyl-1-pyrrolidone, N-vinyl-3-methyl-1-pyrrolidone, N-vinyl-4-methyl-1-pyrrolidone, N-vinyl-5-methyl-1-pyrrolidone, N-vinyl-6-methyl-1-pyrrolidone, N-vinyl-3-ethyl-1-pyrrolidone, N-vinyl-4,5-dimethyl- 1-pyrrolidone, N-vinyl-5,5-dimethyl-1-pyrrolidone, N-vinyl-3,3,5-trimethyl-1-pyrrolidone, N-vinyl-1-piperidone, N-vinyl-3-methyl-1-piperidone, N-vinyl-4-methyl-1-piperidone, N-vinyl-5-methyl-1-piperidone, N-vinyl-6-methyl-1-piperidone, N-vinyl-6-ethyl-1-piperidone, N-vinyl-3,5-dimethyl-1-piperidone, N-vinyl-4,4-dimethyl-1-piperidone, N-vinyl-1-caprolactam, N-vinyl-3-methyl-1-caprolactam, N-vinyl-4-methyl-1-caprolactam, N-vinyl-7-methyl-1-caprolactam, N-vinyl-7-ethyl-1-caprolactam, N-vinyl Examples of monomers having a lower hydrophilicity include N-vinyl lactams such as N-vinyl-3,5-dimethyl-1-caprolactam, N-vinyl-4,6-dimethyl-1-caprolactam, and N-vinyl-3,5,7-trimethyl-1-caprolactam, N-vinyl formamide, N-vinyl-N-methyl formamide, N-vinyl-N-ethyl formamide, N-vinyl acetamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl phthalimide, N-vinyl amide, vinyl acetic acid, 1-butenoic acid, 2-butenoic acid, ethylene sulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, maleic anhydride, and pyromellitic anhydride. Examples of monomers having a lower hydrophilicity include vinyl monomers such as acrylic acid esters, methacrylic acid esters, vinyl acetate esters, and styrene. Grafting can be performed using one monomer or a mixture of multiple monomers.

Grafting of the monomer can be carried out by (1) adding a catalyst or initiator (hereinafter collectively referred to as "initiator"), (2) heating with or without the presence of an initiator, or (3) irradiating with ultraviolet light with or without the presence of a catalyst or initiator. Examples of the initiator include peroxides (benzoyl peroxide, t-butyl hydroxyperoxide, di-t-butyl hydroxyperoxide, etc.), azo compounds (2,2'-azobisisobutyronitrile), diserium ammonium nitrate (IV), persulfates (potassium persulfate, ammonium persulfate, etc.), redox initiators (combinations of oxidizing agents: persulfates, hydrogen peroxide, hydroperoxides, etc. with inorganic reducing agents: copper salts, iron salts, sodium hydrogen sulfite, sodium thiosulfate, etc., or organic reducing agents: alcohols, amines, oxalic acid, etc., or combinations of oxidizing agents: hydroperoxides, etc. with inorganic reducing agents: copper salts, iron salts, sodium hydrogen sulfite, sodium thiosulfate, etc., or organic reducing agents: dialkyl peroxides, diacyl peroxides, etc., and reducing agents: tertiary amines, naphthenates, mercaptans, organometallic compounds (triethylaluminum, triethylboron, etc.), etc.), and other known radical polymerization initiators. In the case of ultraviolet irradiation, in addition to the initiator, a photosensitizer such as benzophenone or hydrogen peroxide may be added as a catalyst. In one embodiment, a vinyl monomer having an amide group may be used, and the amide group may be subjected to Hofmann rearrangement by the method described in JP-A-8-109228.

A general grafting method can be used for grafting the monomer. Specific examples are shown below. In the case of a water-soluble initiator, the necessary amount is dissolved in water. In the case of a water-insoluble initiator, it is dissolved in an organic solvent (e.g., acetone, methanol, etc.) that is miscible with water, such as alcohol or acetone, and then mixed with water so as not to precipitate the initiator. Grafting is performed by adding the material and monomer to the initiator solution. In one embodiment, the inside of the treatment vessel is replaced with nitrogen. In one embodiment, grafting is performed under heating and/or ultraviolet irradiation.

In one embodiment, the surface modification of the present disclosure includes a step of treating (e.g., applying) a polymer to the surface of the material. Examples of polymers that can be used in this step include polyvinyl alcohol, carboxymethyl cellulose, ethylene-vinyl alcohol copolymer, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, poly-α-hydroxyacrylic acid, polyvinylpyrrolidone, polyalkylene glycols (polyethylene glycol, polypropylene glycol, etc.), sulfonated versions of these, sodium alginate, starch, silk fibroin, silk sericin, gelatin, various proteins, polysaccharides, etc.

In one embodiment, the step of treating the surface of the material with the polymer may be carried out in the presence of a catalyst or initiator. The catalyst and initiator may be the same as the initiator used in the grafting with the monomer. In one embodiment, this step is carried out by adding a solution (e.g., an aqueous solution) containing the polymer to the material. For example, the material is placed in a solution containing the polymer and the initiator and heated to a temperature of 10-80°C, 60-90°C, etc.

In one embodiment, the surface modification of the present disclosure includes a step of washing off excess polymer attached to the surface. For example, the material treated with the hydrophilic polymer may be boiled and washed for 1 to 10 minutes with an aqueous solution of fatty acid sodium salt (concentration 1 to 10% by weight), and then thoroughly washed with water. In one embodiment, the surface of the material treated with the hydrophilic polymer after washing can be washed to such an extent that when the total reflection infrared absorption spectrum is measured, there is no difference between the infrared absorption spectrum and the infrared absorption spectrum of the material that has only been subjected to the oxidation treatment. When the material is treated with a monomer or polymer with poor hydrophilicity, for example, methyl methacrylate or a polymer thereof, or vinyl acetate or a polymer thereof, the material can be washed with chloroform at 40° C. for 10 to 60 minutes, and further washed with chloroform, acetone, or methanol. In one embodiment, the material is washed to such an extent that the absorption at around 1710 cm ⁻¹ due to the carbonyl group of the treated material increases by about 0 to 5% in absorbance in the total reflection infrared absorption spectrum measurement, compared to the material that has only been subjected to the oxidation treatment. In one embodiment, the material can be effectively cleaned by heating and cleaning in an ultrasonic cleaner. In one embodiment, the degree of cleaning and the cleaning agent used can be appropriately selected by one skilled in the art based on the strength of the adhesive material or composite material.

