JP2002201297A - Method for modifying polymeric material, and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve the surface modification of a polymeric material to give excellent durability without a reduction in strength. SOLUTION: A polymeric material is modified by a process comprising a combination of a step of impregnation, a step of activation, a step of grafting a monomer, and a step of treatment with a hydrophilic polymer. The hydrophilicity, adhesiveness and the like of a polymeric material comprising e.g. a polyolefin can be improved by the process without the deterioration of its strength in practical use. As a result, it can realize the use of the material in many applications where water absorbency and adhesiveness are required, for example, as an absorbent material such as a wiping and cleaning material, a water-retentive material, a material for a microbial culture medium, a member for writing utensils, a battery separator, a synthetic paper, a filter medium, medical, sanitary and cosmetic goods, and textile products for clothing, and for the improvement in adherence of reinforcing fibers for a composite material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for modifying a polymer material. In particular, the present invention relates to a modification method for improving water absorption and adhesiveness without reducing the strength of a polymer material.
The present invention also relates to a polymer material obtained by such a modification method and its use.

[0002]

2. Description of the Related Art Polyolefin materials such as polypropylene and polyethylene are excellent in lightness, strength, chemical resistance and the like, and are widely used in molded articles such as films, nonwoven fabrics, automobile parts and electric equipment parts. However, polyolefin materials have low polarity and high crystallinity due to their chemical structure, and thus have poor hydrophilicity and are hardly subjected to chemical modification. Conventionally, to improve the hydrophilicity and adhesion of these materials, ozone treatment, plasma treatment, ultraviolet irradiation treatment, high pressure discharge treatment, corona discharge treatment,
Various surface activation treatments such as sand blast treatment, solvent etching treatment, chromium mixed acid treatment, and flame treatment have been attempted. However, even with these surface treatments,
It does not reach the point of imparting water absorption enough to absorb water several times its own weight. For example, a method of improving the plating property, the coating property, and the adhesive property by performing an ozone oxidation treatment has been studied (Japanese Patent Publication No. 3-103448). However, in order to impart desired surface characteristics only by ozone treatment, the ozone treatment must be severe, and the strength of the object to be treated is significantly reduced, which causes a problem that the object is not practically used. Further, water absorption cannot be sufficiently imparted only by the ozone oxidation treatment. All of the other treatment methods described above have problems such as difficulty in achieving high activation without a decrease in strength, an increase in equipment costs, and a burden on waste disposal.

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

On the other hand, there has been proposed a method of imparting hydrophilicity by treating a nonwoven fabric made of polyolefin fibers with a hydrophilic resin in the presence of a persulfate (JP-A-11-6711).
183 publication). With this method, the nonwoven fabric could be given hydrophilicity to a practical level, but the durability of the hydrophilicity was not always sufficient. For example, when heated and washed with a detergent, the hydrophilicity is considerably lost. Further, when a film or a molded product other than the nonwoven fabric was treated, sufficient hydrophilicity could not be imparted, or the adhesiveness with an adhesive could not be improved. There is also known a method of imparting hydrophilicity by coating a nonwoven fabric with polyvinyl alcohol (JP-A-1-248460). However, although the resulting coating has high hydrophilicity, there is a problem that the durability of the hydrophilicity is not sufficient because it is merely a coating.

Further, the present inventor has proposed that the surface of a polymer material is first activated, and then a monomer such as acrylamide is graft-polymerized, or the amide group of the grafted compound is subjected to Hoffman rearrangement. A method for modifying the surface of a polymer material with improved dyeing properties has been proposed (JP-A-8-109228). On the basis of this method, a polymer material having hydrophilicity can be produced, but there is a limit to the type of polymer material to be treated in this method. Furthermore, the present inventor should treat the polymer material in the order of (1) the step of activating and (2) the step of treating with a hydrophilic polymer. Or, a polymer material
(1) an activation treatment step (2) a treatment with a hydrophilic polymer and (3) a grafting step of a monomer, or a polymer material is subjected to (1) a solvent treatment step, Japanese Patent Application No. 11-3750 proposes a method for modifying a polymer material, which comprises the steps of (2) an activation treatment step and (3) a treatment step with a hydrophilic polymer.
55, PCT / JP00 / 090420). According to these methods, a polymer material having excellent hydrophilicity can be easily manufactured at low cost. However, these additives reduce the effect of the activation treatment when processing a molded article of a polymer material containing additives such as stabilizers and antioxidants to obtain strong durable hydrophilicity. There are cases.

