JP2011208133A - Medical use instrument - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer material which is not accompanied by the strength deterioration of a material, and excels in durability, and to which water absorptivity, hydrophilicity, adhesion, printability, antistatic property or the like is given to be modified.SOLUTION: The modified polymer material is obtained by a modifying method. The modifying method is characterized by a step (1) of treating a polymer material by a solvent or impregnating treatment, a step (2) of activating the polymer material, a step (3) of treating the polymer material with a polymer solution under the presence of a catalyst or an initiator, a step (4) of carrying out grafting a monomer on the polymer material, and a step (5) of cleaning the grafted polymer material, in the order.

Description

The present invention relates to a polymer material having improved water absorption, adhesiveness, paintability, printability, and chargeability without reducing the strength of the polymer material, its use, a method for modifying the polymer material, and Containing composite materials.

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. Various surfaces such as ozone treatment, plasma treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, corona discharge treatment, sandblast treatment, flame treatment, etc. have been conventionally used to improve the hydrophilicity, adhesiveness, printability and chargeability of these materials. Attempts have been made to apply an activation treatment. However, even if these surface treatments are performed, the polyolefin material does not provide water absorption enough to absorb water several times its own weight. Moreover, practical improvement was not made | formed also about the hydrophilic property, adhesiveness, coating property, and printability of polyolefin material. For this reason, various attempts have been made to modify polymer materials such as polypropylene. For example, a method for improving the plating property, paintability, adhesiveness, and printability by applying ozone oxidation treatment has been studied (see Patent Document 1). However, if the desired surface characteristics are to be imparted only by ozone treatment, it is necessary to make the ozone treatment severe, and there is a problem that the strength of the object to be treated is remarkably lowered and it cannot be put to practical use. Further, water absorption cannot be sufficiently imparted only by ozone oxidation treatment.

In addition, 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 ( Patent Document 2). 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 of imparting hydrophilicity by treating a nonwoven fabric made of polyolefin fibers with a hydrophilic resin in the presence of a persulfate has been proposed (see Patent Document 3). In this method, the nonwoven fabric could be given hydrophilicity to a practical level, but the hydrophilic durability was not always sufficient. Further, when a film or a molded product other than the nonwoven fabric is processed, sufficient hydrophilicity cannot be imparted, or adhesiveness, paintability, printability, and chargeability with an adhesive cannot be improved. For example, hydrophilicity is lost when heated with a detergent.

A method of imparting hydrophilicity by coating a nonwoven fabric with polyvinyl alcohol is also known (see Patent Document 4). However, although the obtained coating has a high hydrophilicity, it is a simple coating, so that there is a problem that the hydrophilic durability is not sufficient. Further, for example, when used as a battery separator, the coating alone has a drawback that it causes contraction in the battery tank, and the battery separator causes a short circuit problem.
Furthermore, with regard to difficult-to-process polymers other than polyolefin, such as silicon resin, fluororesin, polyamide, polyester, and polyurethane, the above-mentioned methods have been used for hydrophilicity, adhesiveness, paintability, printability, and chargeability. No practical improvements were made.

In addition, the inventor previously improved the dyeability by first activating the surface of the polymer material, and then graft-polymerizing monomers such as acrylamide, or further transferring the amide group of the grafted compound to Hofmann. A method for modifying the surface of the polymer material was proposed (see Patent Document 5).

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 (1) Impregnation treatment step, (2) Activation treatment step, (3) Hydrophilic polymer treatment step, and (4) Monomer grafting step combination method (See Patent Document 6)).
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.

Japanese Patent Publication No. 3-103448 Japanese Patent Laid-Open No. 11-7937 JP-A-11-67183 JP-A-1-248460 JP-A-8-109228 JP 2002-201297 A

The technical demands as described above exist not only for polyolefins but also for other polymer materials having superior surface activity. It may be required to modify the original surface properties of the polymer to give the desired surface properties. For example, for difficult-to-process materials such as polypropylene material, polyethylene material, ultrahigh molecular weight polyethylene material, polyester material, polycarbonate material, silicon resin, fluororesin, polyimide, etc. Although bonding is possible, there was a limit to the bonding strength. In addition, when these materials are coated with water-based or oil-based paints, in order to obtain a result (full scale 100/100) that the paint film does not peel at all in the peel test (cross cut test), the influence of the components of the material is required. There was a case.

The present invention aims to overcome the above-mentioned drawbacks, and provides a method for modifying the surface of a polymer material which is not accompanied by a decrease in the strength of the material and has excellent durability, and a polymer material modified by the modification method. It is to provide. In particular, it is intended to impart durable hydrophilicity, adhesiveness, paintability and chargeability to difficult-to-process polymer materials. Further, the present invention is a medical / hygiene / cosmetic product made of the material thus modified, that is, disposable sanitary products, gauze, paste for disinfection, various cleansing applications / facial cleansing packs, water absorbent materials for napkins, Water-retaining materials such as agricultural and dry land greening materials, microbial medium materials, synthetic paper, filter media, wiping and cleaning materials, orthodontic brackets, medical device materials (infusion devices for infusions and infusions, cannulae, artificial organs) , Joints, various tubular, thread-like, plate-like molded products), polymer materials with durable hydrophilicity, adhesiveness, paintability, chargeability, and composite materials with polymer materials, etc. For the purpose. Giving adhesion means enabling adhesion using an adhesive, adhesion using a solvent without using an adhesive, and adhesion of an adhesive tape.
(Improvement of printability) Even if conventional surface modification treatment is applied to polyolefin resin, polycarbonate resin, silicone resin, acrylic resin, polyester resin, fluororesin, etc., which are difficult to modify the surface, durability I could not achieve a certain printing. Durability means that 100/100 is obtained by a cross-cut cellophane tape peeling test, and further, printing is not peeled off by a water resistance test immersed in warm water at 40 ° C. for one week. It is an object of the present invention to produce a surface-modified polymer material so as to enable durable printing with water-based ink, oil-based ink, water-based paint, oil-based paint, and UV ink.

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 conducted solvent treatment, impregnation treatment, activation treatment, treatment with a polymer solution, The inventors have found that it is effective to combine grafting and washing, and have completed the present invention.

That is, the present invention comprises (1) an activation treatment, (2) a treatment with a polymer solution in the presence of a catalyst or an initiator, (3) a monomer grafting step, and (4) The present invention relates to a modified polymer material obtained by a modification method characterized by processing in the order of washing steps, a coating property, a printability, a chargeable polymer material, and a modification method.

Alternatively, in the present invention, the polymer material is treated in the order of (1) an activation treatment, (2) a treatment with a polymer solution in the presence of a catalyst or an initiator, and (3) a washing step. The present invention relates to a modified polymer material having adhesion and paintability obtained by a modification method characterized by the above and a modification method.

Alternatively, the present invention provides (1) a solvent treatment step, (2) an activation treatment step, (3) a treatment with a polymer solution in the presence of a catalyst or an initiator, and (4) washing. The present invention relates to a polymer material having a modified adhesive property, paintability, printability, and chargeability obtained by a modification method characterized by processing in the order of the steps and a modification method.

Alternatively, in the present invention, the polymer material is contacted with (1) a compound impregnating the polymer material, and the impregnation amount within 1000 microns from the surface is 0.1 to 40% by weight (vs. polymer) Impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group to the surface of the polymer material, (3) catalyst, initiator, heating A modified adhesive obtained by a modification method characterized in that the step of grafting the monomer in the presence of at least one of ultraviolet irradiation and (4) the washing step are performed in this order. The present invention relates to a coating material, a printability, a chargeable polymer material and a modification method.

Alternatively, the present invention comprises (1) a solvent treatment step, (2) an activation treatment step, (3) a treatment with a polymer solution in the presence of a catalyst or an initiator, A modified polymer material obtained by a modification method characterized in that it is processed in the order of a grafting step of a monomer and (5) a washing step; and a polymer material having improved adhesiveness, paintability, printability and chargeability. The present invention relates to a reforming method. A printable polymer material is a material that has improved printability with water-based inks, oil-based inks, and ultraviolet curable inks (UV inks), and shows good results in which the print inks are difficult to peel off in a cross-cut peel test. is there.

Alternatively, in the present invention, the inner wall of a sample tube made of a polymer material is brought into contact with (1) a compound impregnating the polymer material, and the impregnation amount within 1000 microns from the surface is 0.1 to 40 wt. % (With respect to polymer material) and impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group to the surface of the polymer material, (3) catalyst A reforming method obtained by a reforming method characterized in that a monomer is grafted in the presence of at least one of initiator, heating, and ultraviolet irradiation, and (4) a washing step. The present invention relates to a sample tube made of a polymer material.

Alternatively, the present invention relates to a polymer material having hydrophilicity obtained by such a modification method, a polymer material that enables adhesion with an adhesive or a solvent, and adhesion of an adhesive tape, paintability with a paint, charging The present invention relates to a polymer material capable of imparting properties.

Alternatively, the present invention relates to a polymer material having hydrophilicity obtained by such a modification method, a polymer material that enables adhesion with an adhesive or a solvent, and adhesion of an adhesive tape, paintability with a paint, charging The present invention relates to a polymer material capable of imparting properties.

