JP2005290117A - Polymer material modification method and apparatus - Google Patents

Abstract

An apparatus for achieving surface modification of a polymer material having excellent durability without lowering the strength of the polymer material such as polyolefin, which is difficult to be surface-treated, and other polymer materials. Provide the configuration. As a result, orthodontic members made of polymer materials with improved adhesion to teeth, ink collectors with improved ink wettability, members for writing materials made of polymer materials such as ink tanks, necks, batting, Excellent electrolyte absorbability, acid resistance and alkali resistance, performance is not lost for a long time, and it is possible to manufacture separators for acid and alkaline batteries with excellent strength, and hydrophilicity is improved. To allow easy manufacture of many of the materials produced.
SOLUTION: Six types of apparatuses combining a cleaning apparatus, an impregnation processing apparatus, an activation processing apparatus, a hydrophilic polymer processing apparatus, a monomer grafting process apparatus, a cleaning apparatus, and a drying apparatus according to the purpose. In this way, the polymer material can be modified. Thereby, hydrophilicity, water absorption, adhesiveness, etc. can be improved without reducing the practical strength of the polymer material such as polyolefin.
[Selection] FIG. 1, FIG.

Description

  The present invention relates to a polymer material reforming apparatus. In particular, the present invention relates to a reforming apparatus that improves water absorption and adhesion without reducing the strength of a polymer material that is difficult to process.

  Polyolefin materials such as polypropylene and polyethylene are excellent in lightness, strength, chemical resistance, and the like, and are widely used for molded products such as films, nonwoven fabrics, automobile parts and electrical equipment parts. However, the polyolefin material has characteristics that it has low polarity due to its chemical structure and high crystallinity, so that it is poor in hydrophilicity and hardly undergoes chemical modification. Conventionally, ozone treatment, plasma treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, corona discharge treatment, sandblast treatment, solvent etching treatment, chromium mixed acid treatment, flame treatment, etc. have been performed to improve the hydrophilicity and adhesion of these materials. Attempts have been made to perform various surface activation treatments. However, even if these surface treatments are performed, water absorption enough to absorb water several times its own weight is not provided. For example, a method for improving the plating property, paintability, and adhesiveness by applying an ozone oxidation treatment was examined (Japanese Patent Publication No. 3-103448). However, if the desired surface characteristics are to be imparted only by the ozone treatment, the ozone treatment must be severe, and there is a problem that the strength of the object to be treated is remarkably lowered and it cannot be put into practical use. Further, water absorption cannot be sufficiently imparted only by ozone oxidation treatment. All of the other treatment methods have problems such as difficulty in improving without a reduction in strength, increased equipment costs, and waste disposal burden.

  In addition to the method of directly activating the surface of the polymer material as described above, a method of forming a layer made of a highly active component on the surface of the polymer material has been proposed. For example, a method has been proposed in which a vinyl monomer having an ester bond is graft-polymerized on a nonwoven fabric of polyolefin fiber, and then the ester bond is hydrolyzed to generate an acid group to thereby have hydrophilicity and ion exchange capacity ( JP-A-11-7937). However, there is a problem that it is not easy to graft a sufficient amount for imparting hydrophilicity even when a vinyl monomer is grafted onto a polyolefin fiber or film by the disclosed method. Moreover, it is necessary to further hydrolyze after the graft polymerization, which is troublesome.

  On the other hand, a method for imparting hydrophilicity by treating a nonwoven fabric made of polyolefin fibers with a hydrophilic resin in the presence of a persulfate has been proposed (Japanese Patent Laid-Open No. 11-67183). In this method, the nonwoven fabric could be given hydrophilicity to a practical level, but the hydrophilic durability was not always sufficient. For example, when heated with a detergent solution, hydrophilicity is considerably lost. Further, when a film or a molded product other than the nonwoven fabric is processed, sufficient hydrophilicity cannot be imparted, or the adhesiveness due to the adhesive cannot be improved.

A method of coating a nonwoven fabric with polyvinyl alcohol to impart hydrophilicity is also known (Japanese Patent Application Laid-Open No. 1-248460). However, although the resulting coating has a high hydrophilicity, it is a simple coating, so that there is a problem that the hydrophilic durability is not sufficient.

  In addition, the inventor first activated the surface of the polymer material, and then graft-polymerized monomers such as acrylamide, or further transferred the amide group of the grafted compound to the Hoffmann transition, thereby achieving particularly high dyeability. An improved polymer surface modification method was proposed (Japanese Patent No. 323471). Based on this method, a polymer material imparted with hydrophilicity can be produced. However, this method has a limit in the types of polymer material to be treated.

  Further, the present inventor treats the polymer material in the order of (1) an activation treatment and (2) a treatment with a hydrophilic polymer. Alternatively, the polymer material is treated in the order of (1) an activation treatment step (2) a hydrophilic polymer treatment step and (3) a monomer grafting step, or the polymer material is Proposed a method for modifying a polymer material characterized by (1) a solvent treatment step, (2) an activation treatment step, and (3) a treatment step with a hydrophilic polymer. Hei 11-375055, PCT / JP0090420). According to these methods, a polymer material imparted with excellent hydrophilicity can be easily produced at low cost. However, these additives reduce the effect of the activation treatment when processing molded articles of polymeric materials containing additives such as stabilizers and antioxidants to determine powerful and durable hydrophilic properties. There is a case.

  The technical demands as described above exist not only for polyolefins but also for other polymer materials having superior surface activity. For example, it may be required to modify the original surface properties of the polymer to give the desired surface properties.

  The present invention provides a polymer material and a fiber material, a film or plate-like or rod-like material using the polymer material, a writing instrument member, an orthodontic member, a battery separator, a microorganism, and the like, by a technique corresponding to the above technical requirements. Medium material, synthetic paper, filter material, wipes, disposable medical / hygiene / cosmetic products (diapers, sanitary products, bandages, gauze, napkins, tapes, puffs, other medical / hygiene products, various cleansing applications and face washing Cosmetics such as packs), adhesive improvement materials, orthodontic members, medical device materials (artificial organs, tubes, threads, plate-shaped molded products), etc., for modifying desired surface properties It relates to the device.

  The apparatus of the present invention is extremely effective for surface modification of ABS resin, polycarbonate resin and many other polymer materials. However, the use of ABS resin or polycarbonate resin tends to be limited due to environmental problems. By molding with polyolefin resin such as polyethylene or polypropylene instead of these resins, these environmental problems can be solved, and products with excellent chemical resistance, light weight and impact resistance, which are the advantages of polyolefin resin, can be obtained. I can expect. Various hydrophilic polymer materials used for stationery and writing instruments for makeup, or materials related to the body such as orthodontic members, various hygiene and medical materials, polyolefin resin moldings and other polymers that do not cause environmental problems The material modified by the present invention is effective.

A battery separator is used to separate a positive electrode and a negative electrode of a chemical battery to prevent a short circuit, and to hold an electrolyte and smoothly perform an electromotive reaction. Various conditions are required depending on the type of battery, and many inventions have been made.
For example, in an alkaline battery, since the electrolyte is strongly alkaline, the battery separator must be an alkali-resistant material. Conventionally used polyamide fiber nonwoven battery separators have the drawback that, by repeated use, nitrogen oxides are eluted from the fibers and the battery life is shortened.

For this reason, separators made of non-woven polyolefin fibers (including composite fibers) made of polyethylene or polypropylene with excellent chemical resistance have been studied, but batteries made of polyolefin materials with excellent water absorption properties are durable. The separator for use is not yet seen. For example, the method most frequently used is a method of impregnating a polyolefin fiber with a surfactant. However, since the surfactant is gradually eluted, it cannot be used for a long time.
Furthermore, a method of applying or impregnating an aqueous dispersion of potassium ionomer such as ethylene / acrylic acid copolymer to core / sheath structure fiber using polypropylene fiber as the core and ethylene / acrylic acid copolymer as the sheath (special feature) No. 200-58023). Also in this case, the hydrophilic durability is not satisfied.

  In addition, after grafting a vinyl monomer having an ester bond to a non-woven fabric of polyolefin fibers (graft copolymerization), the ester bond is hydrolyzed to generate an acid group, thereby providing hydrophilicity and ion exchange ability. It has been proposed (Japanese Patent Laid-Open No. 11-7937). However, there is a problem that it is not easy to graft a sufficient amount for imparting hydrophilicity even when a vinyl monomer is grafted onto a polyolefin fiber or film by the disclosed method. Further, there is a problem that it is necessary to further hydrolyze after grafting, which is troublesome.

  A method of imparting hydrophilicity by coating a polyolefin non-woven fabric with polyvinyl alcohol is also known (JP-A-1-248460). However, although the obtained coating has high hydrophilicity, there is a problem that hydrophilic durability is not sufficient because it is a simple coating. Moreover, when used alone, there is a drawback that the battery layer shrinks and causes a short circuit problem for battery separators.

The most promising treatment method would be a method of grafting a polypropylene non-woven fabric by irradiating a hydrophilic vinyl compound with ultraviolet rays in the presence of a catalyst (Japanese Patent Laid-Open No. 11-185722). Grafting with a vinyl monomer is expected to be ideally hydrophilic, but is actually very difficult for polyolefins. Even if it seems that grafting has occurred, it is often the case that a vinyl polymer (homopolymer) polymerized alone is simply impregnated.

  A method for imparting hydrophilicity by treating a nonwoven fabric made of polyolefin fibers with a hydrophilic resin in the presence of a persulfate is disclosed (Japanese Patent Laid-Open No. 11-67183) in a strong alkaline aqueous solution. When heated to about ℃, there is a problem with durability.

  The inventor of the present invention previously found a method of activating the surface of a polymer material and then treating it with a catalyst and a hydrophilic polymer (Japanese Patent Application No. 11-375055). However, a method that can be applied to a wider range of materials is desired.