[0006] The above technical requirements exist not only for polyolefins, but also for other polymer materials having better surface activity. For example, there are cases where it is required to modify the intrinsic surface properties of the polymer to impart desired surface properties.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for modifying the surface of a polymer material which is excellent in durability without reducing the strength of the material and aims at overcoming the above-mentioned disadvantages. . The present invention is also directed to medical, hygiene, and cosmetic products comprising such modified materials, that is, disposable diapers, sanitary products, bandages, gauze, disinfecting adhesive cloths, various clean use / face-wash packs, napkins, and the like. Water-absorbing materials, water-retaining materials such as agricultural / dry land greening materials, microbial medium materials,
Synthetic paper, filter media, wiping and cleaning materials, orthodontic brackets, medical device materials (artificial organs, joints, various tubular, thread-like, plate-like molded products), polymer materials with improved adhesiveness and An object is to provide a composite material with a polymer material and the like.

[0008]

Means for Solving the Problems The inventor of the present invention has intensively studied surface modification methods for various polymer materials to achieve the above object, and has found that impregnation treatment, activation treatment, and vinyl monomer The present inventors have found that it is effective to combine grafting and treatment with a hydrophilic polymer, and have completed the present invention. That is, the present invention relates to (1) bringing the surface of a polymer material into contact with a compound (referred to as an impregnating agent) impregnating the polymer material to a depth of 100
An impregnation step in which the impregnation amount within a micron is in the range of 0.1 to 40% by weight (based on a polymer material), and the shape of the material is not substantially changed; (2) an activation step for introducing a carbonyl group And (3) a method of modifying a polymer material, wherein the treatment is performed in this order by a step of grafting a monomer.

Alternatively, the present invention provides a method for forming a surface of a polymer material,
(1) The polymer material is brought into contact with a compound having an impregnating property, and impregnated within a range of 0.1 to 40% by weight (based on the polymer material) within a depth of 100 μm from the surface, An impregnation process that does not substantially change the shape of the material,
(2) an activation treatment step for introducing a carbonyl group, (3)
The present invention relates to a method for modifying a polymer material, wherein the treatment is performed in this order by a step of treating with a hydrophilic polymer.

[0010] Alternatively, according to the present invention, the surface of a polymer material is
(1) The polymer material is brought into contact with a compound having an impregnating property, and impregnated within a range of 0.1 to 40% by weight (based on the polymer material) within a depth of 100 μm from the surface, An impregnation process that does not substantially change the shape of the material,
(2) an activation treatment step for introducing a carbonyl group, (3)
The present invention relates to a method for modifying a polymer material, wherein the treatment is performed in this order by a step of treating with a hydrophilic polymer and (4) a step of grafting a monomer.

[0011] Alternatively, the present invention provides a polymer material having a surface modified by such a modification method, and a water-absorbing material, a water-retaining material, a material for a microorganism culture medium, a synthetic paper using the same,
Filtration material, cloth for wiping and cleaning, disposable medical / hygiene / cosmetic products (diapers, sanitary products, bandages, gauze, napkins, tapes, other medical / hygiene products, cosmetic products such as various clean use / face-wash packs), adhesive The present invention relates to an orthodontic material, an orthodontic bracket, a medical device material (artificial organ, tube, thread, plate-like molded product), and the like.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Polymer material) The polymer material used in the present invention refers to a polymer alone, a mixed material or a modified product thereof, or a mixture or a composite of such a polymer material with glass, metal, carbon material or the like. It means a polymer material contained in the obtained material. As the synthetic polymer, any of a thermoplastic polymer and a thermosetting polymer can be used. Various methods are exemplified as the synthesis method, and 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 homopolymers or copolymers thereof (2) Polycondensate: polyester, polyamide, etc., or a mixture or modified product of these polymers; (3) Addition condensate: phenolic resin (Kynol: trade name, manufactured by Nippon Kainol Co., Ltd.) including),
Urea resin, melamine resin, xylene resin, etc., or a mixture or modified product of these polymers; (4) polyaddition product: polyurethane, polyurea, etc., or a mixture or modified product of these polymers; Ring polymer: homopolymer or copolymer such as cyclopropane, ethylene oxide, propylene oxide, lactone, lactam, or a mixture or modified product of these homopolymers or copolymers, (6) cyclopolymer: Homopolymers or copolymers such as divinyl compounds (eg, 1,4-pentadiene) and diyne compounds (eg, 1,6-heptadiyne), or mixtures or modified products of these homopolymers or copolymers, 7) Isomerized polymer: for example, an alternating copolymer of ethylene and isobutene; (8) electrolytic polymer: pyrrole; Diphosphate, homopolymers or copolymers, such as acetylene or a mixture or reformate these homopolymers or copolymers, (9) an aldehyde or ketone polymer, (10) polyethersulfone,
(11) polypeptides and the like. Examples of the natural polymer include a single substance or a mixture of cellulose, protein, polysaccharide, and the like, and a modified product thereof.