In particular, the present invention relates to polyolefin, silicon resin, fluorine resin, polyimide resin, polyoxymethylene resin, and polyaramid resin. Polymer material Water retention material, Microbial medium material, Synthetic paper, Filter material, Wipe cleaning cloth, Disposable medical / hygiene / cosmetic products (diapers, sanitary products, bandages, gauze, napkins, tapes, other medical / hygiene products, Various cleansing applications, cosmetic products such as face-wash packs, etc.), adhesive improvement materials, orthodontic brackets, medical equipment materials (infusion and infusion connection tools, cannula, catheter, artificial organ, tube, thread, plate-like Molded products), various sealing materials (mechanical seals, gaskets, packing materials, etc.) and the like.

The polymer material treated in the process of the present invention can be strongly bonded to a material which is generally said not to be bonded with an adhesive so that the material is broken or the adhesive layer is broken. Further, by modifying the silicon resin product that has not been attached to the adhesive tape, the adhesive tape can be attached to the silicon resin product. Even polymer materials that cannot be painted with oil-based and water-based paints in the untreated state can be painted with the polymer materials treated in the process of the present invention, providing excellent coating durability and perfect marks for coating film peeling tests. It becomes. The coated polymer material can be printed with water-based or oil-based ink, and can be printed with ultraviolet curable ink and cured / fixed by ultraviolet irradiation.
In particular, polyethylene resin, polypropylene resin, polycarbonate resin, silicon resin, polyimide, aromatic polyamide, fluorine resin, especially ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, which have been difficult until now Such a material can be applied with a strong water-based paint that is 100/100 in the cross-cut test. Furthermore, if these materials are modified, printing with water-based or oil-based ink, UV ink printing, bonding with various adhesive agents, solvent bonding, and sticking of an adhesive tape become possible.

Next, embodiments of the present invention will be described in more detail based on examples.

The materials, reagents, and test methods used will be described.
(Polymer material)
The polymer material used in the present invention is a material obtained by mixing or combining a polymer single material, a mixed material or a modified material thereof, or a polymer, a glass, a metal, a carbon material, or the like. Means the polymeric material involved. As the synthetic polymer, any of a thermoplastic polymer and a thermosetting polymer can be used. Although various methods are illustrated as a synthesis method, 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 a monomer selected from the group consisting of olefins, vinyl compounds other than olefins, vinylidene compounds and other compounds having a carbon-carbon double bond, or Mixtures or modifications of these homopolymers or copolymers, fluororesin: polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene Examples of the copolymer include polyvinylidene fluoride, polychlorotrifluoroethine, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, and polyvinyl fluoride.

Examples of the polymer material other than polyolefin include 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, such as vinyl chloride, styrene, Homopolymers or copolymers such as acrylic acid, methacrylic acid, esters of acrylic acid or methacrylic acid, vinyl acetate, vinyl ethers, vinyl carbazole, acrylonitrile and the like can be mentioned. Vinylidene compounds other than olefins are compounds containing vinylidene groups, and include homopolymers or copolymers such as vinylidene chloride, vinylidene fluoride, and isobutylene. Examples include acrylonitrile copolymers (acrylic fibers and molded products thereof, ABS resins, etc.), copolymers containing butadiene (synthetic rubber), and the like.

Vinyl compounds other than the above olefins are compounds 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. Can be mentioned. 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, 1-butenoic acid, ethylene tetrafluoride, ethylene trifluoride chloride, and double bonds. A compound containing one or more compounds such as butadiene, isoprene, chloroprene and the like can be mentioned.

(1) Polycondensate: Polyester (including polyethylene terephthalate and aliphatic and wholly aromatic polyester), polycarbonate, polybenzoate, polyimide, polyamide (including aliphatic polyamide and aromatic polyamide including nylon), or the like Mixtures or modified products of these polymers, (2) addition condensates: phenolic resins (Kinol: trade name, including those manufactured by Nippon Kainol Co., Ltd.), urea resins, melamine resins, xylene resins, etc., or polymers thereof (3) Polyaddition product: polyurethane, polyurea, etc., or a mixture or modification of these polymers, (4) Ring-opening polymer: cyclopropane, ethylene oxide, propylene oxide, lactone, Homopolymers or copolymers such as lactams, Or a mixture or modified product of these homopolymers or copolymers, (5) cyclized polymers: divinyl compounds (for example, 1,4-pentadiene), diyne compounds (for example, 1,6-heptadiine), etc. Homopolymers or copolymers, or mixtures or modifications of these homopolymers or copolymers, (6) Isomerized polymers: for example, alternating copolymers of ethylene and isobutene, (7) Electrolytic polymers: Homopolymers or copolymers of pyrrole, aniline, acetylene, etc., or mixtures or modifications of these homopolymers or copolymers, (8) silicon resins, silicone resins, (9) polymers of aldehydes and ketones, ( 10) polyethersulfone, (11) polypeptide, and the like. Examples of the natural polymer include cellulose, protein, polysaccharide and the like alone or as a mixture, and modified products thereof.

In the present invention, the above addition polymer is particularly preferably used. Although the monomer which comprises an addition polymer is not specifically limited, As olefin, arbitrary things, such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, etc. An α-olefin homopolymer or a copolymer of two or more of these, or a mixture of these homopolymers and / or copolymers can be appropriately used.

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 α-olefins, and copolymers of polypropylene, propylene and other α-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.

Examples of the polymer compound other than the above include silicon resin, silicon resin, polyacetal, polyphenol, polyphenylene ether, polyalkyl paraoxybenzoate, polyimide, polybenzimidazole, poly-p-phenylenebenzobisthiazole, and poly-p-phenylenebenzo. Bisoxazole, polybenzothiazole, polybenzoxazole, acetate in the fiber, regenerated cellulose fiber (rayon, cupra, polynosic, etc.), vinylon, fiber of vinyl alcohol and vinyl chloride copolymer (polyclar, trade name: Corderan, etc.), Etc. can be illustrated. 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, a molded product 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 to be modified. For example, any form of a fiber, a woven fabric, a nonwoven fabric, a cloth, a plate, a film, a sheet, a tube, a rod, a hollow container, a three-way cock, a box, a foam, and a 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.) can also be made hydrophilic by the present invention to improve wettability, adhesiveness, paintability, and chargeability. It 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.

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, various silicon resins, fluororesins, 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.

(Solvent treatment process)
Solvent treatment is to immerse a polymer or a material containing a polymer in a solvent that is not soluble in the polymer under conditions that do not dissolve the polymer. The polymer was immersed in a solvent at a temperature of about room temperature to about 80 ° C. for about 5 seconds to 60 minutes, and the polymer was not deformed and absorbed only about 0.1 to 10% of its weight on the surface. State. This can be achieved by quickly drying only the surface of the material after applying it to the solvent. If the polymer is a non-woven fabric or fiber, it is not always necessary, but it is effective when the material has a small surface area such as a film or plate, or a material that contains many antioxidants and other additives. It is. In the case of polypropylene, it is immersed in a solvent treatment liquid (toluene, xylene, decalin, tetralin, cyclohexane, etc.) at room temperature to 50 ° C. for 10 seconds to 30 minutes, and then the surface is dried to finish. It is preferable to immediately perform the next activation process. For the solvent treatment liquid of polyethylene, decalin, tetralin, xylene, α-chloronaphthalene and the like are effective. In addition, each polymer is combined with a solvent and temperature so as not to dissolve the polymer. For example, in the case of a circular polyolefin nonwoven fabric having a diameter of about 5 to 10 μm in diameter, immerse it in toluene at room temperature for 10 seconds, squeeze it, shake it off with a centrifugal dehydrator, apply the wind of an electric fan, When is apparently evaporated, finish. In the case of polyolefin films, plates, and molded articles, they are immersed in a solvent treatment liquid at 50 ° C. for about 30 seconds to 30 minutes, and then squeezed to the above-described degree and dried. The weight increase in these cases is about 1 to 5%.

(Impregnation treatment)
The impregnation treatment is a method in which a compound having an affinity for a polymer material is used as it is or as a solution or dispersion, and the compound is contacted at a temperature below its softening point to impregnate the compound from the surface. . 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. When the thickness of the polymer material is less than 1000 microns, it is 0.1 to 40% by weight, and the material thickness is 1000 microns. In the above case, it is 0.1 to 40% by weight with respect to the material portion within a depth of 1000 microns from the surface of the material. In the case of a polymer material having a thickness and a diameter of about 10 mm or less, the amount of impregnation is preferably about 0.1 to 10% by weight.

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 +1 or −1 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, α-chloronaphthalene, dichlorobenzene. A mixture of 1 volume of methanol and 1 volume of methanol can be used for polystyrene, 1 volume of toluene and 10 volumes of methanol, and a polyethylene terephthalate can be a mixture of 1 volume of phenol and 10 volumes of hexane.

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 30 seconds and then subjected to a centrifugal dehydrator (rotation number: 500 to 1000 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 1 to 5 mm), it is immersed in an impregnating agent at room temperature to 70 ° C. for about 1 second 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 sodium carbonate aqueous solution and methanol at room temperature for 1 second to 10 minutes, rinsed with methanol, and then 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 many antioxidants and other additives.