  Currently, nonwoven fabric made of glass fiber material is often used for the lead-acid battery separator. In addition, a separator in which glass fibers and cellulose fibers are combined with a resin (Japanese Patent Laid-Open No. 59-73842), or about 30% acid-resistant synthetic fibers mixed with inorganic substance powder and glass fibers and solidified with a resin binder There are separators (JP-A-8-13001, JP-A-11-260335). These are heavy and expensive, and those using a resin have a problem of peeling between the resin and the glass fiber.

  A synthetic pulp (polyethylene fiber non-woven fabric) impregnated with a surfactant (Japanese Patent Laid-Open No. 6-302313) has the drawback that when immersed in sulfuric acid, the surfactant dissolves and the electrolyte absorbability decreases. By applying at least one treatment selected from a sulfonation treatment, a fluorination treatment, and a grafting treatment with a vinyl monomer to a material comprising a polyolefin resin, a separator having a long-term liquid retention can be obtained. It is also said that a surfactant may be used in combination to increase the permeation rate of the electrolytic solution (Japanese Patent Laid-Open No. 8-273654). However, this technique has the following problems.

  First, sulfating treatment uses fuming sulfuric acid, but the material turns brown and becomes brittle. On the other hand, the increase in water absorption cannot be said to be sufficient, and the danger at the time of handling chemicals or treating waste liquid is extremely great. Fluorination treatment is also extremely dangerous for chemicals and equipment, but the hydrophilicity obtained is not sufficient.

  There is an acid battery separator (Japanese Patent Laid-Open No. Sho 62-268900, Japanese Patent No. 2513467) obtained by attaching and polymerizing polyethylene glycol diacrylate and a hydrophilic vinyl monomer to a polyolefin synthetic pulp. According to the publication, in addition to using ammonium persulfate as a catalyst, any polymerization method may be used. However. For polyolefin, it is extremely difficult to graft by any method. The adhesion polymerization in this case is considered to be that a resin formed by polymerizing a monomer is impregnated into a polyolefin synthetic pulp and solidified. Therefore, in the strongly acidic electrolyte solution in the lead-acid battery, there is a high possibility that the polyolefin material and the hydrophilic resin will be peeled by contact with the electrolyte solution for a long time and repeated charge and discharge.

Hydrophobic polyolefin nonwoven fabric has excellent water absorption, so that it can be used in battery separator applications in sulfuric acid with a concentration of 40% by weight for lead-acid batteries, and 30% for alkaline batteries. It must be able to withstand long-term use as long as possible by repeatedly charging and discharging in a potassium hydroxide aqueous solution of about%. For this purpose, development of a treatment method for obtaining a hydrophilic polymer material excellent in chemical resistance, oxidation resistance and the like is desired. Moreover, it is industrially desired that the method can be processed more easily, cheaply and in large quantities.
Japanese Patent Application No.11-375055 JP-A-1-248460 Japanese Patent Publication No. 3-103448 JP 2000-58023 A JP-A-11-7937 JP-A-1-248460 JP-A-8-130001 JP-A-11-260335 JP-A-6-302313 JP-A-8-273654 JP-A 62-268900 Japanese Patent No. 2513467

  An object of the present invention is to provide an apparatus for performing a method for modifying a surface of a polymer material that is not accompanied by a decrease in strength of the material and has excellent durability. In addition, the present invention is for medical / hygiene / cosmetic products made of such modified materials, that is, disposable diapers, sanitary products, bandages, gauze, disinfecting adhesive cloths, various cleansing applications / face-wash packs, napkins, etc. Water-absorbing materials, writing instrument members, orthodontic members, battery separators, water-retaining materials such as agricultural and dry land greening materials, microbial medium materials, synthetic paper, filter media, wiping cleaning materials, medical equipment materials (artificial It is an object of the present invention to provide an apparatus for producing organs, joints, various tubular, thread-like, plate-like molded products), polymer materials with improved adhesion, composite materials with polymer materials, and the like.

  In addition, the present invention is excellent in electrolytic solution absorbability, acid resistance, alkali resistance, oxidation resistance, etc., lightweight and excellent in mechanical strength, and is truly hydrophilized by chemical bonding, for a long time in the electrolytic solution. It is an object of the present invention to provide a battery separator made of a hydrophilic polymer material that does not lose its performance even when placed, and an apparatus for carrying out a method for easily and inexpensively manufacturing the battery separator.

  As a result of intensive studies on surface modification methods for various polymer materials in order to achieve the above-mentioned object, the present inventor mainly conducted impregnation treatment, activation treatment, grafting of vinyl monomer, and hydrophilic polymer. The present invention has been completed by finding that it is effective to combine the processing apparatus according to the above.

  According to the present invention, the surface of the polymer material is brought into contact with (1) a compound impregnating the polymer material (referred to as an impregnating agent), and the impregnation amount within a depth of 100 microns from the surface is 0.1. Impregnation treatment step in which impregnation is carried out in the range of ˜40% by weight (with respect to polymer material) and the shape of the material is not substantially changed, (2) activation treatment step for introducing carbonyl group, and (3) monomer By the step of grafting, an effective reforming process can be performed by combining apparatuses for processing in this order.

  Alternatively, according to the present invention, the surface of the polymer material is brought into contact with (1) a compound impregnating the polymer material, and the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40 weight. % (With respect to polymer material), impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group, (3) treatment with a hydrophilic polymer Therefore, an effective reforming process can be performed by combining apparatuses that process in this order.

  Alternatively, according to the present invention, the surface of the polymer material is brought into contact with (1) a compound impregnating the polymer material, and the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40 weight. % (With respect to polymer material), impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group, (3) treatment with a hydrophilic polymer And (4) By the step of grafting the monomer, an effective reforming process can be performed by combining the apparatuses for processing in this order.

Alternatively, according to the present invention, the surface of the polymer material is treated in this order by (1) an activation treatment step for introducing a carbonyl group and (2) a treatment with a hydrophilic polymer in this order. An effective reforming process can be performed by combining the devices.

  Alternatively, according to the present invention, the surface of the polymer material may be (1) an activation treatment step for introducing a carbonyl group into the polymer material, (2) a treatment step with a hydrophilic polymer, and (3) By the step of grafting the polymer, an effective reforming process can be performed by combining the apparatuses for processing in this order.

  Alternatively, according to the present invention, the surface of the polymer material is treated in this order by (1) an activation treatment step for introducing a carbonyl group into the polymer material and (2) a step of grafting the monomer. An effective reforming process can be performed by combining the apparatuses.

  According to the present invention, a polymer such as polyolefin, which is difficult to be modified, or a material composed of other polymer materials is obtained without impairing the form, strength, and appearance of the material. Improvements in hydrophilicity, water absorption, adhesiveness, and the like are possible, and a wide range of uses can be expected for these materials.

The present invention is described in detail below.
(Polymer material) The polymer material to be treated in the present invention is a polymer single material, a mixed material or a modified material thereof, or a mixture or composite of these polymer material and glass, metal, carbon material or the like. Means a polymer material contained in the material obtained by As the synthetic polymer, any of a thermoplastic polymer and a thermosetting polymer can be used. Various methods are exemplified as the synthesis method, but the polymer material of the present invention includes a synthetic polymer obtained by any of these methods. For example, (1) addition polymer: homopolymer or copolymer of monomers selected from the group consisting of olefins, cyclic olefins, vinyl compounds other than olefins, vinylidene compounds, and other compounds having a carbon-carbon double bond Or a mixture or modified product of these homopolymers or copolymers, (2) polycondensate: polyester, polyamide, etc., or a mixture or modified product of these polymers, (3) addition condensate: phenol resin (Kinol: trade name, including products manufactured by Nihon Kynol Co., Ltd.), urea resin, melamine resin, xylene resin, etc., or a mixture or modification of these polymers, (4) polyaddition products: polyurethane, polyurea, etc Or a mixture or modified product of these polymers, (5) ring-opening polymer: cyclopropane, ethylene oxide Homopolymers or copolymers such as id, propylene oxide, lactone and lactam, or mixtures or modifications of these homopolymers or copolymers, (6) cyclized polymers: divinyl compounds (eg, 1,4 A homopolymer or copolymer such as pentadiene) or a diyne compound (for example, 1,6-heptadiyne), or a mixture or modification thereof, (7) an isomerized polymer: for example, an alternating copolymer of ethylene and isobutene (8) Electropolymer: Homopolymer or copolymer of pyrrole, aniline, acetylene, etc., or a mixture or modified product of these homopolymers or copolymers, (9) Aldehyde or ketone polymer, ( 10) polyethersulfone, (11) polypeptide, and the like. Examples of natural polymers include cellulose, protein, polysaccharides and the like alone or as a mixture, and modified products thereof.

  In the present invention, the above addition polymer is particularly preferably used. The monomer constituting the addition polymer is not particularly limited, but the olefin may be any alpha such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, and octene-1. An olefin homopolymer or a copolymer of two or more of these, or a mixture of these homopolymers and / or copolymers can be appropriately used.

  In the present invention, the vinyl compound other than olefin is a compound having a vinyl group, such as vinyl chloride, styrene, acrylic acid, methacrylic acid, acrylic acid or methacrylic acid ester, vinyl acetate, vinyl ethers, vinyl carbazole, acrylonitrile. Etc. A vinylidene compound other than olefin is a compound containing a vinylidene group, and examples thereof include vinylidene chloride, vinylidene fluoride, and isobutylene. Examples of compounds having carbon-carbon double bonds other than olefins, vinyl compounds and vinylidene compounds include maleic anhydride, pyromellitic anhydride, 2-butenoic acid, ethylene tetrafluoride, ethylene trifluoride chloride and the like and double bonds Examples of the compound include two or more, such as butadiene, isoprene, chloroprene and the like.