In one embodiment, the material surface-modified by the method of the present disclosure can be interfacially adhered or bonded to a second material to form an adhesive material. In one embodiment, the material surface-modified by the method of the present disclosure can be the same material as the second material, or a different material. In one embodiment, the second material can be surface-modified (e.g., surface-modified by the method of the present disclosure). In one embodiment, in the step of interfacially adhering or bonding with the second material, an adhesive can be used or not. In one embodiment, in the step of interfacially adhering or bonding with the second material, plating (wet coating) or vapor deposition (dry coating) can be used as a coating technique, and physical vapor deposition (vacuum vapor deposition, ion plating, sputtering) or chemical vapor deposition can be used as a thin film by vapor deposition. Any known adhesive can be used as the adhesive, such as starch, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl alcohol, epoxy resins, and polymerizable cyanoacrylate. In one embodiment, the step of interfacially adhering or bonding with the second material may be performed by applying a small amount of a solvent capable of dissolving both the material surface-modified by the method of the present disclosure and the second material, and then adhering the applied portion. Although interfacially adhering or bonding with polytetrafluoroethylene or polyimide may be relatively difficult, strong bonded materials or composites made from these materials may also be achieved according to the method of the present disclosure. The material surface-modified by the method of the present disclosure may be strongly bonded to the second material even after a period of time (e.g., about 30 minutes to about 30, about 30 minutes days, about 1 hour, about 2 hours, about 5 hours, about 10 hours, about 15 hours, about 20 hours, about 1 day, about 2 days, about 5 days, about 10 days, about 15 days, about 20 days, about 25 days, about 30 days, etc.) has elapsed without immediate interfacially adhering or bonding with the second material. Therefore, articles including the material surface-modified by the method of the present disclosure are also objects of the present disclosure.

In one embodiment, the present disclosure provides a method for manufacturing an article including a fiber composite material in which a fiber material is contained within a second material. In one embodiment, the fiber material in the method can have the characteristics of the fiber material in the step of oxidizing the surface of the fiber material described herein. In one embodiment, the method includes the steps of (1) oxidizing at least one of the fiber material and the second material, (2) interfacially adhering or bonding the fiber material and the second material after the step of oxidizing, and (3) melting the second material to obtain a fiber composite material. In one embodiment, the second material can be a semi-solid material such as rubber, but melting the second material in such a case refers to, for example, increasing fluidity by subjecting it to high temperature, and does not necessarily involve a phase change from solid to liquid. In this embodiment, typically, the second material is a thermoplastic resin, and may be, for example, a resin such as polyester, polypropylene, polyethylene, polyolefin, acrylic, polyvinyl acetate, AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyallyl diglycol carbonate, copolymers containing butadiene, synthetic rubber, polyether ether ketone (PEEK), rayon, cupra, polystyrene (PS), polyphenylene sulfide (PPS), polyaramid, polyimide, polyamide (nylon), polymethylpentene (Mitsui Chemicals' TPX (registered trademark)), vinylon, silicone, etc. In one embodiment, the second material may be a soft material such as rubber. In one embodiment, in order to strengthen the bond in step (2), the second material may be in a form that increases the contact area with the fibrous material, such as powder, granules, or film. In one embodiment, in step (2), the material may be subjected to pressure (e.g., pressing) and/or heat. In one embodiment, both the fiber material and the second material are oxidized. The melting of the second material may be performed at any suitable temperature, and in one embodiment, is performed below the temperature at which the second material is denatured or decomposed. In one embodiment, the method includes the steps of (1) oxidizing the fiber material, (2) mixing the fiber material with the uncured second material (fluid) after the oxidizing step, and (3) subjecting the mixture of step (2) to conditions under which the second material is cured. In this embodiment, typically the second material is a thermosetting resin (e.g., epoxy resin). In this embodiment, the conditions under which the second material is cured can be appropriately determined by one skilled in the art depending on the second material used.

(Composite materials)
In one aspect, the present disclosure provides an article including a high-strength composite material (e.g., a fiber composite material). The method of the present disclosure can greatly improve the interfacial adhesion between materials, and thus can provide a high-strength composite material. In one aspect, the composite material (e.g., a fiber composite material) included in the article of the present disclosure can be characterized as not being cut at or beyond the breaking point (the point at which the load on the measuring device is greatly reduced when the load is increased in a bending test or a tensile test) within the article, if necessary. The fiber and the second material can each have the material, shape, and/or properties described in the method of making a fiber composite material described herein. In one embodiment, the weight percentage of the fiber material in the composite material of the present disclosure can be about 40% or less, about 30% or less, about 20% or less, about 10% or less, or about 5% or less. Even when a smaller percentage of fiber material is used than in conventional fiber composite materials, the composite material of the present disclosure can have sufficient strength, which can be preferable in manufacturing, and can also have the advantage of reducing the burden of waste disposal of carbon fiber, which can be a problem.

In one embodiment, the composite material included in the article of the present disclosure may have a high strength not previously achieved within the article, if necessary. In one embodiment, the composite material included in the article of the present disclosure does not break at or beyond the breaking point (e.g., at a displacement distance or load that is 5% or 10% increased from the breaking point) when a three-point bending test or tensile test is performed on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm at a support point distance of 40 mm, and the material is at least partially connected. In one embodiment, the composite material included in the article of the present disclosure has a bending strength of about 1.1 times or more, about 1.2 times or more, about 1.5 times or more, about 1.7 times or more, or about 2 times or more than a composite material produced under the same conditions except for not performing the oxidation treatment step, when a three-point bending test is performed on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm at a speed of 2 mm / min and a support point distance of 40 mm. In one embodiment, the composite material included in the article of the present disclosure exhibits an improvement in bending strength of about 10 MPa or more, about 20 MPa or more, about 50 MPa or more, about 70 MPa or more, or about 100 MPa or more when a three-point bending test is performed on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm, at a speed of 2 mm/min and a distance between support points of 40 mm, compared to a composite material produced under the same conditions except that the oxidation treatment step is not performed.

In one embodiment, the composite material included in the article of the present disclosure has a tensile shear strength of about 1.1 times or more, about 1.2 times or more, about 1.5 times or more, about 1.7 times or more, or about 2 times or more, when a tensile test is performed on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm, at a tensile speed of 20 mm/min and a support distance of 40 mm, compared to a composite material produced under the same conditions except for not performing the oxidation treatment step. In one embodiment, the composite material included in the article of the present disclosure has a tensile shear strength of about 50 kgf or more, about 70 kgf or more, about 100 kgf or more, or about 200 kgf or more, when a tensile test is performed on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm, at a tensile speed of 20 mm/min and a support distance of 40 mm, compared to a composite material produced under the same conditions except for not performing the oxidation treatment step.