(Activation process)
The step of activating the polymer material in the present invention means a treatment for introducing a carbonyl group on the surface of the material. 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, 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 is the ratio of the absorbance at the absorption of 973Cm- ¹ based on the crystalline portion of methyl groups of the absorbance and unaltered 1710cm- around ¹ based on introducing carbonyl groups is about 0.1 or less 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. By doing so, an effective surface activation treatment can be achieved without reducing the material strength.

(Ozone treatment)
The purpose of the ozone treatment is to perform a reforming reaction mainly including an oxidation reaction by bringing the surface of the 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, oxygen or air flow is used, ozone is generated at a flow rate of 10 ml to 10 L / min at a concentration of −10 to 100 g / m ³ , and the treatment is performed at a temperature of 10 to 80 ° C. for 30 seconds to 10 hours. Can do. For example, in the case of polypropylene or polyvinyl chloride fiber, treatment at an ozone concentration of 10 to 40 g / m ³ and room temperature for about 30 seconds to 30 minutes is appropriate. In the case of a film shape, a treatment at an ozone concentration of about 10 to 80 g / m ³ and at room temperature for about −1 minute to 1 hour 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 some of them are converted to functional groups such as hydroxyl groups and carbonyl groups. .

(Plasma treatment)
In the plasma treatment, a polymer material is placed in a container containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen, air, etc., exposed to plasma generated by glow discharge, and a functional group containing oxygen, nitrogen, etc. on the surface of the material. The purpose is to introduce. 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. The plasma processing apparatus can be replaced by a corona discharge apparatus.

(UV 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)
In the high-pressure discharge treatment, a belt conveyor for moving the polymer material to be processed is installed in the tunnel-shaped processing device, and a large number of electrodes are attached to the inner wall surface of the processing device while moving the polymer material. In this method, a high voltage of hundreds of thousands of volts is applied to and discharged in the 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)
In the corona discharge treatment, a corona discharge is generated by applying a high voltage of several thousand volts between a grounded metal roll and a wire-like electrode placed at a distance of several millimeters. In this method, the polymer material to be processed is passed through the gap. 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.

(Monomer grafting process)
In the present invention, the monomer to be grafted is not limited as long as it can be grafted, but is preferably a compound having at least one carbon-carbon double bond, such as a vinyl compound or a similar compound. Of the monomers, hydrophilic monomers are preferred. Examples of hydrophilic monomers include (meth) acrylamide, 1-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, 1-dimethylamino Alkylene glycol mono (meth) such as ethyl (meth) acrylate, (alkyl) aminoalkyl (meth) acrylate such as 1-butylaminoethyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate Polyalkylene glycol mono (meth) acrylates such as acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, ethylene glycol Allyl ether, ethylene glycol vinyl ether, (meth) acrylic acid, aminostyrene, hydroxystyrene, vinyl acetate, glycidyl (meth) acrylate, allyl glycidyl ether, vinyl propionate, N, N-dimethylmethacrylamide, N, N- Diethylmethacrylamide, N- (1-hydroxyethyl) methacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine, N-vinyl-1-pyrrolidone, N-vinyl-3-methyl-1-pyrrolidone, N-vinyl-4-methyl -1-pyrrolidone, N-vinyl-5-methyl-1-pyrrolidone, N-vinyl-6-methyl-1-pyrrolidone, N-vinyl-3-ethyl-1-pyrrolidone, N-vinyl-4,5-dimethyl -1-pyrrolidone, N-vinyl-5 -Dimethyl-1-pyrrolidone, N-vinyl-3,3,5-trimethyl-1-pyrrolidone, N-vinyl-1-piperidone, N-vinyl-3-methyl-1-piperidone, N-vinyl-4-methyl -1-piperidone, N-vinyl-5-methyl-1-piperidone, N-vinyl-6-methyl-1-piperidone, N-vinyl-6-ethyl-1-piperidone, N-vinyl-3,5-dimethyl -1-piperidone, N-vinyl-4,4-dimethyl-1-piperidone, N-vinyl-1-caprolactam, N-vinyl-3-methyl-1-caprolactam, N-vinyl-4-methyl-1-caprolactam N-vinyl-7-methyl-1-caprolactam, N-vinyl-7-ethyl-1-caprolactam, N-vinyl-3,5-dimethyl-1-caprolactam, N-vinyl N-vinyllactam, such as ru-4,6-dimethyl-1-caprolactam, N-vinyl-3,5,7-trimethyl-1-caprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N- N-vinylamide such as vinyl-N-ethylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylphthalimide, vinylacetic acid, 1-butenoic acid, ethylenesulfone At least one monomer selected from the group consisting of acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, maleic anhydride, pyromellitic anhydride, or at least selected from these groups Two types Mixtures of the body is preferred.
In the present invention, when chemical resistance and water absorption are required, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylamide, hydroxyalkyl (meth) acrylate, alkylene glycol mono (meth) acrylate, N-vinyl lactam and N The use of single compounds or mixtures such as vinylamide is particularly preferred.

Furthermore, for the purpose of improving adhesiveness, paintability and printability, vinyl monomers such as acrylic acid esters, methacrylic acid esters, vinyl acetate, and styrene, which are less hydrophilic than hydrophilic monomers, are used. Can be used. In order to improve the hydrophilization, it is preferable to use only a hydrophilic monomer. However, by using a mixture of a hydrophilic monomer and a poorly hydrophilic monomer, the grafting rate is increased and the graft polymer is increased. In some cases, the hydrophilic monomer contained therein can 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.), azo compounds (2,2′-azobisisobutyronitrile), dicerium ammonium nitrate ( IV), persulfates (potassium persulfate, ammonium persulfate, etc.), redox initiators (oxidizers: persulfates, hydrogen peroxide, hydroperoxides, etc., inorganic reducing agents: copper salts, iron salts, hydrogen sulfites Sodium, sodium thiosulfate, etc. or organic reducing agent: combination with alcohol, amine, oxalic acid, etc., and oxidizing agent: hydroperoxide, etc. and inorganic reducing agent: copper salt, iron salt, sodium bisulfite, sodium thiosulfate, etc. Or organic reducing agent: dialkyl peroxide, diacyl peroxide and the like and reducing agent: tertiary amine, naphthenate Mercaptans, organometallic compounds (triethyl aluminum, triethyl boron) combined with), and other known radical polymerization initiator and the like. When acrylic acid is used as a monomer, water-soluble polymerization initiators such as dicerium ammonium nitrate (IV) and potassium persulfate are preferably used, such as benzoyl peroxide and 2,2′-azobisisobutyronitrile. The water-insoluble initiator can be dissolved in methanol or acetone and mixed 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. 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.

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 JP-A-8-109228 of the present inventor can also be preferably used.

(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 polymer solution)
The polymer solution treatment of the activated polymer material is preferably performed 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 polymer solution treatment step, the 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 the hydrophilic durability, a treatment at a high temperature for a long time (for example, about 11 hours) is also performed.

(Washing process)
When the polymer material modified by the method of the present invention is to be improved in durability, hydrophilicity, adhesion, and paintability, the surface of the polymer material after polymer treatment or grafting treatment A process of sufficiently washing excess polymer adhering to the film becomes essential. Unlike normal cleaning, this is a process of carefully cleaning and removing the polymer adhering to the treated polymer material. For example, a polymer material treated with a hydrophilic polymer is boiled and washed with an aqueous solution of sodium fatty acid (concentration 1 to 10% by weight) for 1 to 10 minutes, and then thoroughly washed with water. For example, when measuring the total reflection infrared absorption spectrum of the surface of an ultrahigh molecular weight polyethylene material after washing, the difference between the infrared absorption spectrum and the infrared absorption spectrum of an ultrahigh molecular weight polyethylene material that has only been subjected to activation treatment is observed. Wash to an unacceptable level. In the case of treatment with a monomer or polymer having poor hydrophilicity, such as methyl methacrylate or its polymer, or vinyl acetate or its polymer, it is washed with chloroform at 40 ° C. for 10 to 60 minutes, Alternatively, thoroughly wash with acetone and methanol. Similarly, in the total reflection infrared absorption spectrum measurement, the absorbance around 1710 cm- ¹ due to the carbonyl group of the bound polymer is such that an increase in absorbance of about 0 to 5% is observed compared to the polymer material only with the activation treatment. Wash until. In order to perform the cleaning step effectively, it is preferable to heat and then clean with an ultrasonic cleaner. Moreover, it is preferable to perform extraction for 1 to 6 hours using the solvent and Soxhlet extractor which melt | dissolve attached polymer. In addition, if a certain cleaning condition is determined for the processing material, it is not necessary to perform total reflection infrared absorption spectrum measurement for the material.