As a preferable addition polymer, a homopolymer of these monomers, a copolymer of two or more monomers, or a mixture of these polymers can be appropriately used. Particularly preferred are polyethylene, copolymers of ethylene and other alpha-olefins, and copolymers of polypropylene, propylene and other alpha-olefins. The copolymer includes a random copolymer and a block copolymer.
In the present invention, polyolefin is preferably used as the polymer material because it is particularly effective for imparting hydrophilicity to polyolefin, which is said to be difficult to treat.

  The polymer material other than polyolefin is a homopolymer or copolymer of at least one monomer selected from the group consisting of vinyl compounds other than olefins, vinylidene compounds, and other compounds having a carbon-carbon double bond. , For example, polymethacrylate resin, polyacrylate resin, polystyrene, polytetrafluoroethylene, acrylonitrile copolymer (acrylic fibers and their moldings, ABS resin, etc.), copolymer containing butadiene (synthetic rubber) ), Etc., and polyamides (including aliphatic polyamides and aromatic polyamides including nylon), polyesters (including polyethylene terephthalate and aliphatic and wholly aromatic polyesters), polycarbonates, polyurethanes, polybenzoates, polyether sulfones Poloacetal, various synthetic rubbers and the like are preferably used.

Examples of the polymer compound other than the above include, for example, polyacetal, polyphenol, polyphenylene ether, polyalkyl paraoxybenzoate, polyimide, polybenzimidazole, poly-p-phenylene benzobisthiazole, poly-p-phenylene benzobisoxazole, polybenzothiazole. Examples include polybenzoxazole, acetate fiber, regenerated cellulose fiber (rayon, cupra, polynosic, etc.), vinylon, fiber of vinyl alcohol and vinyl chloride copolymer (polyclar, trade name: corderan, etc.), etc. it can. Furthermore, natural fibers such as carbon fibers, cotton, hemp and other plant fibers, and animal fibers such as silk and wool can also be used. Also, a mixture or composite of a plurality of these polymer materials can be preferably used.
The polymer material used in the present invention is not limited to those described above, and can be applied to all polymer compounds.

  The polymer material may contain an antioxidant, a stabilizer, a nucleating agent, a flame retardant, a filler, a foaming agent, an antistatic agent, and other additives that are usually added to other polymer materials. In general, stabilizers such as antioxidants obstruct surface activation, and thus their presence is considered to be undesirable, and measures such as preparing additive-free materials or removing stabilizers are desirable. ing. On the other hand, the present invention can achieve effective surface modification even when the polymer material contains an additive such as a stabilizer. Therefore, it is characterized in that a molded product containing an additive obtained by a normal production method can be used as it is as a polymer material.

  In the present invention, there is no particular limitation on the form of the molded article of the polymer material subjected to the modification treatment. For example, any form of fiber, woven fabric, non-woven fabric, cloth, plate, film, sheet, tube, rod, hollow container, box, foam, and laminate can be used. In particular, from the viewpoint of improving water absorption, molded articles such as fibers, woven fabrics, nonwoven fabrics, cloths, films, and sheets can be easily treated. In particular, porous films and sheets produced for filters and synthetic papers can be subjected to durable and effective hydrophilic treatment. Further, by applying the processing method of the present invention to a molded body for a member or part that has been previously molded into a predetermined shape, a polymer material that could not be used conventionally can be used. Various plastic products (bolts, nuts, chains, parts of electric appliances, caps, covers, etc.) are also made hydrophilic by the present invention, so that wettability and adhesion are improved, and chargeability is reduced. .

As fibers and fiber products, various fibers, woven fabrics and nonwoven fabrics can be preferably used. The form of the fiber may be any of a single component fiber, a mixture of a plurality of types of fibers, a blended fiber, and a composite fiber (core-sheath type, parallel type, multicore type, archipelago type, radial type, etc.) Good.

  For battery separator applications, the shape of the polymer material to be modified is preferably a non-woven fabric, a porous sheet, a porous film, a non-woven fabric, a plate-like composite material containing fibers, a woven fabric, or the like. . When manufacturing an alkaline battery separator, a nonwoven fabric having a pore diameter of 1 to 200 μm, a porosity of 30 to 80 vol%, a thickness of 20 to 500 μm, a fiber diameter of 0.1 to 100 μm, and a basis weight of 5 to 100 g / m 2 is preferable. Used. Thereby, it is easy to get wet with the electrolytic solution, the electrolytic solution retention property is large, the permeability of oxygen gas generated from the positive electrode during charging is excellent, and a high strength battery separator is obtained. For lead-acid battery separators, a composite material in which a coarse sheet made of glass fiber is heat-sealed with polyolefin fiber or hardened with resin is also preferably used. A separator for a lead acid battery of an acid battery needs to have an appropriate thickness and an excellent strength and liquid retention. For this purpose, a nonwoven fabric having a pore diameter of 1 to 200 μm, a porosity of 30 to 80% by volume, a thickness of 500 to 1200 μm, a fiber diameter of 0.1 to 100 μm, and a basis weight of 100 to 300 g / m 2 is preferably used.

  In performing surface modification of the polymer material, it is preferable to remove impurities by washing the surface of the polymer material with an appropriate liquid. For example, polyolefin, polyvinyl chloride, polyvinylidene chloride and the like are preferably washed with alcohol or toluene. Acetate, nylon, polyester, polystyrene, acrylic resin, polyvinyl acetate, polycarbonate, polyurethane and the like are preferably washed with alcohol. Cellulosic materials such as rayon and cupra are preferably washed with alcohol after washing with a detergent.

(Impregnation treatment) In the impregnation treatment, a compound having an affinity for a polymer material is used as it is or as a solution or dispersion, and the polymer material is contacted at a temperature below its softening point to impregnate the compound from the surface. It is a method to make it. At this time, the polymer material is not substantially deformed. A compound used for this purpose is called an impregnating agent. This impregnation treatment step can be said to be a step in which the impregnating agent soaks into the amorphous region of the polymer compound and creates a gap inside the material. There exists an effect | action which makes the activation process and grafting process etc. which are performed next easy. The impregnated impregnating agent is removed by washing after subsequent processing steps. A preferable range of the impregnating amount of the impregnating agent with respect to the polymer material is expressed by a weight increase rate, and is 0.1 to 40% by weight when the thickness of the polymer material is less than 100 microns, and the thickness of the material is 100 microns. In the above case, it is 0.1 to 40% by weight with respect to the material portion within a depth of 100 microns from the surface of the material. In the case of a polymer material having a thickness and a diameter of about 20 mm or less, the amount of impregnation is preferably about 0.1 to 10% by weight for simplicity.

  The compound that can be used as the impregnating agent may be any of organic, inorganic, gas, liquid, and solid as long as the compound has an affinity for the polymer material. The liquid impregnating agent can be used as it is or as a mixture such as a solution or dispersion with another liquid, as long as it is solid, as a solution or dispersion or emulsion, or as a gas. The impregnating agent in the present invention includes a so-called solvent, but is not limited thereto. The impregnating agent is selected according to the type of the polymer material to be treated. Compounds used for carrier dyeing of synthetic fibers, particularly polyester-based synthetic fibers, and commercially available assistants for carrier dyeing can be preferably used. In addition, various compounds corresponding thereto can be used. These can be applied to a wide range of polymer materials such as polyolefin, polystyrene, polyacrylic resin, and polyurethane in addition to polyester. Examples of this include diphenyl, ortho or parahydroxybiphenyl, other diphenyl derivatives, or sodium salicylate or derivatives thereof, halogenated aromatic compounds (eg mono, di or trichlorobenzene), etc. It can be used as an organic liquid solution as a solvent, an aqueous dispersion, or an emulsion using a surfactant. Alternatively, an organic liquid having an affinity for the polymer material can be used as the impregnating agent. In this case, the standard of selection of the organic liquid is a single liquid or a mixture of a plurality of liquids close to the solubility parameter (SP value) of the polymer material to be processed. It is preferable to treat with a solvent having a difference of about +2 or −2 from the solubility parameter of the polymer. Solvents with differences within this range can be used if they are processed at a low temperature in a short time. Just soak into the surface of the polymer, do not dissolve. Even organic solvents that are soluble at high temperatures can be used if they are treated in a short time at low temperatures that do not exhibit solubility. Examples of liquid impregnating agents include polypropylene, toluene, xylene, decalin, tetralin, cyclohexane, a mixture of 1 volume of dichloroethane and 4 volumes of ethanol, and polyethylene includes 1 volume of toluene, xylene, alpha-chloronaphthalene, dichlorobenzene. A mixture of 1 volume of toluene and 10 volumes of methanol can be used for polystyrene, and a mixture of 1 volume of phenol and 10 volumes of hexane can be used for polyethylene terephthalate.

  Conditions such as temperature and time of the impregnation treatment are appropriately selected depending on the shape of the material. For example, in the case of a nonwoven fabric made of polyolefin fibers having a fiber diameter of about 5 to 10 μm, the impregnating agent is immersed in a room-temperature impregnating agent (for example, toluene) for 2 minutes and then subjected to a centrifugal dehydrator (rotation number: 500 to 200 times / min). Shake off and finish when the surface impregnating agent is apparently dry. In the case of a polyolefin film, plate and molded product (thickness of about 2 to 5 mm), it is immersed in an impregnating agent at room temperature to 70 ° C. for about 5 to 30 minutes and then drained as described above. The impregnation weight ratio in these cases is about 1 to 10% by weight. In the case of wool, it is immersed in a mixture of an aqueous sodium carbonate solution and methanol at room temperature for 1 to 10 minutes, rinsed with methanol, and drained with a centrifuge. This impregnation treatment is effective in the case of a material having a large surface area such as a film or a plate, or a material containing a lot of antioxidants and other additives.

(Impregnation treatment apparatus) The impregnation treatment apparatus is an apparatus for effectively performing the impregnation treatment. Depending on the shape, the polymer material to be treated is introduced into a tank containing the above impregnating agent with a roller or a belt conveyor, immersed in a predetermined temperature for a predetermined time, and then subjected to a centrifugal dehydrator. It consists of a dryer that dries. Therefore, it consists of a tank for impregnating immersion, a centrifugal dehydrator, and a dryer.