In one embodiment, the composite material of the fiber and the second material of the present disclosure may have a bending strength of at least about 1.1 times, at least about 1.2 times, at least about 1.5 times, at least about 1.7 times, or at least about 2 times that of the second material alone when evaluated by a three-point bending test with a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 2 or 3 mm, at a speed of 2 mm/min and a support point distance of 40 mm. The resin composite material (e.g., fiber-resin composite material) of the present disclosure has high interfacial adhesion between materials, so that the resin portion can be further mixed with the same or different types of resin (e.g., by mixing molten resins together) while maintaining the strength of the composite material. Therefore, the resin composite material (e.g., fiber-resin composite material) of the present disclosure can be used not only as a final product but also as a core material, and can be used to produce various molded products.

In one embodiment, the adhesive material that interfacially adheres or bonds the first material and the second material included in the article of the present disclosure may have a cut surface of at least one of the first material side half material and the second material side half material obtained by cutting the adhesive material along the interface between the first material and the second material, and when measured by X-ray photoelectron spectroscopy (XPS), the oxygen atom/carbon atom ratio and/or (C-O bond)/(total carbon bond)% within a depth of 10 nm of the material surface may be a value that is achieved on the material surface by the oxidation treatment step of the present disclosure. In one embodiment, the adhesive material that is interfacially adhered or bonded to the first material and the second material included in the article of the present disclosure is such that, for the cut surface of at least one of the first material side half material and the second material side half material obtained by cutting the adhesive material along the interface between the first material and the second material, the increase in the percentage of oxygen atoms and/or (C-O bonds)/(total carbon bonds)% among all atoms excluding hydrogen within a depth of 10 nm from the material surface as measured by X-ray photoelectron spectroscopy (XPS) compared to the central region of the material can be the value of the increase in this percentage achieved at the material surface by the oxidation treatment step of the present disclosure compared to the same material that is not treated.

(Surface Modification Materials)
In one aspect, the present disclosure provides an article comprising a material surface-modified by the method of the present disclosure. In one embodiment, the surface-modified material is used as an adhesive material to provide an adhesive material or a composite material. Since the material surface-modified by the method of the present disclosure can provide a high-strength adhesive material or composite material without being molded into an adhesive material or composite material immediately after surface modification, an article comprising the surface-modified material before interfacial adhesion or bonding of materials may also be useful. In one embodiment, the surface-modified material can be used for applications other than providing an adhesive material or a composite material, for example, the method of the present disclosure can enable surface modification without impairing the strength of the material, so the surface-modified material may be suitable for coating (e.g., coating with a hydrophilic material). Articles comprising the surface-modified material coated in this manner are also contemplated in the present disclosure.

In one embodiment, the surface-modified material of the present disclosure is surface-modified to provide an improvement in shear strength of about 150 N or more, about 200 N or more, about 250 N or more, about 300 N or more, about 350 N or more, about 400 N or more, or about 450 N or more, when a tensile test is performed on a test piece of a surface-modified material having a width of 10 mm and a thickness of 1 mm, bonded to an aluminum plate having a thickness of 0.2 mm so that the bonded area is 10 mm x 10 mm, at a speed of 20 mm/min and a support point distance of 60 mm, compared to a bonded material made from a material made under the same conditions except that the oxidation treatment step is not performed.

The present disclosure has been described above by showing preferred embodiments for ease of understanding. Below, the present disclosure will be described based on examples, but the above description and the following examples are provided for illustrative purposes only and are not provided for the purpose of limiting the present disclosure. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in this specification, but is limited only by the scope of the claims.

In the following examples, the polymerization inhibitor contained in the monomer reagent was simply adsorbed and removed by passing the monomer reagent through a glass column packed with activated carbon. Basically, grafting was performed under a nitrogen atmosphere.

[Example 1: Evaluation of oxidation by FTIR and XPS measurements]
The oxidized material was evaluated by FTIR and XPS measurements.

Oxidation treatment A polypropylene plate (10 mm x 80 mm x 0.5 mm) (As One 61-6034-78) was oxidized by plasma treatment in the atmosphere. The device used was an atmospheric pressure plasma device (Sakigake Semiconductor (Kyoto) tabletop direct type TK-50) connected to a sample feeder that was manufactured by the company, with the output scale set to 60 V (maximum scale 130).

Analysis by Fourier transform infrared spectroscopy (FTIR) The oxidized samples were washed with a solvent (nax Silicon Off SP: Nippon Paint) and water, and then dried, and then measured by the attenuated total reflection method (ATR) using a Fourier transform infrared spectrophotometer IRPrestige-21 (Shimadzu Corporation, Kyoto). The results are shown in Figures 1 and 2.

It is said that the FTIR ATR method can measure the bonding state within a depth of about 10 μm from the surface. Figure 1 shows the spectra of six samples with different oxidation times. In general, when a sample is oxidized, carbonyl groups are produced, so the change in absorbance near the carbonyl group absorption band, 1730 cm ^-1 , is observed. In Figure 1, no significant difference in absorbance near 1730 cm ^-1 is seen.

In order to make a relative comparison of absorbance, the absorbance ratio "absorbance at 1730 cm ^-1 /absorbance at 1440 cm ^-1 " was calculated using the absorbance at the absorption peak of 1440 cm ^-1 , which remains almost unchanged during the strong oxidation treatment process, as the denominator, and the relationship with the oxidation time was plotted in Figure 2. The absorbance ratio is dispersed with respect to the oxidation treatment time, and no correlation is observed. From a comparison with the XPS results described below, it was determined that the slight oxidation preferred for this surface treatment is difficult to measure with the sensitivity of FTIR-ATR.

In addition, when the material was subjected to a strong oxidation treatment, ignoring the destruction of the material, an increase in absorbance at 1727 cm ⁻¹ was observed by IR measurement, which was confirmed by measuring an ultra-high molecular weight polyethylene (UHMWPE) sample (Figure 3).

Analysis by X-ray photoelectron spectroscopy (XPS) The polypropylene sample measured by the ATR method of FTIR was measured by an X-ray photoelectron spectroscopy (XPS). The results are shown in Figures 4, 5, 6, and 7. The XPS measurement was performed under conditions that allowed the bonding state to be measured at a depth of about 10 nm from the surface. The conditions for the XPS analysis were as follows.
Equipment: PHI-5000VersaProbe II (ULVAC-PHI, Inc., Kanagawa), radiation source: CrKα radiation, AlKα radiation, take-off angle: 90°.

4 shows (A) C1s narrow spectrum and (B) O1s narrow spectrum in XPS measurement of polypropylene samples with different oxidation treatment times. Table 1 shows the relationship between the amount of C1s (%), the amount of O1s (%), and the O/C atomic ratio obtained from the spectrum.