(Use)
The polymer material modified by the method of the present invention is greatly improved in hydrophilicity, water absorption, adhesiveness, paintability and the like, and has excellent durability. It can be applied to various uses by utilizing the above. Adhesion improvement means modification of a polymer material that is difficult to adhere to, and adhesion using an adhesive: general adhesives such as starch, polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl alcohol, epoxy resin Can be bonded to paper, wood, metal, etc. with an adhesive such as a system, polymerizable cyanoacrylate, etc., or solvent bonding: When bonding a polymer material to another polymer material, apply a small amount of both solvents. When the coated part is brought into close contact, it means that both strong bonding can be performed after the solvent evaporates. In addition, the polymer material having improved adhesiveness according to the present invention can be applied with a paint which has been difficult until now. The paint can be applied with any paint such as oil-based acrylic resin paint, oil-based nitrocellulose paint, water-based synthetic resin paint, metal powder-containing paint, heat-resistant paint, fluorescent paint, etc. .
Furthermore, the modification method of the present invention can be applied to many polymer materials including polyolefins such as polypropylene and polyethylene, silicon resins, silicon resins, fluororesins, and polyimides, which are said to be particularly difficult to modify. For polyolefin nonwoven fabrics or mixed nonwoven fabrics made of polyolefin and other polymers, it is possible to give water absorption of about 7 to 10 times its own weight, and the resulting water absorption is alkali resistance, acid resistance, oxidation resistance. Excellent in properties. 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.

(4) Medical / hygiene / cosmetic products: Means various disposable items. 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, a cheap, easy and durable hydrophilization 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 / hygiene / cosmetic article, the material shape is preferably woven fabric 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.

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

(6) Filter material:
Filter media made of a porous film made of a hydrophobic material such as polyolefin, polysulfone, or polyester has higher strength than paper filter media, but is poor in hydrophilicity, so it is not suitable for aqueous solution filtration. Is appropriate. 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) Orthodontic bracket:
By the treatment method according to the present invention, the adhesion of the polymer material can be improved. Since it can be utilized for various materials that require adhesiveness, composite materials, and reinforcing fibers blended in fiber-reinforced plastics, the adhesiveness between the orthodontic bracket made of plastic and the teeth can be improved.

(8) Medical device material parts: Infusion fluid drain tube, drainage device, connection filter, infusion kit drip tube and its connection tube / tube, tube connection three-way cock, various catheters, artificial blood vessels , Artificial organs, artificial joints, tubular, thread-like, plate-like polymeric material parts. In particular, medical devices are often used by joining tubular members made of different materials, for example, a soft member and a hard member so as not to be detached, and according to the present invention, a plurality of different tubular members are joined by solvent bonding. This makes it possible to prevent dissolution of the adhesive in the infusion solution. For example, the protrusion at the tip of a polypropylene drip tube is surface-modified so that untreated polybutadiene or polyvinyl chloride tubes and solvents (chloroform, toluene, tetrahydrofuran, methanol, ethanol, acetone, ethyl acetate, water, Etc., or a mixture thereof). Further, the hydrophilicity of these materials can be improved to improve the 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. If the inner wall of the silicone rubber tube that connects the outer surface of the three-way cock for connection made of polypropylene is modified, both can be solvent-bonded.

(9) Modification of polymer material sample tube / pipette tip, catheter, tube: If the inner surface of polypropylene or other polymer chemical sample tube or blood sampling tube is modified to make it hydrophilic, If a solution obtained by mixing a blood anticoagulant with a hydrophilic polymer solution is applied and heat-treated, coagulation after blood collection can be prevented. In addition, surface treatment of catheters, other tubes, and blood contact parts is performed, and anticoagulant active substances such as heparin, urokinase, streptokinase, thrombomodulin, plasminogen activator, hirudin, prostacyclin, and antithrombin are adhered. When applied with a resin (such as a water-soluble polymer or an acrylic resin solution), heated and dried, an anti-blood coagulation action can be imparted.
For example, when a hydroxyl group bonded to a hydrophilized polymer material is used and treated with a phosphate compound such as phosphorylcholine (PC) having an anti-protein adsorption action and a silane coupling group bonded, The surface of the molecular material is covered with PC. If a sample tube made of polypropylene having a hydrophilic inner wall is treated with a PC compound, it becomes possible to prevent adhesion of proteins in the blood when blood is collected. If anti-protein adsorbing action is expected, 1-methacryloyloxyethyl phosphorylcholine (MPC), which is a monomer obtained by converting PC to mecacrylic acid ester, is used as a monomer in the “grafting process” of the basic operation of this technology. Alternatively, it is effective to use a macromonomer obtained by introducing a vinyl group into an oligomer obtained by polymerizing MPC.

An amino-based silane MPC polymer obtained by allowing an amino-based silane coupling agent to act on a polymer obtained by polymerizing MPC is applied to the modified polymer material and then heated to apply MPC to the modified polymer material. It is possible to bind the polymer. The coupling agent used for the coupling treatment is, for example, N- (1-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-β. -(N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride, allyloxy-1-aminoethylaminomethyldisilazane, 3-allylaminopropyltrimethoxysilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Examples thereof include amino silane coupling agents such as trichlorosilane.

(10) Seal material: Sealing gasket, gasket, and other surfaces molded from silicon resin, polyester resin, polyimide resin, polyamide resin, fluorine resin, etc. The surface of the material molded for sealing is modified by the method of the present invention. And adhesiveness can be provided. By adhering these modified sealing materials having improved adhesiveness to another molded article made of graphite, stainless steel, ceramics, etc., a sealing material having a laminated structure with a flexible surface can be obtained.

(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 fiber reinforced plastic. It is preferable to improve the adhesiveness of the synthetic fiber and mix it with plastic to make a composite material, because a material that is strong and easy to recover can be produced.

(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) Inkjet paper: Since a material obtained by hydrophilizing a paper-like molded body of a polymer material exhibits hydrophilicity similar to that of paper, it can be further processed into an inkjet printer paper. For example, binders (eg, gelatin, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide) used to form a coating layer (porous fine particle type or polymer type) for producing inkjet printer paper for hydrophilic polyethylene synthetic paper. Hydrophilic polymers such as polyvinyl alcohol) and inorganic fine particles (eg, white inorganic pigments such as calcium carbonate, alumina, zeolite, magnesium hydroxide, colloidal alumina) or organic fine particles (eg, acrylic acid alkyl ester, methacrylic acid alkyl ester). , A polymer obtained by emulsion polymerization of monomers such as styrene and a styrene derivative), and it becomes possible to produce a synthetic paper for printing for a lightweight inkjet printer.

(14) Material with improved adhesiveness: In addition to improving the adhesiveness of the orthodontic bracket and the reinforcing fiber for composite material, the adhesive properties of various polymer films and molded products are improved, Adhesion with different materials can be improved. In particular, solvent bonding is also possible. The polymer material having improved adhesiveness by this method can be applied with a pressure-sensitive adhesive for pressure-sensitive adhesive tapes, making it possible to produce pressure-sensitive adhesive tapes that were not possible before.

  The polymer material modified by this method can be strongly attached to various adhesive tapes. For example, the holding portion of a drip injection needle (cannula) is made of silicon rubber, polypropylene, polyethylene or the like. When the silicone rubber modified by the method of the present invention is used as a clamping tube, the modified silicone rubber tube portion can be attached to the injection device mounting portion with a medical adhesive tape.

(15) 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.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention should not be construed as being limited to these examples. The materials, reagents, and test / evaluation methods used are shown below.

(A) Material containing polymer material (B) Reagents (1) Polyvinyl alcohol (degree of polymerization 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) Methacrylic acid mail (PVA): manufactured by Wako Pure Chemical Industries, Ltd., product number 160-11485 (average polymerization degree chill: manufactured by Wako Pure Chemical Industries, Ltd., product number 139-01716)
(6) Sodium persulfate (SPS): manufactured by Wako Pure Chemical Industries, Ltd., product number 195-04985
(7) 2,2′-Azobisisobutyronitrile (AIBN): Wako Pure Chemical Industries, Ltd., product number 019-0931
(8) Dicerium ammonium nitrate (IV) (CAN): Wako Pure Chemical Industries, Ltd., product number 036-01741
(9) Benzophenone: Wako Pure Chemical Industries, Ltd., product number 013-01071
(10) Methanol: Wako Pure Chemical Industries, Ltd., product number 136-09475
(11) Sodium hydroxide: manufactured by Wako Pure Chemical Industries, Ltd., product number 194-01135
(12) Hydrochloric acid: Wako Pure Chemical Industries, Ltd., product number 080-01066
(13) Toluene: Wako Pure Chemical Industries, Ltd., product number 104-01866, this liquid itself was used (impregnating agent A).
(14) Sodium dodecylbenzenesulfonate (DBS): Tokyo Chemical Industry Co., Ltd., product number D1138, used as a surfactant.
(15) Decahydronaphthalene (cis, trans mixture): Wako Pure Chemical Industries, Ltd., product number 048-O0066, this liquid itself was used (impregnating agent B).
(16) Orthohydroxybiphenyl (OHB): Wako Pure Chemical Industries, Ltd., product B number 080-O1401, 1 g of orthohydroxybiphenyl and 0.1 g of sodium hydroxide, 0.1 g of surfactant (sodium dodecylbenzenesulfonate) Was used as a solution obtained by mixing 100 ml of water (impregnating agent C).
Alternatively, a solution obtained by dissolving 0.5 g of orthohydroxybiphenyl in 300 ml of methanol was used by dispersing in water used as a carrier (carrier D).
(17) Sodium salicylate (SS): manufactured by Wako Pure Chemical Industries, Ltd., product number 195-O3145 (impregnating agent D)
1 g of sodium salicylate was dissolved in 100 ml of water and mixed with 0.5 ml of 10% hydrochloric acid and dispersed in water (impregnant E).
(18) Diphenyl (DP): Wako Pure Chemical Industries, Ltd., product number 040-18411. A solution obtained by mixing 1.5 g of diphenyl and 0.1 g of a surfactant (sodium dodecylbenzenesulfonate) in 100 ml of water was used (impregnating agent F).
(19) Carriert (trade name, manufactured by Toho Chemical Co., Ltd.): A carrier for dyeing polyester-based synthetic fibers, and an aromatic ether-based anionic surfactant. Used by dispersing in water (carrier 1).
(20) Carrier TW100 (trade name, manufactured by Nikka Chemical Co., Ltd.): A carrier for dyeing synthetic fibers for polyester / wool blends, methylnaphthalene and other blended products, used by dispersing in water (carrier 1).