(Activation treatment step) The step of activating the polymer material in the present invention means a treatment for introducing a carbonyl group into the material surface. In addition to the carbonyl group, it also includes introducing a functional group containing oxygen or nitrogen, an unsaturated bond, or the like. A preferable method for the activation treatment is various treatments such as plasma treatment, ozone treatment, ultraviolet irradiation treatment, corona discharge treatment, and high-pressure discharge treatment. For the purpose of the present invention, any known equipment can be used. The degree of the activation treatment is appropriately adjusted according to the purpose of the modification, but in the present invention, the minimum activation treatment that can confirm the introduction of the carbonyl group is preferable. Conventionally proposed activation treatment methods are often excessive treatments for the purpose of the present invention. As a criterion for judgment, it is effective to measure the infrared absorption spectrum of the processed polymer material. For example, the ratio of the absorbance of the absorption based on the introduced carbonyl group and the absorbance of the absorption based on the structure of the unchanged crystal part can be determined by the baseline method to know the degree of oxidation. For example, in the case of polypropylene, the ratio of the absorbance near 9710 cm −1 based on the introduced carbonyl group and the absorbance at 973 cm −1 of the absorption based on the unchanged crystalline partial methyl group may be about 0.2 or less. preferable. Alternatively, when polypropylene and other polymer materials are also included, the absorbance near 1710 cm −1 based on the carbonyl group after treatment may increase by about 1% to 20% compared to the absorbance at the same position before treatment. preferable.

  A preferable method for setting the activation treatment conditions is to obtain a relationship between the treatment time and the carbonyl absorption in advance for the target polymer material, and based on this relational expression, the activation treatment to the extent that the material strength is not reduced. Define the conditions. Even if there is a minimum amount of carbonyl group that can be detected by infrared absorption spectroscopy, if intensity decreases, it is appropriate to interpolate to the time corresponding to the absorbance that cannot be measured by infrared absorption based on this relational expression. The correct processing time. In this way, an effective surface activation treatment can be achieved without reducing the material strength.

(Ozone treatment) The purpose of ozone treatment is to carry out a reforming reaction mainly consisting of an oxidation reaction by bringing the surface of a polymer material into contact with ozone molecules. The ozone treatment is performed by exposing the polymer material to ozone. The exposure method can be performed by an appropriate method such as a method of holding in an atmosphere in which ozone exists for a predetermined time, a method of exposing in 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. The obtained ozone-containing gas can be introduced into a container, tank, or the like that holds the material to perform ozone treatment. Various conditions such as the ozone concentration in the ozone-containing gas, the exposure time, and the exposure temperature can be appropriately determined according to the type and shape of the polymer material and the purpose of the surface modification. Usually, ozone or air flow is used, ozone is generated at a flow rate of 20 ml to 10 L / min at a concentration of 10 to 200 g / m3, and the treatment is performed at a temperature of 10 to 80 ° C. for a time of 1 minute to 10 hours. it can. For example, in the case of polypropylene or polyvinyl chloride fiber, treatment at an ozone concentration of 10 to 40 g / m3 and room temperature for about 10 to 30 minutes is appropriate. In the case of a film shape, treatment with an ozone concentration of about 10 to 80 g / m 3 and a room temperature of about 20 minutes to 3 hours is appropriate. The generated ozone concentration when air is used is about 50% when oxygen is used. It is presumed that hydroperoxy groups (—O—OH) and the like are introduced into the surface of the polymer material by ozone treatment due to the ozone treatment, and most of them are converted to functional groups such as hydroxyl groups and carbonyl groups. .

(Plasma treatment) In plasma treatment, a polymer material is placed in a container containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen, air, or the like, exposed to plasma generated by glow discharge, and oxygen, nitrogen, etc. on the surface of the material. It aims at introducing the functional group containing. When an inert gas such as argon or neon is present at a low pressure, it is considered that the surface of the polymer material is attacked by the generated plasma and radicals are generated on the surface. Then, it is considered that radicals are combined with oxygen by being exposed to air, and a carboxylic acid group, a carbonyl group, an amino group, or the like is introduced into the surface of the polymer material. In addition, it is thought that a functional group is directly introduced by a plasma treatment in a small amount of nitrogen, carbon dioxide, oxygen or air. Discharge forms of plasma generation are classified into (1) DC discharge and low frequency discharge, (2) radio wave discharge, (3) microwave discharge, and the like.

(Ultraviolet irradiation treatment) The ultraviolet irradiation treatment is a method of irradiating the surface of the polymer material with ultraviolet rays in the air. As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. The surface of the polymer material may be treated with an ultraviolet absorbing solvent before irradiation. Although the wavelength of ultraviolet rays can be selected as appropriate, in order to reduce deterioration of the material, it is preferably around 360 nm or less. When the polymer material is irradiated with ultraviolet rays, the ultraviolet rays are absorbed by chemical structures such as double bonds in the surface region of the molded product, the chemical bonds are broken by the absorbed energy, and oxygen in the air is generated in the generated radicals. It is considered that a carbonyl group, a carboxyl group, and the like are generated by bonding and via a peroxide structure in the middle.

(High-pressure discharge treatment) High-pressure discharge treatment is performed by installing a belt conveyor to move the polymer material to be processed in the tunnel-like treatment device, and moving the polymer material on the inner wall of the treatment device. In this method, a high voltage of several hundreds of thousands of volts is applied between the attached electrodes and discharged in air. It is considered that oxygen in the air and the surface of the object to be processed are activated by the discharge, oxygen is taken into the surface of the polymer material, and a polar group is generated.

(Corona discharge treatment) Corona discharge treatment generates corona discharge by applying a high voltage of several thousand volts between a grounded metal roll and a knife-like electrode placed at intervals of several millimeters. The polymer material to be processed is passed between the electrode and the roll. This method is suitable for the processing of films or laminae.

  Methods other than ozone treatment activate the surface by irradiating the material, and it is necessary to devise a shadowed portion that is not exposed to radiation. Accordingly, ozone treatment is preferable for treating a fiber aggregate such as a non-woven fabric or the entire material having a shadow portion depending on the form of the material. In addition, ozone treatment is preferable because it is inexpensive in terms of equipment costs.

(Activation treatment apparatus) The activation treatment apparatus is carried out by applying a known apparatus for performing the ozone treatment, plasma treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, and corona discharge treatment. The polymer material that has been subjected to the impregnating treatment or the polymer material that has just been washed is introduced into the processing apparatus by a roller or a belt conveyor, depending on the shape, and processed at a predetermined temperature for a predetermined time. Send to the device part. However, the polymer material processed by the activation processing apparatus may be temporarily taken out in this process without being sent to the next processing process apparatus, and may be introduced again into an apparatus for performing the next process several days later.

(Monomer Grafting Process) The monomer to be grafted in the present invention is not limited as long as it can be grafted, but is a compound having at least one carbon-carbon double bond, such as a vinyl compound or a similar compound. Compounds are preferred. Of the monomers, hydrophilic monomers are preferred. Hydrophilic monomers include acrylic acid, methacrylic acid, vinyl acetic acid, 2-butenoic acid, ethylene sulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, maleic anhydride, anhydrous Preference is given to at least one monomer selected from the group consisting of pyromellitic acid or a mixture with at least one monomer selected from these groups. In the present invention, it is particularly preferable to use acrylic acid or methacrylic acid from the viewpoint of chemical resistance and water absorption.

  Furthermore, vinyl monomers such as acrylic acid esters, methacrylic acid esters, vinyl acetate, and styrene, which are less hydrophilic than hydrophilic monomers, can also be used. It is preferable to use only a hydrophilic monomer, but by using a mixture of a hydrophilic monomer and a poorly hydrophilic monomer, the grafting rate increases and the hydrophilicity contained in the graft polymer. The monomer may be able to impart the hydrophilicity of the material.

  Monomer grafting is (1) a method in which a catalyst or an initiator (hereinafter collectively referred to as “initiator”) is present, and (2) a method in which heating is performed in the presence or absence of an initiator. Or (3) Any method in which ultraviolet irradiation is carried out in the presence or absence of a catalyst or an initiator is preferred. Initiators include peroxides (benzoyl peroxide, t-butylhydroxyperoxide, di-t-butylhydroxyperoxide, etc.), ceric ammonium nitrate (IV), persulfates (potassium persulfate, ammonium persulfate, etc.), Redox initiator (oxidizer: persulfate, hydrogen peroxide, hydroperoxide, etc., inorganic reducer: copper salt, iron salt, sodium bisulfite, sodium thiosulfate, etc., or organic reducer: alcohol, amine, Combination with oxalic acid and the like, and oxidizing agent: hydroperoxide and the like and inorganic reducing agent: copper salt, iron salt, sodium bisulfite, sodium thiosulfate and the like, or organic reducing agent: dialkyl peroxide, diacyl peroxide and the like and reducing agent : Tertiary amine, naphthenate, mercaptan, organometallic compound (triethylaluminium , A combination of triethyl like element)), and other known radical polymerization initiator and the like. When acrylic acid is used as a monomer, a water-soluble polymerization initiator such as dicerium ammonium nitrate (IV) or potassium persulfate is preferably used, but benzoyl peroxide, N, N-azobisisobutyronitrile, etc. The water-insoluble initiator can be used by dissolving in methanol or acetone and mixing with water. In the case of ultraviolet irradiation, a photosensitizer such as benzophenone or hydrogen peroxide may be added as a catalyst in addition to these polymerization initiators.

  For grafting of the monomer, a general grafting method can be used. That is, any reaction of a liquid phase, a gas phase, and a solid phase is possible. By reaction mixture is meant a solution containing initiator, monomers and their solvents, or a gas such as air or nitrogen containing monomer vapors. Specific examples are shown below.