Table 2 shows the types of carbon bonds and their abundance ratios obtained by waveform analysis of the C1s narrow spectrum.

Based on these results, the relationship between the O/C atomic ratio and the oxidation treatment time from the results in Table 1 is shown in Figure 5, and the relationship between the proportion of each bond and the oxidation treatment time from the results in Table 2 is shown in Figure 6. Furthermore, Figure 7 shows an enlarged plot of (C-O-H bond %)/(total carbon bond %).

It was confirmed that, with an increase in the oxidation treatment time, the number of C-C bonds and C-H bonds decreased, while the O/C atomic ratio, the number of C-O-H bonds, C=O bonds, and O=C-O bonds all increased. Although the FTIR measurements in Figures 1 and 2 could not confirm the change in oxygen bonds with the oxidation treatment time, it was found that the oxidation state could be confirmed by XPS measurement. It is noted that Figures 5, 6, and 7 show that the increase in the amount of carbon-oxygen bonds becomes gradual when the oxidation treatment time is 10 seconds/ ^cm2 or more.

[Example 2: XPS measurement of ozone oxidized polyphenylene sulfide fiber]
Polyphenylene sulfide (PPS) fiber (TORCON®, Toray, Tokyo) was oxidized with ozone and then subjected to XPS measurement. The X-ray photoelectron spectrometer used was Thermo Fisher Scientific (USA) K-Alpha (radiation source: AlKα radiation, take-off angle: 90°).

The results of XPS surface analysis of untreated and ozone-oxidized PPS fibers are shown in Table 3. It was confirmed that the ozone oxidation treatment of PPS fibers increases the O/C atomic ratio and increases the number of C-O-H bonds and O-C=O bonds.

The ozone oxidation treatment in this example was carried out according to the following procedure.
Ozone oxidation treatment The test piece was placed in a 2L hard glass container (with a gas inlet and outlet), and oxygen containing ozone at a concentration of 40 g/ ^m3 was blown into the sample at a flow rate of 1000 ml/min using an ozone generator (ON-1-2 model manufactured by Japan Ozone Co., Ltd.) with an ozone generation rate of 2 g/h and a flow rate of 1000 ml/min for 20 minutes. Next, oxygen not containing ozone was blown in for 10 minutes. The ozone concentration was determined by iodometric titration.

Analysis of the oxidation of a polymethylpentene (PMP) resin sheet and XPS measurement of the treated sample also confirmed that the oxidation treatment increases the O/C atomic ratio and increases the number of C-O-H bonds and O-C=O bonds.
PMP resin sheet: 0.5 mm thick, TPX (registered trademark) resin (Mitsui Chemicals, Tokyo)

[Example 3: Change in strength of polypropylene fabric due to plasma discharge oxidation]
Next, polypropylene multifilament fabric (plain woven fabric made of yarn twisted together microfilaments with a diameter of 0.25 mm: size: width 100 mm, length 200 mm, thickness 0.6 mm, basis weight 20 g/ ^m2 ) was oxidized by plasma discharge. Plasma discharge was performed for 15 seconds, 30 seconds, 60 seconds, and 150 seconds per ^{1 cm2} area. The plasma discharge device was the same as in Example 1. After the oxidation treatment, a tensile strength test was performed.

Tensile strength test: Testing machine: Universal testing machine AUTOGRAPH AGS-H (Shimadzu Corporation, Kyoto) was used, the test was performed at a tensile speed of 10 mm/min and a test piece support point distance of 600 mm.

The results are shown in Figure 8. The vertical axis indicates the relative strength of the material when the strength of the untreated material is taken as ¹⁰⁰ %. As the oxidation treatment time increases, the material strength decreases. In this case, the strength decrease may be significant because the sample is made of thin fibers. It was confirmed that when this fiber cloth with an oxidation time of 10 seconds/ ^cm2 or less is used as a reinforcing material for a composite material, the material strength is increased. Also, if the polypropylene material is in the form of a plate with a thickness of 0.1 mm or more, the decrease in material strength due to oxidation of 20 seconds/cm2 or less is at a negligible level.

[Example 4: Decrease in material strength due to ozone oxidation]
A polypropylene multifilament fabric (a plain woven fabric made of threads twisted together with microfilaments having a diameter of 0.25 mm: size: width 100 mm, length 200 mm, thickness 0.6 mm, basis weight 20 g/m ² ) was subjected to ozone oxidation treatment. Next, the tensile strength was tested.

Ozone oxidation treatment was carried out in the same manner as in Example 2.
Tensile strength test was carried out in the same manner as in Example 3.

The results are shown in Figure 9. As with the plasma oxidation treatment, prolonged oxidation treatment caused a decrease in tensile strength. Compared to Figure 8, the time axis in Figure 9 is in minutes, so the decrease in material strength due to oxidation is more gentle with ozone treatment than with plasma treatment under the ozone treatment conditions used.

[Example 5: DHM treatment and XPS measurement of sample]
The DHM (Durable Hydrophilic Modification) process is completed by performing a surface coating step on the oxidized material. XPS measurements were performed on the plasma oxidized samples (irradiation time 5 seconds/ ^cm2 ) that had undergone the surface coating step. The results are shown in Table 4. It was confirmed that the O1s/C1s ratio and the proportion of each functional group containing oxygen increased in each sample compared to the samples that had only been plasma treated.

The oxidation and coating steps in the DHM treatment in this example were carried out according to the following procedure.
Oxidation Treatment: Using the atmospheric pressure plasma treatment method of Example 1, the material was oxidized at an irradiation dose of 10 seconds/ ^cm2 , and the sample was washed with methanol and water.
Coating step: Prepare reaction liquid A with a volume ratio of 400 water, 100 methanol, 1 acrylic acid, and 0.1 methyl methacrylate. The oxidation treatment material is placed in a flat tray, and reaction liquid A is added to cover the treatment material to a depth of about 5 mm. The tray is covered with a 0.5 mm thick hard glass plate (not sealed), and ultraviolet irradiation ^* is performed for 20 minutes from a distance of 100 mm. The material is removed and washed with methanol, and then the treatment material is thoroughly washed with hot water and dried to complete the treatment. The weight increase of the sample after treatment was 0.1% or less compared to the weight of the sample before treatment.
^* Ultraviolet light irradiation: A high-pressure mercury lamp (Toshiba Lighting & Technology Corporation, product name H1500L, total length 360 mm, light emission length 200 mm, lamp voltage 315 V, lamp power 1500 W) is irradiated onto the sample without a filter. To prevent overheating, a strong breeze is blown between the lamp and the sample using a homemade "cooling fan with slits in the blower."