(C) Ozone treatment:
Put the test piece in a hard glass container (with gas inlet and outlet) with a volume of 1L or 10L, and from an ozone generator (OS-1N manufactured by Mitsubishi Electric Corp.), the amount of ozone generated is 1 g / h, and the concentration is 10 g / h. oxygen containing ozone m ³ was blown from 10 to 110 minutes at 800 ml / min flow rate. 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 and measuring the infrared absorption spectrum to determine the change in 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. The infrared absorption spectrum was measured using Shimadzu Prestige 21.

(D) Plasma treatment:
A test piece (cloth, film, etc.) was placed between the electrodes in the reaction vessel of the atmospheric pressure plasma processing apparatus (Yamato Scientific YAP500, output 500 W). In an atmosphere in which argon, helium, nitrogen, and oxygen gases were flowed at a flow rate of 1 to 1000 mL / min, the supply power was set to a value between 300 and 500 W, and irradiation was mainly performed for 10 seconds to 1 minute. After the discharge, the treated specimen was taken out. The degree of treatment was judged by the decrease in the contact angle of water with the film. In addition, the company's low-temperature plasma processing equipment was also used.

(E) UV irradiation treatment:
In the case of activation treatment, the sample was directly irradiated with a high-pressure mercury lamp (Toshiba high-pressure mercury lamp H400P) from a distance of 5 to 30 cm. Air was blown using a cooling fan, and the temperature rise on the sample surface was suppressed to about 60 ° C. to prevent the sample from being deteriorated.
In the case of grafting, the reaction mixture was placed in a reaction vessel made of hard glass, 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 5 to 30 cm. When the sample was not flat, the reaction tube revolved around the lamp while rotating so that the light was uniformly irradiated.

(F) Measurement of water contact angle:
A contact angle measuring device (CA-X manufactured by Kyowa Interface Science Co., Ltd.) was used. At 10 ° C., a water droplet having a diameter of about 1 mm was dropped from the syringe onto the surface of the test piece and was calculated from the size of the image magnified by the video camera.
Shows only the longitudinal direction.

(G) 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: 150, and boiling washed for 5 minutes with stirring. 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.

(H) Tensile strength test:
The test piece is cut into a 1.5 cm × 7 cm rectangle, and the 1 cm or 1 cm portion from both ends is fixed to the clamp of a tensile tester (SV55-0-10M manufactured by Imada Seisakusho Co., Ltd.), the grip interval is 5 cm, and the tensile speed is 100 mm. Pulled at / min. Measurements were made in each direction of the vertical and horizontal eyes. In each example, only the longitudinal direction was shown.

(I) Adhesive peel strength test:
(1) For film:
The 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 plywood (thickness 1 mm, size 10 mm × 10 mm) or sticky note ((thick The weight is 0.2 mm, the size is 10 mm x 10 mm, and a weight of 500 g is put on the polyethylene film for 11 hours.The unbonded part of the plywood is 10 mm and the unbonded end of 10 mm is a tensile tester. (Shimadzu Corporation Autograph AGS-H) was clamped and pulled at a pulling speed of 50 mm / min to determine the energy required to peel the bonded part (adhesive peeling energy). The relative value was determined by setting the adhesion release energy of the untreated material in 1.0 to 1.0. Acrylate-based: In the case of sticky notes and (Aron Alpha Toa Gosei Co., Ltd.), paper applications adhesives for stationery (trade name: Kokuyo Co., Ltd., split) is.
(2) In the case of plate:
Depending on the size of the test piece, the test piece and other materials were bonded with an adhesive. The bonding part was 1 cm in length with the full width of the material. A portion 1 cm from both ends was sandwiched between clamps and pulled at a pulling speed of 50 mm / min to obtain a load required for peeling off the bonded portion.

(J) Paint:
As the oil-based paint, Nippe Home Products Co., Ltd., Nippe Home Paint / Spray Lacquer (trade name, color: chocolate, component: synthetic resin (acrylic), pigment, organic solvent, use: iron / wood) was used. For water-based paints, use Asahi Pen Co., Ltd., water-based supercoat (trade name, color: ocean blue, component: synthetic resin (silicone, acrylic, fluorine), pigment, UV deterioration inhibitor, rust inhibitor, water 1) It was. After the polymer material was painted, it was dried. The drying time was 80 ° C., the water-based paint was 1 hour, and the oil-based paint was 1 hour. However, the drying time was 50 ° C. for 5 hours.

(K) Cross-cut test (cross cut test):
A cross-cut test for coating evaluation is performed as follows in accordance with JISK5400. Using a cutter knife on the painted surface, draw parallel lines of 11 vertical and horizontal lines at 1 mm intervals to make a grid-like cut so that 100 squares can be formed in 1 cm ² . Adhere cellophane adhesive tape to the grid area and pull away. The determination is “100/100 No peeling, pass” if there is no peeling at all, and if there is a peeled grid, the number of remaining grids is recorded. In this study, it was always compared with untreated material.

(L) Blood coagulation test:
Tris buffer solution (manufactured by SIGMA, registered trademark TRIZMABASE) was added to the treated or untreated polymer material so that the total amount was 180 μL in 50 μL of bovine plasma (manufactured by SIGMA). After this solution was kept at a temperature of 37 ° C. for 5 minutes, 10 μL of 11.5 NIH unit / mL bovine thrombin (manufactured by SIGMA) was added and applied. The blood was kept in a constant temperature bath at a temperature of 37 ° C., and the anticoagulant activity was confirmed by confirming the presence or absence of coagulation of the solution after 3 minutes.

(M) Blood protein adhesion test: 500 μL of 1 μg / mL FITC (fluorescein isothiocyanate) labeled bovine serum albumin solution is added to the polymer material and then adsorbed at 37 ° C. for 1 hour. It was. The adhesion amount of the albumin solution after adsorption was calculated by measuring fluorescence intensity.

Solvent adhesion by modification of polypropylene drip tube and polybutadiene tube for medical drip device 1) Small diameter tubular protrusion provided at the end of polypropylene drip tube, which is a part of drip device, by masking as activation treatment Only the surface of the part was treated with an oxidant. Oxidation was performed with ozone treatment at room temperature for 60 seconds.
2) Next, a chloroform solution of polyvinyl acetate (concentration: 1% by weight) was applied to the activated tubular protrusion as a polymer treatment and heated at 80 ° C. for 1 minute.
3) The protrusion was immersed in chloroform, washed at room temperature for 10 minutes, and dried for 1 minute.
4) A drop of chloroform was applied to the treated tubular protrusion, and a polybutadiene tube was inserted. This was left to dry for 5 minutes.
5) The connecting portion of the drip tube and the polybutadiene tube was pulled to the left and right with a load of 30 kgf, and the connection portion could not be removed. The connection part of the untreated object was removed with a load of 1 kgf.

As the activation treatment of 1) of Example 3, ultraviolet irradiation was performed for 30 seconds from a distance of 5 cm. Other operations were performed in the same manner as in Example 3, and the same effects as in Example 3 were obtained.

As the activation process of 1) of Example 3, plasma treatment was performed for 30 seconds. Other operations were performed in the same manner as in Example 3, and the same effects as in Example 3 were obtained.

As an activation treatment of Example 3 1), a corona discharge treatment was performed for 60 seconds. Other operations were performed in the same manner as in Example 3, and the same effects as in Example 3 were obtained.

Solvent adhesion by modification of polypropylene three-way cock and silicone rubber tube 1) As the activation treatment, in the same manner as in Example 1, the inside of the silicon rubber tube 1 cm in length and inside the polypropylene three-way cock Ultraviolet irradiation was performed from a distance of 5 cm for 30 seconds on the outside 1 cm in length from the end.
2) Next, as a grafting treatment, an acetone solution of vinyl acetate and methacrylic acid (volume ratio of 1: 1, concentration of 5% by weight) was applied to the activated tubular protrusion and heated at 80 ° C. for 5 minutes. .
3) Next, as a cleaning process, the sample was immersed in chloroform at 45 ° C. and placed in an ultrasonic cleaner for 10 minutes. Further, it was rinsed with chloroform, washed and dried.
4) Solvent adhesion: One drop of chloroform was applied to a 1 cm long portion of the treated polypropylene three-way cock, and a silicone rubber tube was inserted. This was left for 1 minute.
5) Even when the joining portion of the polypropylene three-way cock and the silicone rubber tube was pulled to the left and right with a load of 40 kgf, the connecting portion could not be removed. The connection part of the untreated object was removed with a load of 1 kgf.