  In the case of a water-soluble initiator, the required amount is dissolved in water. In the case of a water-insoluble initiator, it is dissolved in an organic solvent (for example, acetone, methanol, etc.) mixed with water such as alcohol or acetone, and then mixed with water so that the initiator does not precipitate. A material subjected to an activation treatment or a hydrophilic polymer treatment described later is added to the initiator solution, and a monomer is added to perform grafting. The inside of the processing container is purged with nitrogen as necessary. In the case of heat grafting, the reaction mixture is heated at an appropriate temperature for an appropriate time. Alternatively, when grafting is performed under ultraviolet irradiation, ultraviolet irradiation is performed at an appropriate temperature and time. Although the ultraviolet lamp is not particularly limited, a high-pressure mercury lamp (for example, trade name: H400P manufactured by Toshiba Corporation) can be used. Although the wavelength may extract ultraviolet rays around 360 nm with a filter, it may irradiate light of all wavelengths. Monomer grafting can be used as a vapor when the monomer is a volatile compound. That is, the treated product is placed in a closed container, a volatile monomer (eg, methyl methacrylate, styrene, etc.) is injected, and the container is decompressed to vaporize the monomer. The reaction vessel is irradiated with ultraviolet rays for grafting.

  A method in which a vinyl monomer having an amide group is used as the monomer and the amide group is Hoffmann-transferred from the method described in Japanese Patent No. 323471 can be preferably used.

  (Monomer grafting apparatus) This is an apparatus for effectively performing the monomer grafting process. A tank containing a monomer and an initiator or a catalyst solution for carrying out the above-mentioned monomer grafting on a roller or a belt conveyor depending on the shape, or containing a monomer vapor After introducing into the tank and immersing or irradiating with ultraviolet rays at a predetermined temperature and for a predetermined time, it is then washed with a cleaning device, subjected to a centrifugal dehydrator and dried to a predetermined degree. Therefore, it consists of a monomer grafting device part, a cleaning device part, a dehydrator part, and a dryer part.

  (Hydrophilic polymer) In the present invention, the hydrophilic polymer means a water-soluble polymer or a polymer that is not readily water-soluble but has hydrophilicity. Specific examples include polyvinyl alcohol, carboxymethyl cellulose, ethylene-vinyl alcohol copolymer, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, poly-α-hydroxyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, Examples include polyalkylene glycols such as polypropylene glycol. These sulfonated products can also be used. Other examples include sodium alginate, starch, silk fibroin, silk sericin, gelatin, various proteins, and polysaccharides.

(Treatment with hydrophilic polymer) When the activated polymer material is subjected to the hydrophilic polymer treatment, it is preferably carried out in the presence of a catalyst or an initiator. As the catalyst and the initiator, the same ones as in the case of grafting with a monomer can be used.
In the treatment step with the hydrophilic polymer, the hydrophilic polymer is preferably used in a solution state. Any water-soluble polymer can be used as an aqueous solution. If it is poor in water solubility, dissolve it in a suitable solvent. The case where a water-soluble polymer is used will be described below.

  When the treatment with the water-soluble polymer is performed in the absence of the initiator, the polymer material subjected to the activation treatment is placed in an aqueous solution of a hydrophilic polymer. When the treatment with the water-soluble polymer is performed in the presence of the initiator, an aqueous solution of the water-soluble polymer is first prepared, and in the case of the water-soluble initiator, a necessary amount is dissolved therein. In the case of a water-insoluble initiator, it is dissolved in an organic solvent mixed with water, such as alcohol or acetone, and then added to an aqueous solution of a water-soluble polymer. A polymer material subjected to an activation treatment is placed in a solution of a water-soluble polymer to which an initiator has been added for treatment. It is desirable to replace the inside of the processing container with nitrogen. However, in a simple manner, a practical process can be performed without nitrogen substitution.

  The temperature of the treatment with the water-soluble polymer and the initiator is not particularly limited, and is usually 10 to 80 ° C., preferably 60 to 90 ° C. In order to improve hydrophilic durability, a treatment at a high temperature for a long time (for example, about 3 to 12 hours) is also performed.

(Hydrophilic polymer processing apparatus) An apparatus for effectively performing the hydrophilic polymer processing. In order to perform the hydrophilic polymer treatment with a roller or a belt conveyor according to the shape of the pretreated polymer material, the polymer material is introduced into a tank containing a solution of the hydrophilic polymer and an initiator or a catalyst, at a predetermined temperature, After reacting for a predetermined time, it comprises a drier that is washed with a washing device, applied to a centrifugal dehydrator, and dried to a predetermined degree. Therefore, it comprises a hydrophilic polymer processing device part, a cleaning device part, a dehydrator part, and a dryer part.

  (Use of material treated with the apparatus of the present invention) The polymer material modified by the method of the present invention has greatly improved properties such as hydrophilicity, water absorption, water retention, adhesiveness, etc. Excellent durability of characteristics. Utilizing hydrophilicity, water absorption and water retention, it can be applied to various uses. Moreover, since it is excellent also in adhesiveness, it can adhere | attach to paper, wood, a metal, etc. with a general adhesive agent, for example, starch, polyvinyl acetate, polyvinyl alcohol, an epoxy resin system, polycyanoacrylate, etc. It can be applied to various materials that require adhesiveness. Furthermore, the modification method of the present invention can be applied to many polymer materials including polyolefins such as polypropylene and polyethylene, which are particularly difficult to modify. Polyolefin non-woven fabric or mixed non-woven fabric made of polyolefin and other polymers can give water absorption of 7 to 10 times its own weight, and further to adhesiveness, alkali resistance, acid resistance and oxidation resistance. Excellent. Although each use is demonstrated below, the use of this invention is not limited to the following.

  (1) Material for wiping and cleaning: Currently, based on a composite fiber of polyester fiber, polyolefin fiber, and synthetic fiber, rayon is blended to impart hydrophilicity, and then an aqueous solution containing a surfactant is used. The impregnated material is commercially available as a household disposable cleaning material or wiper. When this disposable cleaning material is manufactured with the fiber of the modified water-absorbing polymer material of the present invention, it is lightweight, high-strength, excellent in water-absorbing property and surfactant-absorbing property, and thus has increased durability. Is obtained. After use, it can be reused by washing with water several times.

  (2) Water-absorbing material: means a polymer material having water absorption produced according to the present invention.

  (3) Water retention material: The hydrophilized polyolefin nonwoven fabric produced by the present invention is useful as a water retention material for supplying water to plants. The material shape as a water retention material for this purpose may be a woven fabric, a nonwoven fabric, or a fiber having no cloth shape, or a cut fibrous waste. About 10-500 micrometers is easy to use the diameter of a constituent fiber. The hydrophilic polyolefin nonwoven fabric and film are used for battery separators having excellent alkali resistance, acid resistance, and oxidation resistance.

  (4) Medical products, hygiene products, cosmetic products or instruments: Means various types of disposable products. Illustrative examples include diapers, sanitary products, bandages, gauze, sanitary napkins, disinfecting affixing cloths and tapes, other medical supplies, and various cosmetics such as cleansing applications, face-wash packs, and pads.

  Disposable diapers or sanitary products contain a water-absorbing material made from pulp, starch, acrylic polymer, etc. on the inside, and the outside is covered with a water-repellent polyolefin nonwoven fabric so that it does not penetrate urine, moisture, blood, etc. It has been broken. Moisture discharged from the body permeates the inner hydrophilic nonwoven fabric and is absorbed by the inner water-absorbing material. Hydrophilic polyolefin nonwoven fabric is the most desirable material as a material that is resistant to moisture and difficult to tear. However, the hydrophilization of the hydrophilized non-woven fabric used on the inside is only impregnated with a surfactant or water-soluble treatment agent that easily drops with water. For this reason, the hydrophilicity is not durable and is easily washed away with water. The effect of surfactants on the skin is also a problem. Therefore, an easy and durable hydrophilic technology is desired. The water-absorbing / water-retaining polyolefin material obtained by the hydrophilization technique of the present invention is an optimal material as a disposable diaper or a cloth for inner sewing of a sanitary product. Further, the polymer material having high water absorption according to the present invention is also used as a water-absorbing material in disposable diapers or sanitary products. Light weight, high strength, safety and withstand repeated use. The hydrophilic or water-absorbing material obtained by the present invention is lightweight and high in strength and can be impregnated with detergents, chemicals, adhesives, etc., so gauze, wiping textiles, pasting disinfecting cloth / tape, etc. Suitable for cosmetic materials. When used as a disposable medical article, hygiene article, or cosmetic article, the material shape is preferably a woven or non-woven fabric, and the basis weight and thickness may be appropriately selected. However, the diameter of the constituent fiber of the woven or non-woven fabric is easy to use about 1 to 500 μm. Further, for medical products, hygiene products, and cosmetic products, it is possible to increase the hydrophilicity of natural rubber or synthetic rubber sponges and other materials, and to improve the adhesion and comfort of chemicals and cosmetics.

  (5) Internal materials such as clothing, beds, and futons: The hydrophilic or water-absorbing polymer material obtained by the present invention is lightweight and high-strength, controls water absorption, and is used for clothing textiles, beds, Suitable for internal materials such as futons.

  (6) Filter material: The filter material made of a porous film made of a hydrophobic material such as polyolefin, polysulfone, polyester, etc. has higher strength than paper filter material, but is poor in hydrophilicity. Not suitable for filtration of aqueous solutions. Currently, surfactants and water-soluble polymers are applied to cope with these problems, but these hydrophilized parts are eluted during filtration and lack durability. A durable, water-absorbing filter medium can be obtained by subjecting the filter medium made of such a hydrophobic material to the hydrophilization treatment of the present invention.

  (7) Microbial medium material: The water-absorbing material obtained by the present invention is excellent in water absorption, strength, and microbial reproduction, and is optimal as a material for microbial medium. The shape of the material for the microbial medium may be a woven fabric, a non-woven fabric, a fiber having no cloth shape, or a cut fibrous waste. About 10-500 micrometers is easy to use the diameter of a constituent fiber.