[Example 6: Adhesion strength test to find optimal oxidation treatment for DHM treatment]
In order to determine the "oxidation time of the oxidation step" of DHM treatment that is effective in improving adhesion, the tensile shear strength of samples made by bonding polypropylene (PP) plates and aluminum plates that had been subjected to DHM treatment with different oxidation times with an epoxy adhesive was measured.

A PP plate (size 10 mm x 80 mm, thickness 1.0 mm) was subjected to DHM treatment with oxidation and coating steps according to the following procedure.
Oxidation treatment was performed by plasma discharge in the same manner as in Example 1. The oxidation treatment was performed for 0 to 20 seconds/ ^cm2 .
Coating Step The coating step of Example 5 was carried out.

The adhesion and tensile shear strength were measured according to the following procedures.
Adhesive Tensile Shear Strength Test Treated PP plate and aluminum plate (thickness 0.2 mm) were bonded using epoxy adhesive Bond Quick 5 (Konishi, Osaka) according to the manufacturer's instructions. That is, approximately equal amounts of liquid A (main agent; epoxy resin) and liquid B (hardener; polythiol) were mixed on an adhesive mixing sheet, and the mixture was evenly applied to a polypropylene sample so that the adhesive area was 10 mm x 10 mm, and an aluminum plate was placed on top of it (adhesive amount was about 80 mg). This adhesive sample was sandwiched between plastic plates, a 1 kg weight was placed on it, and it was left at room temperature for 36 hours. A tensile test was performed under the following conditions to measure the tensile shear strength (N).
Equipment used: Tabletop load testing machine FTN1-13A (Aiko Engineering Co., Ltd.), tensile speed: 20 mm/min, the space between the holders was 4 cm long PP plate - 1 cm long adhesive portion - 1 cm long aluminum plate, and both ends of the PP plate and the aluminum plate were fixed with the holders to perform the tensile test.

The results are shown in Figure 10. In the figure, the area enclosed by a square is the area where material destruction was observed during the adhesion test. The modified sample with oxidation treatment of 3-7 sec/ ^cm2 showed material destruction of the PP, so it can be said that it has the highest adhesive strength. The surface modified samples with oxidation treatment of 3, 4, 6, and 7 sec/ ^cm2 showed material destruction of the PP plate at the strength values in Figure 10. On the other hand, the modified sample with oxidation treatment of 5 sec/ ^cm2 did not peel off the adhesive part, and the PP plate stretched, making it impossible to measure at a stress of 425 N. The modified sample with oxidation treatment of 5 sec/ ^cm2 showed the most preferable adhesion because the PP plate stretched. At oxidation times before and after oxidation treatment of 3-7 sec/ ^cm2 , the adhesive strength of the modified sample was low, but the adhesive strength was higher than that of the untreated sample.

From the results of XPS measurements and adhesive strength tests on polypropylene, it is believed that materials with an oxidation level of about 0.03-0.30 O/C atomic ratio and about 3-20% C-O bond ratio when measured by XPS, or materials with an oxidation level of about 0.01-0.15 increase in O atomic ratio (ratio of O atoms among atoms excluding hydrogen) or about 1-15% increase in C-O-H bond ratio compared to untreated materials when measured by XPS, are particularly suitable for improving the adhesiveness of materials. The decrease in strength of the material is almost 0% in the case of plate-shaped materials and 2-3% in the case of thin fibers. It has been confirmed that the strength of thin fibers increases when modified fibers are used in composite materials. Therefore, it can be said that the decrease in material strength at the same oxidation level is not a problem. The same view was confirmed for materials other than polypropylene.

[Example 7: Durability of treatment]
It is said that if the plasma-treated silicone rubber sheet is not bonded immediately after treatment, it will lose its adhesiveness. Therefore, the plasma-treated silicone rubber sheet and the DHM-treated silicone rubber sheet were left for a specified time, and then bonded to an aluminum plate, and the adhesive tensile shear strength was compared. For comparison, an untreated silicone rubber sheet was also bonded to an aluminum plate. The results are shown in Table 5. If the plasma-treated silicone rubber sheet is not bonded within about an hour, it will lose its adhesiveness. Also, the adhesive strength was considerably smaller than that of the DHM-treated sample.

The oxidation treatment and DHM treatment in this example were carried out according to the following procedures.
Plasma treatment: Using Kasuga Denki Real Plasma APJ-500 (high frequency power supply AGI-B202), the sample was irradiated for 5 seconds/ ^cm2 (1 second irradiation per ¹ cm2 sample area) in air under atmospheric pressure with output of 300 W, 200 V, and sample-electrode distance of 10 mm. The degree of oxidation was the same as in Example 6.
DHM treatment The following coating steps were carried out on the material obtained by oxidizing the silicon rubber sheet by the above plasma treatment. The oxidized material was placed in a reaction solution and heated at 80°C for 10 minutes. Specifically, a reaction solution was prepared by adding 10 mg of azobisisobutyronitrile (AIBN) to a solution of 800 water, 200 methanol, 1 hydroxyethyl methacrylate (HEMA), and 0.1 methyl methacrylate (MMA) in volume ratio. The reaction solution was placed in the reaction solution and heated at 80°C for 10 minutes. The material was removed from the reaction mixture, washed with methanol, boiled and washed with water, and dried.

(Fiber-resin composite material (FRP) with thermosetting resin (epoxy resin) as the base material)
[Example 8: Composite material of polypropylene fiber and epoxy resin]
Untreated or modified polypropylene (PP) fiber/epoxy resin FRPs were prepared. The bending strength of each sample was measured. The results are shown in Table 6. Even though there was a slight decrease in fiber strength due to the modification, the material strength of the prepared FRPs was increased.

The materials used in this example were as follows:
Polypropylene (PP) fiber: polypropylene plain weave fabric, specific gravity = 20 g/m ² , component yarn: multifilament (diameter 0.5 mm), monofilament fiber diameter = 30 μm
Epoxy resin: Base: Liquid epoxy resin, Hardener: Diamine-based Hardener: GM-6800 (Bleny Giken, Gunma)

The DHM treatment, FRP manufacturing method, and test method in this example were as follows.
DHM treatment: The same as in Example 5, except that the oxidation time was 5 seconds/cm ² .
-Manufacturing method of FRP of PP fiber/epoxy resin Hand lay-up method: Six sheets of PP cloth were stacked in a stainless steel mold (concave mold), epoxy resin mixed with a hardener was poured in, and it was left for one day to harden. The size of the molded part (concave mold) of the mold was 80 mm in length and 10 mm in width; it was manufactured according to the JIS standard. The size of the manufactured FRP = 10 mm x 80 mm x 2.6 mm.
Tensile shear strength test of materials Measurement was performed using a universal testing machine AUTOGRAPH AGS-H (Shimadzu Corporation, Kyoto).
- Three-point bending strength test of materials (JIS-K7171 compliant)
The test was performed using the same tester as above. The bending speed was 5 mm/min, and the distance between supporting points was 40 mm.