As the activation process of Example 7 1), ozone oxidation was performed for 30 seconds. Other operations were performed in the same manner as in Example 7, and the same effects as in Example 7 were obtained.

As the activation treatment of Example 7 1), plasma treatment was performed for 30 seconds. Other operations were performed in the same manner as in Example 7, and the same effects as in Example 7 were obtained.

As the activation treatment of Example 7 1), a corona discharge treatment was performed for 60 seconds. Other operations were performed in the same manner as in Example 7, and the same effects as in Example 7 were obtained.

Instead of the monomer of 2) of Example 7, an aqueous solution (weight concentration 2%) of carbomethylcellulose and starch at a mixing weight ratio of 1: 1 was performed for 30 seconds as a polymer treatment. Other operations were performed in the same manner as in Example 7, and the same effects as in Example 7 were obtained.

Solvent adhesion by modification of polypropylene tube and polyurethane tube of medical infusion device For the outer wall portion of the polypropylene tube and the inner wall portion 10 mm from the end of the polyurethane tube, before the activation treatment of Example 3, the solvent As treatment, toluene was applied to polypropylene, and benzyl alcohol was applied to urethane, and left for 15 minutes. Subsequent operations were the same as in Example 7. As in Example 7, solvent bonding became possible.

Solvent Adhesion by Modification of Polyester Parts and Polyurethane Tubes for Medical Infusion Devices Treated in the same manner as in Examples 7 to 11, and solvent adhesion became possible.

Polypropylene tubular containers for medical infusion devices and tubular tubes made of soft polymer materials (nylon elastomer, low density polyethylene, silicone rubber tube, made of polyvinyl chloride) are treated in the same manner as in Examples 7 to 10 to obtain a solvent. Adhesion was improved. Moreover, adhesion by a UV curable adhesive (manufactured by Toa Gosei Co., Ltd .: photocurable adhesive Aronix LCR0618A) is also possible.

Modification that enables painting of a polypropylene molded product with a water-based paint 1) As an activation treatment, the surface of the polypropylene molded product was irradiated with ultraviolet rays from a distance of 5 cm for 60 seconds.
2) A toluene solution of polymethyl methacrylate and polymethacrylic acid (volume ratio 1: 1, concentration 1% by weight) was applied and heated at 60 ° C. for 10 minutes.
3) Ultrasonic cleaning was performed by immersing in 60 ° C. toluene for 30 minutes. Further, it was rinsed with toluene at room temperature and then dried for 10 minutes.
4) A water-based paint was applied to the treated part. The water-based paint is manufactured by Asahi Pen Co., Ltd., water-based supercoat (trade name, color: ocean blue, component: synthetic resin (silicone, acrylic, fluorine), pigment, UV deterioration inhibitor, rust inhibitor, water 1). Using.
5) As a result of performing a crosscut test after drying at 80 ° C. for 1 hour, an evaluation of 100/100 was obtained at which no peeling occurred.
6) An oil-based paint was applied to the treated part.
Nippe Home Products Co., Ltd., Nippe Home Paint / Spray Lacquer (trade name, color: chocolate, component: synthetic resin (acrylic), pigment, organic solvent, application: iron / wood) was used as the oil-based paint.
7) After drying at 80 ° C. for 1 hour, a cross cut test was performed. As a result, an evaluation of 100/100 was obtained at which no peeling occurred.
8) Water resistance test of coating: The molded product made of modified polypropylene coated with the water-based paint was immersed in water at 40 ° C. for 10 days. This sample was dried and then subjected to a cross-cut test. As a result, an evaluation of 100/100 was obtained at which no peeling occurred.

As the activation treatment of Example 15 1), ozone oxidation was performed for 30 seconds. Other operations were performed in the same manner as in Example 15, and the same effects as in Example 15 were obtained.

As the activation treatment of Example 15 1), plasma treatment was performed for 30 seconds. Other operations were performed in the same manner as in Example 15, and the same effects as in Example 15 were obtained.

As the polymer treatment in Example 15 2), an aqueous solution (weight concentration 2%) of carbomethylcellulose and starch at a mixing weight ratio of 1: 1 was performed for 30 seconds. Other operations were performed in the same manner as in Example 15, and the same effects as in Example 15 were obtained.

Improving the printability of polypropylene molded products 1) About polypropylene plate-shaped molded products treated in the same manner as in Example 15, UV ink (Toyo Ink, FDSS series for inkjet (color 193 red)) with a thickness of 3.0 μm An ink layer was formed. The ink layer was irradiated with a UV lamp (metal halide lamp 1.5 kW) at an irradiation distance H = 50 mm and a moving speed V = 5 mm / sec.
2) Next, the ink layer was heated at a temperature of 70 ° C. for 1 minute and then allowed to stand at room temperature for 1 hour. After the ink layer was fixed, a cross-cut cellophane tape peeling test was performed as a durability test, and 100/100 was obtained. Further, even in a water resistance test immersed in warm water at 40 ° C. for 1 week, printing was not peeled off.

Improving the printability of polycarbonate, acrylic resin, and polyester resin plate-like molded products About the polycarbonate, acrylic resin, and polyester resin plate-like molded products treated in the same manner as in Examples 15 to 18, the same UV ink as in Example 19 was used. Improved printability was obtained.

Improving the printability of polyethylene, polypropylene, polycarbonate, acrylic resin, and polyester resin plate-shaped moldings About polyethylene, polypropylene, polycarbonate, acrylic resin, and polyester resin plate-shaped moldings treated in the same manner as in Examples 15 to 18, Good printability was obtained in a printability test using an aqueous pigment ink (platinum INK-G-1500), a solvent pigment ink (Roland ECO-SOLMA ink), and an aqueous pigment ink for ink jet printers (Canon BCI-3eBK). It was.

Modification that enables coating of silicon resin plate-shaped molded product with water-based paint The same treatment as in Examples 15 to 18 enabled the coating with the water-based paint. In addition, painting with oil-based paint has become possible. As a result of the cross-cut test, an evaluation of 95/100 to 100/100 was obtained.

Hydrophilization of the inner wall of a polypropylene sample tube and application of an antithrombotic drug 1) The inner wall of a polypropylene sample tube (capacity 5 ml) was subjected to ozone treatment for 10 seconds as an activation treatment.
2) Next, an aqueous solution (concentration 5% by weight) of a hydrophilic polymer (carboxymethylcellulose) was applied to the activated tubular protrusion, and ultraviolet irradiation was performed for 1 minute.
3) After the treatment, the product was boiled and washed with boiling water for 10 minutes, rinsed thoroughly with water, and then dried.
4) The inner wall of the treated polypropylene sample tube was wetted with pure water to a contact angle of 10 degrees or less.
5) A coating solution in which the anticoagulant drug anticoagulant active substance heparin was mixed was applied to the inner wall of the treated polypropylene sample tube and then heated at 60 ° C. for 1 hour.
6) The treated polypropylene sample tube was thoroughly washed with water at 60 ° C.
7) Good results were obtained in the blood coagulation test.

As an activation treatment of Example 23 1), ozone oxidation was performed for 30 seconds. Other operations were performed in the same manner as in Example 23, and the same effects as in Example 23 were obtained.

As the activation treatment of Example 23 1), plasma treatment was performed for 30 seconds. Other operations were performed in the same manner as in Example 23, and the same effects as in Example 23 were obtained.

Instead of the polymer treatment in Example 23 2), as an grafting treatment, an acetone solution of vinyl acetate and methacrylic acid (volume mixing ratio 1: 1, concentration 5% by weight) was added to the activated tubular protrusion. And heated at 80 ° C. for 5 minutes. For 30 seconds. Other operations were performed in the same manner as in Example 23, and the same effects as in Example 23 were obtained.

Hydrophilization of the inner wall of a polypropylene sample tube and application of an antithrombotic drug 1) The inner wall of a polypropylene sample tube (capacity 5 ml) was placed for 15 minutes after applying ethyl acetate as a solvent treatment. As activation treatment, ultraviolet irradiation was performed for 10 seconds.
2) Next, an aqueous solution of polyacrylic acid (concentration 1% by weight) was applied to the activated tubular protrusion, and ultraviolet irradiation was performed for 1 minute.
3) After the treatment, it was washed with boiling water for 10 minutes, and it was confirmed that polyacrylic acid was no longer dissolved.
4) The inner wall of the treated polypropylene sample tube was wetted with pure water to a contact angle of 10 degrees or less.
5) Amino group-containing silane obtained by mixing N- (1-aminoethyl) -3-aminopropylmethyldimethoxysilane with MPC polymer in a sample tube made of treated polypropylene and leaving it at 40 ° C. for 14 hours. The coated MPC polymer was applied, and an aqueous potassium persulfate solution (concentration: 10% by weight) was applied, left at 50 ° C. for 1 hour, and then repeatedly washed with 60 ° C. water.
6) 500 μL of 1 μg / mL FITC-labeled bovine serum albumin solution was added to the inside of the treated polypropylene sample tube and adsorbed at 40 ° C. for 1 hour. The amount of adsorption was calculated by measuring the fluorescence intensity of the albumin solution after adsorption. The amount of protein adsorbed on the inner wall of the surface-modified polypropylene sample tube decreased compared to the untreated polypropylene sample tube.