  (8) Orthodontic member: The adhesion of the polymer material can be improved by the treatment method of the present invention. Since it can be used for various materials that require adhesiveness, composite materials, and reinforcing fibers to be blended with fiber-reinforced plastics, the adhesiveness between plastic orthodontic members (eg, brackets) and teeth can be improved. The orthodontic bracket is a pedestal (size example: dimensions 2.23 × 3.0 × 3.8 mm, weight = about 31 mg / piece) made of a polymer material (such as plastic or a composite material made of plastic and reinforcing fibers). ) Orthodontic appliance reinforced with metal (slot) such as aluminum or gold. The shape of the portion to be bonded to the tooth surface may be either a flat die or a die provided with an undercut in the base portion (so-called mechanical base structure). (2) Dentures for dental treatment and other members: Dentures for dental treatment and other members molded into various shapes made of acrylic resin, polypropylene resin, cyclic olefin polymer, ceramic material and the like.

Materials constituting the dental treatment material are ceramic materials, polymer materials: nylon, polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polystyrene (PST), mixed sample of PP and PE (P / E) ), Cyclic olefin polymers or copolymers thereof, such as TOPAS, ARTON, ZEONEX, ZEONOR, etc. under the trade names. The device of the present invention can preferably improve the polymeric material for the bracket for the ROTH type mandibular anterior teeth (AN). The ROTH type bracket means a bracket having a torque proposed by Dr. ROTH (a tilt angle in the front-rear direction with respect to the teeth) and an angulation (a tilt angle in the left-right direction with respect to the teeth).

(10) Medical equipment material parts:
Means artificial blood vessels, artificial organs, artificial joints, tubular, thread-like, plate-like polymer material parts. The hydrophilicity of these materials can be improved to improve medical compatibility. Examples thereof include those used in contact with the human body or human tissue (catheter, drainage device), body fluid absorbing materials, contact lenses, synthetic fiber bandages, gauze infusion devices, and the like.

  (11) Polymer material composite material: It can be used for a polymer material composite material having improved strength by improving the adhesion of the reinforcing fiber to be blended with the composite material and the fiber reinforced plastic.

  (12) Synthetic paper: Synthetic paper made of a polyolefin such as polyethylene and polypropylene, or a polymer material such as polyester is used as an alternative to paper by adding air bubbles and fillers to give whiteness. By making the surface hydrophilic according to the present invention, it is possible to improve adhesion and printability.

  (13) Materials with improved adhesiveness: In addition to improving the adhesiveness of orthodontic members and reinforcing fibers for composite materials, improving the adhesiveness of various polymer films and molded products, the same or different Adhesion with the material can be improved.

  (14) Other uses of hydrophilic film: According to the present invention, high hydrophilicity can be imparted to a polymer film such as polyolefin or polyester. For example, a water-absorbing polyester film is excellent in adhesiveness and easily wetted with water, so that an anti-fogging effect can be obtained by sticking to glass or a mirror.

  (15) Battery separator use: The separator of the present invention not only has high physical strength, but chemically has excellent acid resistance and alkali resistance, has a high absorption rate of various electrolytes, and has excellent liquid retention. . Further, by selecting the basis weight value of the material, it is possible to suppress the air permeability. Therefore, it can be used for both primary batteries and secondary batteries. Regardless of the shape of cylinders, buttons, flats, squares, etc., secondary batteries must be open or sealed. It doesn't matter. More specifically, examples of the primary battery include an alkaline manganese battery using an alkaline electrolyte, a mercury battery, a silver oxide battery, an air battery, a silver chloride battery, a lithium battery, and a manganese battery using an acidic electrolyte. It is done. Secondary batteries include alkaline storage batteries that use alkaline electrolyte (Edison batteries), nickel-cadmium batteries (Jungner batteries), nickel-hydrogen batteries, silver-zinc batteries, silver-cadmium batteries, nickel-zinc batteries, nickel- Examples include iron batteries and lead-acid batteries using an acidic electrolyte. Conventional batteries using paper separators can be used instead of paper separators.

(A) Material containing polymer material (1) Polymer materials used in Examples and Comparative Examples are as follows.
Polypropylene nonwoven fabric (thickness 150 μm, basis weight 50 g / cm 2), polypropylene / polyethylene mixed nonwoven fabric (thickness 300 μm, basis weight 76 g / cm 2),
Polyethylene terephthalate (polyester) nonwoven fabric (thickness 180 μm, basis weight 57 g / cm 2), glass fiber / polyethylene mixed nonwoven fabric (thickness 100 μm, basis weight 213 g / cm 2), carbon fiber (thickness 150 μm, basis weight 50 g / cm 2), wool fiber ( Thickness 500 μm, basis weight 188 g / cm 2, polypropylene film (thickness 20 μm, basis weight 17 g / cm 2), polyethylene terephthalate film (thickness 60 μm, basis weight 72 g / cm 2), HMPE plate (thickness 700 μm, basis weight 467 g / cm 2), porous Polysulfone film (thickness: 179 μm, basis weight 50 g / cm 2)

  No operation was performed to remove the antioxidant, stabilizer and other additives contained in the polymer material. The abbreviations have the following meanings. PP: polypropylene, PE: polyethylene, PET: polyethylene terephthalate, PSU: polysulfone, PP / PE: a mixture of polypropylene and polyethylene, HMPE: ultrahigh molecular weight polyethylene d.

(2) Orthodontic member: Specific examples of the polymer material processed into the orthodontic bracket are as follows. Bonding surface is flat: Polypropylene bracket (Polypropylene K5016 from Chisso Corporation), Nylon 12 bracket (Grillamide TR55 from Swiss MMS), Nylon 6 bracket (Toyobo's transparent nylon T714E), Polycarbonate bracket ( GE plastic lexan), glass fiber reinforced polyethylene terephthalate (Toyobo Co., Ltd. EMC335), glass fiber reinforced polycarbonate bracket (ORMCO's SPIRIT bracket (with glass filler)). Adhesive surface is flat or mechanical base: ZEONEX bracket (manufactured by Chisso Corp., cyclic olefin polymer), Arton bracket (manufactured by JSR Corp., grade G, F, D, FX, cyclic olefin co-polymer) Combined), Topas bracket (Mitsui Chemicals Co., Ltd., cyclic olefin copolymer), Zeonoa bracket (Chiso Co., Ltd. 1020R, cyclic olefin polymer). Bonding surface is mechanical base: Glass fiber reinforced polycarbonate bracket 2 (Sankin Kogyo Co., Ltd. clear bracket).

(3) Writing instrument members for stationery and cosmetics 1) PP collector with cross-sectional comb shape: temporary ink reservoir with cross-sectional comb shape made of a molded product made of polypropylene, outer diameter 6 to 8 mm, inner diameter 2 to 4 mm, mass 0. 61 g, length 28 mm. It is abbreviated as PP collector 1.
2) Single-piece PP collector: a disk made of polypropylene and having a hole in the center, with embossing on the surface (40 protrusions per piece). Several of these are stacked to form a temporary ink reservoir. The gap between the discs is defined by the height of the emboss. Outer diameter 19.8 mm, inner diameter 5.0 mm, thickness 0.188 mm, weight 0.055 g. It is abbreviated as PP collector 2.
3) Cross-section comb-shaped ABS collector: cross-section comb-shaped temporary ink reservoir made of ABS resin (acrylonitrile, butadiene, styrene copolymer), outer diameter 6-8 mm, inner diameter 2-4 mm , Mass 0.79g, length 28mm. Abbreviated as ABS collector 1.
4) Single-sheet shaped ABS collector: a disc made of an ABS resin molded body with a hole in the center and embossed on the surface (40 protrusions per piece). Several of these are stacked to form a temporary ink reservoir. The gap between the discs is defined by the height of the emboss. Outer diameter 19.8 mm, inner diameter 5.0 mm, thickness 0.188 mm, mass 0.061 g. Abbreviated as ABS collector 2.
5) Ink tank shaft: made of polypropylene, outer diameter 7 mm (tip) to 10 mm (outlet), inner diameter 2 mm (tip) to 8 mm (outlet), mass 2.2 g, length 87 mm.
6) Pen core 1: Procky fine pen core under the trade name, made of polyethylene terephthalate (PET), length 27.0 mm, outer diameter 2 mm, mass 0.0627 g, made by bundling and fusing fibrous PET .
7) Pen core 2: made of polyethylene terephthalate, length 37.0 mm, outer diameter 4 mm, mass 0.185 g. It was made by bundling and fusing fibrous PET.
8) Relay core: made of polyethylene terephthalate, length 22.5 mm, outer diameter 1.8 mm, mass 0.0505 g. It was made by bundling and fusing fibrous PET.

9) Panicle 1: Made of polybutylene terephthalate, length 150 mm, outer diameter (root) 2.0 mm, mass 0.0548 g. The head is a writing part of a brush pen and performs writing while maintaining the state of containing ink and ink. Alternatively, it can be used as a makeup brush. Since it consists of a bundle of thin filaments of synthetic polymer, it has the property of absorbing water, water-based inks, and cosmetic agents by capillary action even if the surface of each fiber is not wet.
10) Neck 2: Made of nylon 66, length 250 mm, outer diameter (base) 5 mm, mass 0.198 g.
11) Filling: A structure in which 0.397 g of polyethylene terephthalate fiber (thickness 2d) is wrapped with a cylinder of polypropylene film (0.074 g), length 78.0 mm, outer diameter 7 mm.
12) Ink occlusion body sponge: polyurethane sponge, weight 16.0 mg, thickness 2.0 mm, shape: trapezoid (upper base 120 mm, lower base 170 mm, height 1905 mm).