[Example 9: Composite material of UHMWPE fiber and epoxy resin]
Untreated or modified ultra-high molecular weight polyethylene (UHMWPE) fiber/epoxy resin FRP was prepared. The bending strength of each sample was measured. The results are shown in Table 7. As with the PP fiber/epoxy resin FRP, the fiber strength was slightly reduced by modification, but the material strength increased when the FRP was made.

The materials used in this example are as follows:
Ultra-high molecular weight polyethylene (UHMWPE) fiber; multifilament yarn (diameter 0.62 mm) made of monofilament (diameter = 30 μm): provided by Toyobo Co., Ltd., product name Dyneema.

The oxidation treatment and coating steps in the DHM treatment and the manufacturing method of the FRP in this example were as follows. The three-point bending strength test was the same as in Example 8.
Oxidation Treatment The ozone oxidation method of Example 2 was used. The oxidation treatment time was 15 minutes.
Coating step: The coating step was carried out in the same manner as in Example 5.
- Manufacturing method of UHMWPE fiber/epoxy resin FRP Hand lay-up method: 40 threads were placed in parallel in a JIS-compliant mold (concave mold), 10 g of epoxy resin mixed with a hardener was poured in, and left for one day to harden. Size of molded FRP = 10 mm x 80 mm x 2.6 mm.

Figure 11 shows the "load-displacement curves" in the three-point bending strength test corresponding to Tables 6 and 7; (A) is PP fiber/epoxy resin, and (B) is UHMWPE fiber/epoxy resin. In the three-point bending test, the untreated PP fiber/epoxy resin and untreated UHMWPE fiber/epoxy resin materials broke into two, but the DHM-treated PP fiber/epoxy resin and DHM-treated UHMWPE fiber/epoxy resin materials remained bent in an "L" shape after the three-point bending strength test and did not separate into two. This indicates high adhesion at the interface between the fiber and the resin.

(Composite material with thermoplastic resin as the base material)
For various materials that were surface-modified according to the method of the present disclosure, composite materials were prepared with various materials and material tests were performed. In composite materials prepared from fibers or films that were untreated or only oxidized and a base resin, the fibers or films were pulled out of the resin in a three-point bending strength test, causing the materials to break. On the other hand, in composite materials prepared from fibers or films that were DHM-treated and various resins, it was observed that the fibers or films did not come out of the resin, and the materials were cut while maintaining adhesion, causing material breakage.

[Example 10: Composite material of PET fiber and polypropylene resin]
A fiber composite material was prepared by combining PET fiber (polyethylene terephthalate; plain woven fabric (NBC Meshtec, Tokyo)) and polypropylene (PP) resin. The same three-point bending test as above was then performed. The results are shown in Table 8.

The oxidation treatment, DHM treatment, and manufacturing method of the composite material in this example were as follows. The three-point bending strength test was the same as in Example 8.
Oxidation treatment Plasma treatment: The PET fiber and PP resin were subjected to the same plasma treatment as in Example 6.
DHM Treatment The oxidized material was subjected to the coating step of Example 7.
・Composite material manufacturing method Spray a release agent onto the mold. Next, alternate packing of polypropylene resin and PET fibers. Fix the mold to an AS ONE small heat press HC300-01, heat to 240°C, leave for 10 minutes without pressure, and then leave for 5 minutes with a pressure of 2 MPa. After that, return to room temperature, and remove the composite material sample from the mold. The mold was designed based on JIS standards. The sample size was 60 mm in length, 10 mm in width, and approximately 2 mm in thickness.

[Example 11: Composite material of carbon fiber and polypropylene resin]
A high-strength fiber composite material was produced from carbon fiber and polypropylene (PP) resin.

Fiber composite materials with different fiber contents were prepared from carbon fiber (CF) and PP film, and three-point bending tests were performed on the fiber composite materials. The carbon fiber was obtained from Mitsubishi Chemical. The results are shown in Table 9.

The oxidation treatment, DHM treatment, and manufacturing method of the composite material in this example were as follows. The three-point bending strength test was the same as in Example 8.
Oxidation Treatment Plasma treatment: The carbon fiber (with resin) and the polypropylene film were subjected to the plasma oxidation treatment in the same manner as in Example 1.
DHM Treatment The oxidized material was subjected to the coating step of Example 7.
・Manufacturing method of composite material Ten sheets of 0.3 mm thick PP film and a bundle of carbon fiber filaments are packed into a mold. The mold is fixed to an AS ONE small heat press machine H300-01, heated to 240°C, and left unpressurized for 10 minutes, then left under a pressure of 2 MPa for 5 minutes. After that, the temperature is returned to room temperature and the sample is removed from the mold.

Fiber composite materials made from surface-modified fibers and resins showed high bending strength. Fiber composite materials made from surface-modified fibers and resins showed maximum strength at a small fiber content of 20%.

[Example 12: Composite material of carbon fiber and amide resin]
High strength fiber composite materials were fabricated from carbon fiber and amide resin.

A fiber composite material was prepared from the surface-modified carbon fiber (CF) and polyamide (PA6) resin, and a three-point bending test was performed on the fiber composite material. The results are shown in Table 10.

The materials used in this example are as follows:
Carbon fiber: Mitsubishi Chemical products Polyamide resin: Sigma-Aldrich PA11 = Nylon-11 pellets

The oxidation treatment and DHM treatment in this example were as follows. The three-point bending strength test was the same as in Example 8.
Oxidation Treatment The carbon fiber (with resin) and PA6 were subjected to the same ozone treatment as in Example 2.
DHM Treatment of CF The oxidized material was subjected to the coating step of Example 7.
・DHM treatment of PA6 The following coating step was carried out on the material that had undergone the above oxidation treatment. Reaction liquid A was made of 400 parts water, 400 parts methanol, and a hydrophilic monomer (vinylpyrrolidone ^* ) in a volume ratio. The material to be treated was placed in a flat tray, and reaction liquid A was added to cover the material to a depth of about 5 mm. The tray was then covered with a 0.5 mm thick hard glass plate (not sealed), and exposed to ultraviolet light for 10 minutes from a distance of 100 mm. The material was removed and washed with methanol. Next, a hydrophilic polymer aqueous solution B ^** was applied to the material, dried, and then boiled and washed with water.
^* Vinylpyrrolidone: 1-vinyl-2-pyrrolidone, Fujifilm Wako Pure Chemical Industries, Ltd.: Product code 228-01285
^** Aqueous hydrophilic polymer solution B: A 1% by weight aqueous solution of a mixture of polyvinylpyrrolidone (PVP) ^*** and carboxymethylcellulose (CMC) ^*** (mixture weight ratio 10:1).
^*** PVP; average molecular weight 40,000; K30 Fujifilm Wako Pure Chemical Industries, Ltd.: Product code 161-03105
^＊＊＊＊ CMC: Sodium carboxymethylcellulose (Fujifilm Wako Pure Chemical Industries, Ltd., product code 4987481229082)

[Example 13: Composite material of polyimide film and polyester resin]
Composite materials were similarly prepared from polyimide (PI) film and polyester resin, and the composite materials were subjected to three-point bending tests. The results are shown in Table 11.