A 10% by weight aqueous solution of poly (1-methacryloyloxyethyl phosphorylcholine) (trade name: Lipidure (manufactured by NOF Corporation)) and an aqueous polyvinyl alcohol solution are formed on the inner wall of a treated polypropylene sample tube obtained in the same manner as in Example 27. A 10 wt% mixture (mixing volume ratio 9: 1) was applied and immersed at 60 ° C. for 1 hour. Next, it was thoroughly washed with water at 60 ° C. After drying, good results were obtained in the blood coagulation test.

Hydrophilization of the inner wall of a polypropylene sample tube and application of an antithrombotic drug 1) As an impregnation treatment for the inner wall of a polypropylene sample tube (5 ml capacity), 0.5 g of 10 ml of orthohydroxybiphenyl was obtained by dissolving in 300 ml of methanol. The solution (Carrier D) was added and placed at 70 ° C. for 10 minutes.
2) As the activation treatment, ozone treatment was performed for 30 seconds.
3) Next, an aqueous solution of polyacrylic acid (concentration 1% by weight) was applied to the activated tubular protrusion, and ultraviolet irradiation was performed for 1 minute.
4) After the treatment, it was washed with boiling water for 10 minutes.
5) The inner wall of the treated polypropylene sample tube was wetted with pure water to a contact angle of 10 degrees or less.
6) The sample was immersed in a 10% by weight aqueous solution of poly (1-methacryloyloxyethyl phosphorylcholine) (trade name: Lipidure (manufactured by NOF Corporation)) at 80 ° C. for 1 hour on the inner wall of the treated polypropylene sample tube. Next, it was washed with 40 ° C. water.
7) After drying, good results were obtained in the blood coagulation test.

As the activation treatment of Example 29 1), ultraviolet irradiation was performed for 30 seconds from a distance of 5 cm. Other operations were performed in the same manner as in Example 29, and the same effects as in Example 29 were obtained.

As the activation treatment of Example 29 1), plasma treatment was performed for 30 seconds. Other operations were performed in the same manner as in Example 29, and the same effects as in Example 29 were obtained.

Improvement of adhesion of ultra high molecular weight polyethylene 1) Ultra high molecular weight polyethylene plate (shape: rectangular parallelepiped, size: length 60 mm, width 10 mm, thickness 3 mm) was subjected to ultraviolet irradiation for 60 seconds as an activation treatment.
2) Next, this activated ultrahigh molecular weight polyethylene plate was coated with an aqueous solution of polyacrylic acid (concentration 1% by weight) and benzoquinone, and irradiated with ultraviolet rays for 1 minute.
3) After the treatment, as a washing step, washing with boiling water was performed for 10 minutes, and ultrasonic washing was performed at 50 ° C. for 10 minutes, and it was confirmed that polyacrylic acid was not dissolved anymore.
4) The treated ultra high molecular weight polyethylene plate was wetted with pure water to a contact angle of 10 degrees or less.
5) An acrylic resin (manufactured by polymethyl methacrylate) having the same size as that of the treated ultra-high molecular weight polyethylene plate was bonded with a cyanoacrylate adhesive at an adhesive part size of 10 cm × 15 cm.
6) After drying, a tensile peeling test (a test to pull in parallel with the bonding surface) was performed. As a result, the acrylic resin part was destroyed at 1 kN (110 kgf). The untreated ultra high molecular weight polyethylene plate did not adhere.

As the activation treatment of Example 32 1), ozone treatment was performed for 120 seconds. Other operations were performed in the same manner as in Example 32, and the same effects as in Example 32 were obtained.

Improvement of adhesiveness of polypropylene The polypropylene plate was treated in the same manner as in Examples 32-33, adhered to an aluminum plate with a cyanoacrylate adhesive, the same tensile peel test was performed, and adhesion was performed at 1.6 kN (166 kgf). The agent part was destroyed (cohesive failure).

Improvement of paintability and adhesiveness of fluororesin ethylene-tetrafluoroethylene copolymer 1) To a plate made of ethylene-tetrafluoroethylene copolymer (shape: rectangular parallelepiped, size: length 100 mm, width 30 mm, thickness 1 mm), A methanol solution of benzophenone as a photosensitizer (concentration: 10% by weight) was applied, and after 10 minutes, ultraviolet irradiation was performed for 2 minutes.
2) Next, the same treatment as in Example 30 was performed.
3) After the treatment, as a washing step, washing with boiling water was performed for 10 minutes, and ultrasonic washing was performed at 50 ° C. for 10 minutes, and it was confirmed that polyacrylic acid was not dissolved anymore.
4) The treated ethylene-tetrafluoroethylene copolymer plate was wetted with pure water to a contact angle of 10 degrees or less.
5) As a result of applying a water-based paint to this treated ethylene-tetrafluoroethylene copolymer plate, drying, and performing a cross-cut test, a favorable evaluation of 100/100 was obtained. Moreover, 100/100 was similarly obtained for the coating with the oil-based paint.
6) This treated ethylene-tetrafluoroethylene copolymer plate was bonded to an aluminum plate with a cyanoacrylate adhesive, and the same tensile peel test as in Example 32 was performed. At 1.8 kN (186 kgf), the adhesive The layer broke and crushed.

As the activation treatment of Example 35 1), ozone oxidation was performed for 30 seconds. Other operations were performed in the same manner as in Example 35, and the same effects as in Example 35 were obtained.

As the activation treatment of Example 35 1), plasma treatment was performed for 30 seconds. Other operations were performed in the same manner as in Example 35, and the same effects as in Example 35 were obtained.

Instead of the polymer treatment of Example 35 2), as an grafting treatment, an acetone solution of vinyl acetate and methacrylic acid (volume mixing ratio 1: 1, concentration 5% by weight) was added to the activated tubular protrusion. And heated at 80 ° C. for 5 minutes. For 30 seconds. Other operations were performed in the same manner as in Example 35, and the same effects as in Example 35 were obtained.

Improvement of Paintability and Adhesiveness of Fluororesin Polyvinylidene Fluoride The same treatment as in Examples 35 to 38 was performed on a plate of polyvinylidene fluoride resin. The obtained sample was tested in the same manner as in Example 35. As a result, 100/100 was obtained in the paintability cross-cut test. In addition, the adhesive layer cohesively failed in adhesion to the aluminum plate.

Improvement of adhesion of fluororesin polytetrafluoroethylene 1) The same treatment as in Examples 35 to 38 was performed.
2) Next, as a cleaning treatment, the substrate was washed with boiling water for 1 minute, and then ultrasonically washed with water at 80 ° C. for 5 minutes. After drying, good hydrophilicity was obtained for the polytetrafluoroethylene plate: water contact angle 15-30 degrees.
3) As a result of applying a water-based paint to this treated polytetrafluoroethylene plate, drying and performing a cross-cut test, an evaluation of 70/100 was obtained. Moreover, 80/100 was obtained by painting with an oil-based paint. The untreated sample was not wetted at all by the aqueous / oil-based paint.

Adhesion test of fluororesin polytetrafluoroethylene 1) The polytetrafluoroethylene plate treated in Example 40 was bonded to an aluminum plate with a cyanoacrylate adhesive. A tensile peel test similar to that in Example 35 was performed, and an adhesive having a considerable strength of 1.4 kN (143 kgf) was obtained. Peeling occurred at the interface of the polytetrafluoroethylene plate. The untreated sample was not wetted at all by the aqueous / oil-based paint.
2) A double-sided tape (manufactured by 3M, 3M-VHB acrylic foam structure joining tape (general use) high soft type Y4608) was applied to the treated polytetrafluoroethylene plate and adhered to the wood block. The bonded polytetrafluoroethylene plate was subjected to a tensile peel test and was not peeled even by a tensile force of 50 kgf / square centimeter. The untreated polytetrafluoroethylene plate was peeled with a tensile force of 0 to 1 kgf / square centimeter in the same tensile peel test.

Adhesion test of modified fluororesin polytetrafluoroethylene The foamable polytetrafluoroethylene sheet was subjected to the same surface modification treatment as in Examples 35-38. The modified expandable polytetrafluoroethylene sheet was cut into a circle having a diameter of 50 mm, and a circular hole having a diameter of 45 mm was formed in the center to form a ring shape. Two modified foamed polytetrafluoroethylene sheets are coated with polyvinyl-vinyl acetate glue (produced by Yamato Co., Ltd., Arabic Yamato), and the ring of these two modified foamed polytetrafluoroethylene sheets is used. The same type of stainless steel ring (thickness 1 mm) was bonded and dried, and a laminated bracket was manufactured. This laminated bracket showed good bracket airtightness when connecting stainless steel tubes having the same cross-section.