(B) Reagents (1) Polyvinyl alcohol (PVA): Wako Pure Chemical Industries, Ltd., product number 160-11485 (average polymerization degree = 1500-1800)
(2) Sodium carboxymethyl cellulose (CMC): Wako Pure Chemical Industries, Ltd., product number 039-01355
(3) Acrylic acid: Wako Pure Chemical Industries, Ltd., product number 011-00776
(4) Methacrylic acid: Wako Pure Chemical Industries, Ltd., product number 138-10805
(5) Methyl methacrylate: manufactured by Wako Pure Chemical Industries, Ltd., product number 139-02726
(6) Sodium persulfate (SPS): Wako Pure Chemical Industries, Ltd., product number 195-04985
(7) Potassium persulfate (KPS): Wako Pure Chemical Industries, Ltd., product number 162-04235
(8) 2,2′-azobisisobutyronitrile (AIBN): manufactured by Wako Pure Chemical Industries, Ltd., product number 019-04932
(9) Dicerium ammonium nitrate (IV) (CAN): Wako Pure Chemical Industries, Ltd., product number 036-01742
(10) Benzophenone: manufactured by Wako Pure Chemical Industries, Ltd., product number 023-01072
(11) Methanol: Wako Pure Chemical Industries, Ltd., product number 136-09475
(12) Sodium hydroxide: manufactured by Wako Pure Chemical Industries, Ltd., product number 194-02135
(13) Hydrochloric acid: Wako Pure Chemical Industries, Ltd., product number 080-01066
(14) Toluene: Wako Pure Chemical Industries, Ltd., product number 204-01866, this liquid itself was used (impregnating agent A).
(15) Sodium dodecylbenzenesulfonate (DBS): Tokyo Chemical Industry Co., Ltd., product number D1238, used as a surfactant.
(16) Decahydronaphthalene (cis, trans mixture): Wako Pure Chemical Industries, Ltd., product number 048-0066, this liquid itself was used (impregnating agent B).
(17) Orthohydroxybiphenyl (OHB): manufactured by Wako Pure Chemical Industries, Ltd., product B number 080-01402, 1 g of orthohydroxybiphenyl and 0.2 g of sodium hydroxide, surfactant (sodium dodecylbenzenesulfonate) 0.2 g Was used as a solution obtained by mixing 200 ml of water (impregnating agent C).
Alternatively, a solution obtained by dissolving 0.5 g of orthohydroxybiphenyl in 300 ml of methanol was used as a carrier dispersed in water (impregnating agent D).
(18) Sodium salicylate (SS): manufactured by Wako Pure Chemical Industries, Ltd., product number 195-O3145, 1 g of sodium salicylate dissolved in 200 ml of water, and water using a solution obtained by mixing 0.5 ml of 10% hydrochloric acid (Impregnant E).
(19) Diphenyl (DP): Wako Pure Chemical Industries, Ltd., product number 040-18412. A solution obtained by mixing 2.5 g of diphenyl and 0.2 g of a surfactant (sodium dodecylbenzenesulfonate) in 200 ml of water was used (impregnating agent F).
(20) Carnant (trade name, manufactured by Toho Chemical Co., Ltd.): Carrier for dyeing polyester-based synthetic fibers, blended product of aromatic ether-based anionic active agent. Used by dispersing in water (carrier 1).
(21) Carrier TW200 (trade name, manufactured by Nikka Chemical Co., Ltd.): Polyester / wool blended synthetic fiber dyeing carrier, methylnaphthalene and other blended products, dispersed in water (carrier 2).

(C) Ozone treatment: Put the test piece into a 2L or 10L hard glass container (with gas inlet and outlet) and 1g of ozone generated from an ozone generator (OS-1N manufactured by Mitsubishi Electric Corporation). / H, oxygen containing ozone at a concentration of 20 g / m 3 was blown in at a flow rate of 800 ml / min for 20 to 120 minutes. Next, oxygen not containing ozone was blown for 10 minutes. The concentration of ozone was determined by iodometric titration. The degree of oxidation is obtained by shaving the surface member of the treated test piece, measuring the infrared absorption spectrum, and changing the absorbance of the absorption peak (carbonyl group absorption) near 1710 cm −1 and the ratio of this absorbance to the absorbance at 973 cm −1. Judged more.

(D) Plasma treatment: A test piece (cloth, film, etc.) was placed between the electrodes in the reaction vessel of the plasma treatment apparatus (Yamato PR500). After reducing the pressure in the reaction vessel to 0.27 Pa, a mixture of argon gas and oxygen gas (volume ratio 1: 1) was introduced until the pressure reached 5.6 Pa. Glow discharge was performed mainly for 30 seconds to 3 minutes at an oscillation frequency of 13.56 MHz with a supplied power value between 40 W and 100 W. After discharge, gas introduction was stopped and the pressure was returned to normal pressure, and then the treated test piece was taken out. The degree of treatment was judged by the decrease in the contact angle of water with the film.

(E) Ultraviolet irradiation treatment: In the case of activation treatment, the sample itself was directly irradiated with a high-pressure mercury lamp (Toshiba high-pressure mercury lamp H400P) from a distance of 10 cm.
In the case of grafting, the reaction mixture was placed in a Pyrex (registered trademark) glass reaction vessel, brought to a temperature of 10 to 70 ° C., and irradiated with a high-pressure mercury lamp (Toshiba high-pressure mercury lamp H400P) from a distance of 20 cm. The reaction tube revolved around the lamp while rotating so that the light was uniformly irradiated. By reaction mixture is meant a solution containing initiator, monomers and their solvents, or a gas such as air or nitrogen containing monomer vapors.

(F) Evaluation of water absorption: Measurement of water absorption rate of nonwoven fabric, woven fabric, fiber bundle, film, plate, porous film:
(1) Water absorption: Put a test piece (size 10 cm × 10 cm) in a beaker containing water and gently agitate with a glass rod for about 1 minute. Next, the test piece is taken out and hung for 3 minutes (water drops do not drop). The weight of the dried test piece was subtracted from the weight of the water-absorbed test piece to obtain an increased weight (water absorption amount), and the percentage with respect to the weight of the dry test piece was defined as the water absorption rate (%).
Water absorption rate (%) = (Water absorption amount / weight of test piece when dried) × 100

(2) Water absorption rate: 1 cm of the lower end of a test piece having a width of 1.5 cm was immersed in water, and the distance (unit: cm / min) of the rise of water per minute was measured.

(G) Measurement of contact angle of water: A contact angle measuring device (Kyowa Interface Science Co., Ltd. CA-X) was used. At 20 ° C., a drop of water having a diameter of about 1 mm from the syringe was dropped onto the surface of the test piece, and was calculated from the size of the image magnified by the video camera.

(H) Washing resistance test: The test piece was placed in a weakly alkaline fatty acid sodium soap (trade name: Lion Powder Soap manufactured by Lion Corporation) 0.4% aqueous solution at a bath ratio of 1: 250 and stirred for 5 minutes. , Boiling cleaning was performed. Thereafter, it was sufficiently washed with water and dried. The water absorption rate, water uptake speed, and tensile strength were measured and compared with those before washing.

(I) Tensile strength test: A test piece is cut into a 1.5 cm × 7 cm rectangle, and 1 cm from both ends is fixed to a clamp of a tensile tester (SV55-0-20M, Imada Seisakusho Co., Ltd.), and the grip interval is 5 cm. As a result, it was pulled at a pulling speed of 100 mm / min. Measurements were made in each direction of the vertical and horizontal eyes. In each example, only the longitudinal direction was shown.

(J) Adhesive peel strength test (1) In the case of a film: A test piece is cut into a size of 30 mm (longitudinal direction) × 5 mm, 0.1 g of adhesive is applied to a 5 mm × 5 mm portion at one end, and a veneer plate (thickness) 2mm, size 20mm x 10mm) or sticky note ((thickness 0.2mm, size 20mm x 10mm), and put a 500g weight between polyethylene films for 12 hours. Unbonded part of plywood 10mm And 10 mm of one end where the film is not bonded was sandwiched between clamps of a tensile tester (AGS-H manufactured by Shimadzu Corporation) and pulled at a pulling speed of 30 mm / min, and the energy required for peeling the bonded portion (adhesive peeling energy) was determined. In order to standardize the bonding conditions, the relative value was determined by setting the adhesive peeling energy of the untreated material similarly performed to 1.0. For plywood, poly cyanoacrylate: For sticky note and (Aron Alpha Toagosei Co., Ltd.), paper applications adhesive for stationery (trade name: Kokuyo Co., Ltd., split) is.

(2) In the case of orthodontic member: about 0.01 g of adhesive is applied to the adhesive surface of the treated or untreated orthodontic bracket, attached to a ceramic plate (size 20 mm x 10 mm), and a looped wire is attached. Attach and fix the unbonded part of the ceramic plate to the lower clamp of the tensile tester (manufactured by Shimadzu Corporation, SV55-0-20M) and fix the wire to the upper clamp at a pulling speed of 110 mm / min. Obtain the load applied before pulling and peeling the bonded part. In order to standardize the bonding conditions, the relative value was determined with the peel strength of the untreated material performed at the same time being 1.0. Polymerizable methacrylic resin-based adhesive (used by mixing methyl methacrylate monomer, polymer, polymerization catalyst, etc.): Trade name Superbond (Sun Medical Co., Ltd.) or homemade product was used.
(3) In the case of an ink absorber sponge: The ink absorber sponge was fixed at a portion of 5 mm from both ends to a clamp of a tensile tester (AGS-H manufactured by Shimadzu Corporation) and pulled at a pulling speed of 100 mm / min.