The materials used in this example are as follows:
Polyimide (PI) film: AS ONE, Polyimide Film Kapton (R), model number 3-1966-07. Thickness 0.25 mm
Polyester resin: PROST Co., Ltd., unsaturated polyester resin for FRP repair, low shrinkage type, with hardener, for general lamination (non-paraffin)

The oxidation treatment and DHM treatment in this example were as follows. The three-point bending strength test was the same as in Example 8.
Oxidation Treatment The PI film was polished five times in one direction with a waterproof abrasive paper (grain size 600, waterproof paper; Starstar Abrasives Industries, STARCKE (Germany)). Next, the ozone treatment of Example 2 was carried out.
-DHM treatment The coating step was carried out on the material that had undergone the above oxidation treatment as follows. Polymerization after electron beam irradiation was carried out as follows. The material that had undergone the polishing and ozone treatment was irradiated with an electron beam (EB) for 5 seconds/ ^cm2 (per sample area) using an electron beam irradiation device (EC90 manufactured by Iwasaki Electric Co., Ltd.) under conditions of an acceleration voltage of 80 kV and an exposure dose of 250 kGy. The material was removed, and a monomer solution (a mixed solution of HEMA 10, MMA 1, water 10, and methanol 4) was applied in a volume ratio, and heated at 60°C for 1 minute. The treated material was removed, washed with water, and dried.

[Example 14: Composite material of high strength fiber fabric and vulcanized black rubber]
Untreated or treated high strength aramid fiber fabric was sandwiched between uncured vulcanized black rubber to prepare a cured fiber-rubber composite material, and a T-peel test was performed. The results are shown in Table 12.

The materials used in this example are as follows:
- Aramid fiber cloth; Esco Corporation Size 1.0 x 1.0 m: Kevlar fiber 100 fabric EA911AV-1, thickness 0.5 mm.
・Vulcanized black rubber; provided by Surie Co., Ltd.

The oxidation treatment, DHM treatment, and method for producing the composite material in this example were as follows.
Oxidation treatment Chemical reaction treatment: 10 ml of sodium hypochlorite solution (Fujifilm Wako Pure Chemical Industries, Ltd. product code 197-02206, available chlorine: 5.0%+) was taken and mixed with 100 ml of water to make an aqueous solution. The solution was placed in a glass container and the material to be treated was placed in it. The solution was gradually heated, 0.2 ml of acetic acid was added, boiled for 3 minutes, cooled to room temperature, and the material was removed. The material was washed with water and naturally dried. The oxidation of the material was confirmed by XPS measurement.
DHM Treatment The following coating step was carried out on the material that had been subjected to the above oxidation treatment. The monomer solution was a mixed solution of 10 parts acrylic acid (AA), 1 part methacrylic acid (MA), 10 parts water, and 4 parts methanol, and the process was carried out as in Example 7.
- Manufacturing method of the composite material After adding a vulcanizing agent, an aramid fiber sample was sandwiched between soft black rubber, a silicone rubber plate was placed on top of it, and a 1 kg weight was applied to pressurize the sample and the material was left for 24 hours to produce a composite material. The fiber content was 20%.

The T-peel test was carried out as follows.
1) Fabric sample size: width 10 mm, length 100 mm
2) Sandwich the cloth between two pieces of black rubber, leave about 10 mm of the cloth end exposed, and heat mold. The adhesive area between the cloth and rubber is 10 mm x 90 mm.
3) Use your hands to peel off about 10 mm of one end of the black rubber (the side with the fabric exposed).
4) The peeled end of the rubber and the protruding portion of the cloth were each attached to a tensile test fixture and pulled at a pulling speed of 10 mm/min.

The surface modification disclosed herein allows for the production of high-strength composite materials with unprecedented adhesion at the fiber-resin interface.

[Example 15: Preparation of specific surface-modified articles]
Examples of articles produced by the surface modification treatment of the present disclosure are given below.
By applying the surface modification treatment of the present disclosure to polypropylene cloth and silicone rubber, water spreads and does not form droplets, and water wettability is dramatically improved (Figure 12).
By applying the surface modification of the present disclosure, paper and foamed polyethylene, and aluminum and foamed polyethylene, which do not normally adhere to each other, were able to adhere to each other (Figure 13).
The surface modification of the present disclosure improved the adhesion of polytetrafluoroethylene (Figure 14).
The surface modification of the present disclosure makes it possible to apply water-based paint to TPX® resin (polymethylpentene) film (Figure 15).
By applying the surface modification of the present disclosure, it became possible to apply water-based coating to silicone resin (Figure 16).

The present disclosure provides articles with excellent properties, such as high strength articles and articles with high hydrophilicity, providing benefits in various industries, such as automobiles, aircraft, medical devices, and electronic devices.

Claims (26)