Production of composite material using modified polypropylene fiber and strength test Polypropylene fiber plain woven fabric (sample size: 100 × 100 mm, thickness: 0.6 mm, basis weight: 10 g / m 2) is the same as in Examples 15-18 Processed. A plain woven fabric of modified polypropylene fiber is bisphenol A-type epoxy resin (low-viscosity epoxy resin Z-1 manufactured by Nissin Resin Co., Ltd.), a curing agent, and a modified alicyclic polyamine (Nisshin Resin Co., Ltd. transparent type curing). The composite material test piece (sample size: 100 × 100 mm, thickness: 1.8 mm) was prepared by being sandwiched between the mixture of the agent (Craft Resin)) for a predetermined time. A composite material test piece was similarly prepared for a plain woven fabric of untreated polypropylene fibers. As a result of measuring the interlaminar shear strength before and after the modification, the interlaminar shear strength was 1.3 MPa for the untreated polypropylene fiber plain woven fabric composite specimen and 18 for the modified polypropylene fiber plain woven composite specimen. The strength was increased to 0.6 MPa. Furthermore, as a result of preparing a composite material test piece using conventional glass fiber or carbon fiber in the same manner, the composite material using glass fiber or carbon fiber breaks and separates, but the composite material of plain woven fabric of modified polypropylene fiber It was found that even when the material was broken, the modified polypropylene fiber was not cut and the material was not separated.

Test for charging property of molded product made of modified polypropylene With reference to the test method for color fastness to friction (JIS L 0849: 2004) for a molded product made of modified polypropylene obtained by the same treatment as in Examples 15 to 18. Then, a triboelectric charge test was conducted. In the triboelectricity test, a polypropylene sample (size 100 × 100 mm) and a woolen fabric (size 100 × 100 mm) were rubbed 30 times and charged with an electrostatic potential meter (Scitostatic STATIRON-DZ3) without grounding. Was measured. As a result, the charge amount was minus 8.00 kV for the untreated polypropylene molded product, minus 3.50 kV for the modified polypropylene molded product, and the chargeability decreased with the modified polypropylene molded product.

For materials other than polypropylene, such as chargeable polyethylene, polyester, polycarbonate, silicon resin, and fluorine resin, the same treatment as in Examples 15 to 18 was performed, and the chargeability decreased.

Claims (28)

(1) an activation treatment, (2) a treatment with a polymer solution in the presence of a catalyst or an initiator, (3) a monomer grafting step, and (4) a washing step. A polymer material having improved adhesion, paintability, printability, and chargeability obtained by a modification method characterized by processing in the order of:   A modification characterized by treating a polymer material in the order of (1) an activation treatment, (2) a treatment with a polymer solution in the presence of a catalyst or an initiator, and (3) a washing step. Polymer material with improved adhesion, paintability, printability and chargeability obtained by the method. The polymer material is treated in the order of (1) a solvent treatment step, (2) an activation treatment step, (3) a treatment step with a polymer solution in the presence of a catalyst or an initiator, and (4) a washing step. A polymer material having improved adhesion, paintability, printability and chargeability obtained by a modification method characterized by the above. The polymer material is contacted with (1) a compound impregnating the polymer material, and the impregnation amount is within a range of 0.1 to 40% by weight (with respect to the polymer material) within 1000 microns from the surface. And an impregnation treatment step that does not substantially change the shape of the material, (2) an activation treatment step for introducing a carbonyl group to the surface of the polymer material, (3) at least one of a catalyst, an initiator, heating, and ultraviolet irradiation Modified adhesiveness, paintability and printability obtained by a modification method characterized in that the monomer is grafted in the presence of (4) and the washing step is performed in this order. Charged polymer material.   (1) Solvent treatment step, (2) Activation treatment step, (3) Treatment with polymer solution in the presence of catalyst or initiator, (4) Monomer grafting step And (5) A polymer material having a modified adhesive property, paintability, printability and chargeability obtained by a modification method characterized by processing in the order of washing steps. The adhesive polymer material refers to a polymer material that can be bonded using an adhesive and can be bonded using a solvent without using an adhesive. The inner wall of the sample tube made of a polymer material is brought into contact with (1) a compound impregnating the polymer material, and the impregnation amount within 1000 microns from the surface is 0.1 to 40% by weight (vs. polymer) Impregnation treatment step that does not substantially change the shape of the material, (2) activation treatment step for introducing a carbonyl group to the surface of the polymer material, (3) catalyst, initiator, heating A modified method obtained by a modification method characterized in that the step of grafting the monomer or polymer in the presence of at least one of ultraviolet irradiation and the step of (4) washing are performed in this order. Sample tube made of polymer material.   The polymer material is a homopolymer of at least one monomer selected from the group consisting of fluororesins, silicone resins, olefins, vinyl compounds other than olefins, vinylidene compounds, and other compounds having a carbon-carbon double bond. Or copolymer, polycarbonate, polyester, polyamide, polyimide, polyurethane, polybenzoate, polybenzoxazole, poly-p-phenylenebenzobisoxazole, polybenzothiazole, poly-p-phenylenebenzobisthiazole, polyalkylparaoxybenzoate, poly 6. The polymer according to claim 1, which is benzimidazole, carbon material, polyphenol, acetate, regenerated cellulose, vinylon, polyclar, casein, wool, silk, or hemp. Method of modifying a fee.   The polymer material is selected from the group consisting of fibers, woven fabrics, knitted fabrics, non-woven fabrics, plates, bars, tubes, hoses, sample tubes for samples, films, sheets, porous films and sheets, and members or products molded into a predetermined shape. The method for modifying a polymer material according to any one of claims 1 to 8, wherein the polymer material is a molded material or a composite material with other materials.   The polymeric material according to any one of claims 1 to 9, wherein the polymeric material is joined so as to make it difficult to separate a tubular member made of different materials, for example, a soft member and a hard member. Modification method.   The high polymer material according to any one of claims 1 to 9, wherein the polymer material is joined by solvent bonding so that a tubular member made of different materials, for example, a soft member and a hard member are difficult to be detached. A method for modifying molecular materials.   12. The polymer material according to any one of claims 1 to 11, wherein the polymeric material is a medical infusion device and is joined so as to make it difficult to separate tubular members made of different materials, for example, a soft member and a hard member. A method for modifying a polymer material as described.   12. The polymer material according to claim 1, wherein the polymer material is a drip device for medical use, and is a drip tube provided with a small-diameter tubular protrusion at an end thereof and a tubular member coupled thereto. A method for modifying polymeric materials.   The activation process is at least one process selected from the group consisting of an oxidant process, an ozone process, a plasma process, an ultraviolet irradiation process, a corona discharge process, and a high-pressure discharge process. The method for modifying a polymer material according to any one of the above.   The polymer solution is polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyhydroxyethyl methacrylate, poly-α-hydroxy vinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinyl pyrrolidone, polyalkylene glycol, starch, glucomannan, fibroin, It is at least one polymer compound selected from the group consisting of sericin, agar, gelatin, egg white protein and sodium alginate, polyacrylic acid ester, polymethacrylic acid ester, silicon resin, and fluorine-containing resin. The method for modifying a polymer material according to claim 1.   The polymer material modification according to claim 1, wherein the monomer is a compound having a carbon-carbon double bond in the grafting step of the monomer. Quality method.   The monomer is acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, vinyl acetate, 2-butenoic acid, ethylene sulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, At least one monomer selected from the group consisting of alkylene glycol monoacrylate, alkylene glycol monomethacrylate, N-vinyl-monoalkyl-caprolactam, N-vinyl-dialkyl-caprolactam, maleic anhydride, and pyromellitic anhydride The polymer material modification according to any one of claims 1, 4, 5, and 7, wherein the polymer material is a mixture of at least one monomer selected from these groups and another vinyl monomer. Method.   8. The method for modifying a polymer material according to claim 1, wherein the monomer grafting step is performed in the presence of a catalyst or an initiator. . The monomer grafting step comprises (1) heat treatment in the presence or absence of a catalyst or initiator, and (2) in the presence or absence of a catalyst or initiator or photosensitizer. The method for modifying a polymer material according to any one of claims 1, 4, 5, and 7, which is carried out by any one or a plurality of methods of ultraviolet irradiation.   The initiator is at least one compound selected from the group consisting of peroxides, ceric ammonium nitrate (IV), persulfates, redox initiators and other radical polymerization initiators. The method for modifying a polymer material according to any one of claims 1 to 7, 16, or 18.   A modified polymer material obtained by the method for modifying a polymer material according to any one of claims 1 to 20.   A composite material comprising a modified polymer material obtained by the method for modifying a polymer material according to any one of claims 1 to 20.   A polymer material with improved solvent adhesion obtained by the method for modifying a polymer material according to any one of claims 1 to 9 and 14 to 20.   21. A polymer material having improved printability with an ultraviolet curable ink obtained by the method for modifying a polymer material according to any one of claims 1 to 9 and 14 to 20.   A gasket manufactured using a polymer material with improved adhesion obtained by the method for modifying a polymer material according to any one of claims 1 to 9 and 14 to 20.   A polymer material with improved adhesiveness of the pressure-sensitive adhesive tape obtained by the method for modifying a polymer material according to any one of claims 1 to 20.   A medical device using a polymer material having improved adhesiveness of the pressure-sensitive adhesive tape obtained by the method for modifying a polymer material according to any one of claims 1 to 20. A medical device comprising a modified polymer material obtained by the method for modifying a polymer material according to any one of claims 1 to 20.