FIG. 1 shows an outline of the apparatus shown in claim 1, and the material delivery apparatus is a partial apparatus for delivering a polymer material to be processed to a cleaning apparatus. When the material is in a form that can be wound up, such as a cloth, a film, or a sheet sponge, the material is wound or folded, and is sent out by a conveyor. Depending on the transfer mechanism, it is roughly classified into a roller type, a lattice type, and a roller mat type.
If the material is a product with a unique shape, such as writing utensils, cosmetic puffs, orthodontic materials, etc., a specific number of materials placed in a bag-like net, holding a material made of silicon rubber The sample embedded in the body is sent out as a sample. In addition, discontinuous plates, bars, fiber materials, and the like are appropriately collected and sent to a cleaning device.
The next cleaning device is a device to clean the material with a volatile water-soluble organic solvent such as methanol or ethanol, or a mixture of these with water, and remove the oil from the material. It has a structure with equipment. A structure having an apparatus that allows the solvent to be used to be distilled and reused after passing through the filtering agent is desirable, but after being used to some extent, it may be discharged from the discharge section and reused. Cover the tank containing the solvent to prevent it from leaking. The impregnation treatment / dryer is a partial device that dries a material in an impregnating agent and then appropriately dries. If the material is highly absorbent, such as a cloth or sponge, a mangle squeezer or a centrifugal dehydrator can be provided to streamline drying. The activation treatment device is made of a material made of non-corrosive oxidation-resistant material, such as a roller, etc., which is connected to a plasma treatment device, a high-pressure discharge device, a corona discharge device, an ultraviolet irradiation device, or an ozone generator. It consists of a device that activates the surface of the material by guiding it to a tank (eg glass, ceramic, Teflon (registered trademark), or made of special stainless steel). The activated material is then introduced into the grafting device. Grafting equipment consists of a method in which a material is immersed in a solution of a monomer and a catalyst or an initiator at a predetermined temperature to perform grafting on the surface, a method in which the volatile monomer is exposed to heated steam, a monomer and It consists of a general graft polymerization apparatus, such as immersing the material in a catalyst or initiator solution and irradiating with ultraviolet rays for a predetermined time. The next washing / drying apparatus is a partial apparatus in which the monomer is dissolved, washed with a solvent that does not dissolve the material, dehydrated, and dried. Then, it introduce | transduces into the apparatus which collects material with the apparatus which collects material in winding-up or folding form.

FIG. 2 shows an outline of the apparatus shown in claim 2 and is immersed in a hydrophilic polymer solution (including an initiator, a catalyst, and a plurality of solvents) instead of the grafting apparatus in the apparatus of FIG. , Mainly washed with water, dehydrated, dried, and wound up by a winding device or the like.

FIG. 3 shows an outline of the apparatus shown in claim 3. The material is treated with a hydrophilic polymer solution treatment apparatus similar to that shown in FIG. 2, washed and dehydrated, and then the grafting apparatus of FIG. Grafting is carried out with the same material, and after washing and drying, it is wound up by a winding device or the like.

FIG. 4 shows an apparatus obtained by removing the impregnation treatment / dryer apparatus from the apparatus shown in claim 1 (FIG. 1).

FIG. 5 shows an apparatus obtained by removing the impregnation treatment / dryer apparatus from the apparatus shown in claim 2 (FIG. 2).

  FIG. 6 shows an apparatus obtained by removing the impregnation treatment / dryer apparatus from the apparatus shown in claim 3 (FIG. 3).

The surface-modified polyethylene plate, polypropylene film, polyester film, and various orthodontic brackets by the apparatus 1 were grafted with vinyl monomers, and effective adhesion improving materials were obtained for each. The adhesive strength of these materials was 10 to 1000 times that of the untreated material. Moreover, as a result of improving the hydrophilicity of the collector for polypropylene-based writing instruments and the writing instrument members made of other materials, a material that easily gets wet with water was obtained.

The modified polypropylene non-woven fabric, urethane or natural rubber sponge, and brush-type writing instrument member were made hydrophilic by the apparatus 2, and an effective material was obtained. In addition, a polypropylene non-woven fabric was made hydrophilic for a battery separator, and a suitable separator material was obtained. In addition, materials for wiping and cleaning, filter media (polyethylene film and polysulfone film), water-absorbing materials, water-retaining materials, synthetic paper, medical supplies, hygiene products or instruments, cosmetics or instruments, medical equipment materials, microbial medium materials As a result, a non-woven fabric such as polypropylene, polyethylene and polyester was subjected to a modification treatment, and an effective water-absorbing material was obtained.

Among the modified treatment materials by the apparatus 3, the polypropylene or polyethylene plate, film, and other molded bodies that are difficult to treat were treated to obtain an effective adhesion improving material.

A polypropylene nonwoven fabric for a modified battery separator and a synthetic polymer filter material were produced by the apparatus 4, and useful materials were obtained. For batteries using a polypropylene nonwoven fabric for battery separators, an effective charge / discharge curve was measured.

The reforming treatment wiping cleaning material, the water absorbing material, the water retaining material, and the microorganism culturing material by the apparatus 5 were hydrophilized, and an effective material was obtained.

The polypropylene nonwoven fabric for modified battery separator, ultrahigh molecular weight polyethylene, collector for writing instruments, etc., were subjected to a hydrophilic treatment, and effective materials were obtained respectively.

As a result, an effective modified polymer material could be rationally produced by the modification treatment apparatus according to the present invention. It was particularly effective in improving the water absorption of polyolefin and polyester nonwoven fabrics. Moreover, it was effective in making the writing instrument member hydrophilic and modifying plastic orthodontic brackets, ultrahigh molecular weight polyethylene, and polyurethane rubber. Moreover, the use of the battery separator obtained by the apparatus of the present invention was also highly durable and effective.

It is the schematic of the apparatus for achieving Claim 1 (Example 1). It is the schematic of the apparatus for achieving Claim 2 (Example 2). (Example 3) which is the schematic of the apparatus for achieving Claim 3. (Example 4) which is the schematic of the apparatus for achieving Claim 4. (Example 5) which is the schematic of the apparatus for achieving Claim 5. (Example 6) which is the schematic of the apparatus for achieving Claim 6.

Claims (14)

The surface of the polymer material is contacted with (1) a compound impregnated with the polymer material, and the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40% by weight (vs. the polymer material) ) And impregnation within the range of the material, the shape of the material is not substantially changed, (2) an activation treatment step for introducing a carbonyl group, and (3) a monomer grafting step in this order. An apparatus for modifying a polymer material, characterized in that: The surface of the polymer material is contacted with (1) a compound impregnated with the polymer material, and the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40% by weight (vs. the polymer material) ) And impregnating within the range, the shape of the material is not substantially changed, (2) an activation treatment step for introducing a carbonyl group, and (3) a treatment with a hydrophilic polymer in this order. An apparatus for modifying a polymer material, characterized in that: The surface of the polymer material is contacted with (1) a compound impregnated with the polymer material, and the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40% by weight (vs. the polymer material) ) Impregnation treatment within a range of substantially no change in the shape of the material, (2) activation treatment step for introducing a carbonyl group, (3) treatment with a hydrophilic polymer, and (4) single An apparatus for modifying a polymer material, wherein the polymer material is processed in this order by a step of grafting a polymer. Modification of the polymer material characterized in that the surface of the polymer material is treated in this order by (1) an activation treatment step for introducing a carbonyl group, and (2) a step of grafting the monomer. Device to do. The surface of the polymer material is modified in this order by (1) an activation treatment step for introducing a carbonyl group, and (2) a treatment step with a hydrophilic polymer. Device to do. The surface of the polymer material is treated in this order by (1) an activation treatment step for introducing a carbonyl group, (2) a treatment step with a hydrophilic polymer, and (3) a step of grafting the monomer. An apparatus for modifying a polymer material characterized by the above. The polymer material is a molded body or other material selected from the group consisting of fibers, woven fabrics, knitted fabrics, nonwoven fabrics, plates, bars, films, sheets, porous films and sheets, and members or products molded into a predetermined shape. 4. The apparatus for modifying a polymer material according to claim 1, wherein the apparatus is a composite material. The apparatus for modifying a polymer material according to any one of claims 1 to 6, wherein the polymer material contains at least one of an antioxidant and a stabilizer. 9. The apparatus for modifying a polymer material according to any one of claims 1 to 6 and 7 to 8, wherein the impregnation treatment is performed at a temperature below the melting point or softening point of the polymer material. . 10. The activation process according to claim 1, wherein the activation process is at least one process selected from the group consisting of an ozone process, a plasma process, an ultraviolet irradiation process, a corona discharge process, and a high-pressure discharge process. An apparatus for modifying the polymeric material as described. A compound in which the monomer has a carbon-carbon double bond, and acrylic acid, methacrylic acid, vinyl acetic acid, 2-butenoic acid, ethylene sulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, It must be at least one monomer selected from the group consisting of vinylcarbazole, maleic anhydride, pyromellitic anhydride, or a mixture of at least one monomer selected from these groups and another vinyl monomer. An apparatus for performing surface modification of a polymer material according to any one of claims 1, 3, 4, 6, and 7 to 10. The hydrophilic polymer is polyvinyl alcohol, carboxymethyl cellulose, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyalkylene glycol, starch, glucomannan, fibroin, sericin, The high protein according to any one of claims 2, 3, 5, 6, and 7 to 11, which is at least one polymer compound selected from the group consisting of agar, protein in egg white, and sodium alginate. Equipment for surface modification of molecular materials. The method of grafting the monomer may be any reaction of gas phase, liquid phase, or solid phase, and (1) a method performed in the presence of a catalyst or an initiator, and (2) presence of a catalyst or an initiator. A method of heating under or in the absence of, or (3) a method of irradiating ultraviolet rays in the presence or absence of a catalyst or an initiator or a photosensitizer, characterized by one or a plurality of methods An apparatus for modifying a polymer material according to any one of claims 1, 3, 4, 6, and 7 to 11. A wiping and cleaning material, a filtering material, a water-absorbing material, a water-retaining material, a synthetic paper, a medical article, and a hygiene, comprising the polymer material modified by the method for modifying a polymer material according to claim 1. Articles or instruments, cosmetics or instruments, medical device materials, microorganism medium materials, writing instrument members, orthodontic members, battery separators, and devices for making batteries using the same.

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