1. A method of making an article comprising a surface-modified material, comprising:
Surface modifying the material, comprising:
(1) subjecting the material to an oxidation treatment;
(2) surface-coating the oxidized material;
and forming an article from the surface-modified material.
Method. The method according to claim 1, wherein the article is selected from the group consisting of battery separators, masks, plastic members, aircraft materials, substrates and coating layers of wind power blades, sporting goods, medical, sanitary and cosmetic products, transplant devices, cosmetic brushes, sponges, writing implement members, various equipment members, building members, civil engineering members, articles with a coating layer on the surface, wrapping materials for motor sliding parts, printing plastics, cell culture-related products, permeable membranes, adhesive tapes, paper, toys, anisotropic conductive films, mounted chips using conductive adhesives, lighting equipment, displays or films on their surfaces, screens, sound-insulating and sound-absorbing articles, vibration-proof articles, conductive articles, and thermally conductive articles. The plastic parts include plates, films, cloth or threads, the aircraft materials include parts of ships, aircraft, automobiles, rockets, railways, robots, agricultural machinery, wheelchairs, nursing equipment or drones, automobile bonnets or automobile seat parts, the sporting goods include golf club shafts, fishing rods, tennis rackets, skiboards or skateboards, the medical, sanitary or cosmetic products include diapers, sanitary products, bandages, gauze, tapes, disinfectant patches, various sanitary or facial packs, napkins, agricultural or dry land greening materials, synthetic paper, filtration materials, wiping and cleaning materials, orthodontic brackets, infusion or drip connection devices, syringes, drainage tubes, cannulas or joints, and the transplant devices include artificial organs, artificial joints, spinal treatment implants or dental treatment implants. The method according to claim 2, wherein the writing implement member includes an ink collector, an ink regulator, an ink tank, an ink guide core, a pen core, a pen shaft, a batting, an ink absorbing sponge or a brush head, the cell culture-related product includes a cell adhesiveness control material or a cell fixation functional material, the building member includes an interior member for application such as wallpaper, a wall material, a floor material, a floor board, a bridge pier or a tunnel inner wall, the article having a surface including the coating layer includes an article having an antibacterial/antiviral coating, a photocatalytic coating, an anti-rust coating, a plated surface or a vapor deposition surface, the paper includes synthetic paper made of a plurality of materials selected from natural fibers, semi-synthetic fibers, chemical fibers and polymers, and the mounted chip using the conductive adhesive includes a silver-epoxy conductive adhesive/tin plating interface. The method of claim 1, wherein the article is a battery separator comprising a surface-modified plastic nonwoven fabric. The method of claim 1, wherein the article is a mask comprising a surface-modified plastic nonwoven fabric. The method according to claim 1, wherein the material includes a material selected from the group consisting of metal materials such as steel and iron alloys, stainless steel, copper and copper alloys, titanium and titanium alloys, aluminum and aluminum alloys, tin, zinc, and tungsten carbide, and oxides thereof, silicon carbide, carbon fiber, cellulose fiber, foam, polymer materials, polyethylene, polypropylene, polytetrafluoroethylene, polyoxymethylene (POM) resin, polyamide (nylon), MC nylon (registered trademark), silicone resin, and fluororesin. The method according to claim 1, wherein the article has the shape of a powder, a fiber, a woven fabric, a nonwoven fabric, a cloth, a plate, a film, a sheet, a tube, a rod, a hollow container, a box, a foam, a laminate, a plate, a square timber, a round timber, a round steel, a round tube, a pipe joint, or a coupling joint. The oxidation treatment is
(i) the oxidation is carried out so that the percentage of C-O bonds/total carbon bonds within a depth of 10 nm of the surface of the material is increased by about 1 to 20% compared to before the oxidation treatment, as measured by X-ray photoelectron spectroscopy (XPS);
(ii) the C-O bond/total carbon bond ratio within a depth of 10 nm of the surface of the material is about 5-15% as measured by X-ray photoelectron spectroscopy (XPS);
(iii) the method of claim 1 is carried out such that the O/C atomic ratio within a depth of 10 nm of the surface of the material is about 0.03 to 0.2 as measured by X-ray photoelectron spectroscopy (XPS). surface modifying the material;
and interfacially bonding or adhering the material to a second material to produce an adhesive material. And forming an article from the adhesive material.
The method of claim 1. The method of claim 9, wherein the article is selected from the group consisting of implant devices, automotive seating materials, various equipment components, building components, civil engineering components, and mandrels for sporting goods. The method of claim 10, wherein the implant device comprises an artificial joint, a spinal implant, or a dental implant, and the sports equipment axle comprises a golf shaft, a fishing rod, or a racquet grip. The method of claim 9, wherein the article is an implant device comprising a titanium and plastic composite material. The method of claim 9, wherein the article is a golf shaft or fishing rod comprising a composite material of surface-modified fibers and resin. The method of claim 9, wherein the interfacial bonding or adhesion step is performed in the presence of an adhesive between the material and the second material. The method of claim 9, further comprising the step of interfacially bonding or adhering the material to a second material approximately one hour after the step of surface-modifying the material. 1. A method of manufacturing an article comprising a fiber composite material, the fiber material being contained within a second material, comprising the steps of:
(1) subjecting at least one of the fiber material and the second material to an oxidation treatment;
(2) a step of interfacially adhering or bonding the fiber material and the second material after the step of performing the oxidation treatment;
(3) melting the second material to obtain the fiber composite material;
(4) molding an article from the fiber composite material;
A method comprising: The method of claim 16, wherein the article is a sports equipment axle. The method of claim 16, wherein the second material is a resin material. The oxidation treatment is
(i) the oxidation is carried out so that the percentage of C-O bonds/total carbon bonds within a depth of 10 nm of the surface of the material is increased by about 1 to 20% compared to before the oxidation treatment, as measured by X-ray photoelectron spectroscopy (XPS);
(ii) the C-O bond/total carbon bond ratio within a depth of 10 nm of the surface of the material is about 5-15% as measured by X-ray photoelectron spectroscopy (XPS);
17. The method of claim 16, wherein (iii) the method is carried out such that the O/C atomic ratio within a surface of 10 nm of the material is about 0.03 to 0.2 as measured by X-ray photoelectron spectroscopy (XPS). The method of claim 16, wherein the weight percentage of the fiber material in the fiber composite material is about 30% or less. The method of claim 1, further comprising a step of washing the material to be oxidized prior to the step of oxidizing. The method of claim 1, wherein the step of oxidizing includes oxidizing by a treatment selected from the group consisting of plasma treatment, ozone treatment, ultraviolet irradiation treatment, corona discharge treatment, high voltage discharge treatment, and chemical oxidation. The surface coating step includes: (a) grafting a hydrophilic vinyl monomer onto the oxidized material;
10. The method of claim 1, comprising (a) grafting a hydrophilic monomer and applying a hydrophilic polymer, or (b) grafting a vinyl ester monomer and subjecting it to hydrolysis. An article manufactured by the method according to any one of claims 1 to 23. 1. An article comprising an adhesive material in interfacial contact or adhesion between a first material and a second material,
An article, wherein a cut surface of at least one of the first material side half material and the second material side half material obtained by cutting the adhesive material along the interface between the first material and the second material has a (C-O bond)/(total carbon bond)% of about 5 to 15% within a depth of 10 nm of the material surface when measured by X-ray photoelectron spectroscopy (XPS). An article containing a fiber composite material that does not break at the breaking point when evaluated by a three-point bending test with a test piece 80 mm long, 10 mm wide, and 2 mm thick, at a speed of 2 mm/min and a support point distance of 40 mm.