In the present invention, the above-mentioned addition polymer is particularly preferably used. The monomer constituting the addition polymer is not particularly limited, but as the olefin, ethylene,
Propylene, butene-1, pentene-1, hexene-
Any α-olefin homopolymer such as 1,4-methyl-pentene-1 and octene-1 or a copolymer of two or more thereof, or a mixture of these homopolymers and / or copolymers It can be used as appropriate. The vinyl compound other than the olefin in the present invention is a compound having a vinyl group, for example, vinyl chloride, styrene, acrylic acid, methacrylic acid, esters of acrylic acid or methacrylic acid, vinyl acetate, vinyl ethers,
Vinyl carbazole, acrylonitrile and the like. The vinylidene compound other than the olefin is a compound containing a vinylidene group, and examples thereof include vinylidene chloride, vinylidene fluoride, and isobutylene. Examples of compounds having a carbon-carbon double bond other than olefins, vinyl compounds, and vinylidene compounds include maleic anhydride, pyromellitic anhydride, 2-butenoic acid, ethylene tetrafluoride, ethylene trifluoride chloride and the like, and a double bond. A compound containing two or more
For example, butadiene, isoprene, chloroprene and the like can be mentioned.

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

The polymer material other than polyolefin is a homopolymer of at least one monomer selected from the group consisting of vinyl compounds other than olefins, vinylidene compounds and other compounds having a carbon-carbon double bond. Copolymers, for example, polymethacrylate resin, polyacrylate resin, polystyrene, polytetrafluoroethylene, acrylonitrile copolymer (acrylic fiber and molded products thereof, ABS resin, etc.), copolymer containing butadiene (Synthetic rubber), etc., polyamides (including aliphatic polyamides and aromatic polyamides including nylon), polyesters (including polyethylene terephthalate and aliphatic and wholly aromatic polyesters), polycarbonates, polyurethanes, polybenzoates, polyethers Tersulfone, poloacetal, various synthetic rubbers and the like are preferably used.

Examples of the polymer compound other than those described above include polyacetal, polyphenol, polyphenylene ether, polyalkylparaoxybenzoate, polyimide, polybenzimidazole, poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole, Examples include polybenzothiazole, polybenzoxazole, acetate for fibers, regenerated cellulose fibers (rayon, cupra, polynosic, etc.), vinylon, fibers of a copolymer of vinyl alcohol and vinyl chloride (polychlor, brand name: Cordelaan, etc.). can do. Further, natural fibers such as carbon fibers, cotton, hemp and other plant fibers, and animal fibers such as silk and wool can also be used. A mixture or composite of a plurality of these polymer materials can also 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 various additives usually added to polymer materials. No problem. In general, stabilizers such as antioxidants hinder surface activation, so their existence is considered to be unfavorable. 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 usual 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, fiber,
Any form of woven fabric, nonwoven fabric, cloth, plate, film, sheet, tube, rod, hollow container, box, foam, or laminate can be used. Particularly, from the viewpoint of improving water absorption, molded products such as fibers, woven fabrics, nonwoven fabrics, cloths, films, sheets, etc. can be easily treated. In particular, porous films and sheets manufactured for filters and synthetic paper can be durable and effective hydrophilization treatment. In addition, by applying the treatment method of the present invention to a molded article for a member or component which has been molded into a predetermined shape in advance, a polymer material which could not be used conventionally can be used. Various plastic products (bolts, nuts,
According to the present invention, the wettability and adhesiveness are improved, and the chargeability is also reduced by making the chain, electric appliance parts, caps, covers, and the like) hydrophilic according to the present invention. As the fiber or fiber product, various fibers, woven or non-woven fabrics thereof can be preferably used. Fiber form is a single component fiber, a mixture of multiple types of fiber, blended fiber,
Any of composite fibers (core-sheath type, side-by-side type, multi-core type, multi-core type, radiation type, etc.) may be used.

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

(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 a dispersion, and the polymer material is brought into contact with the polymer material at a temperature lower than its softening point, whereby the compound is treated. This is a method of impregnating from the surface. At this time, the polymer material does not substantially deform. The compounds used for this purpose are called impregnating agents. This impregnating step can be said to be a step in which the impregnating agent penetrates into the non-crystalline region of the polymer compound to form a gap inside the material. This has the effect of facilitating the subsequent activation treatment, grafting treatment and the like.
The impregnated impregnant is removed by washing after a subsequent processing step. When the preferable range of the impregnating amount of the impregnating agent with respect to the polymer material is represented by a weight increase rate, the thickness of the polymer material is 1%.
If the thickness is less than 000 microns, it is 0.1-40% by weight, and if the thickness of the material is 1000 microns or more, it is 0.1-40% by weight for a portion of the material 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 20 mm or less, the impregnation amount is simply 0.1%.
About 10 to about 10% by weight is preferred.

The compound that can be used as the impregnating agent is not limited to organic or inorganic compounds, and may be any of gas, liquid and solid, as long as it is a compound having an affinity for the polymer material. The liquid impregnating agent can be used as it is or as a mixture of a solution and a dispersion with another liquid. If it is a solid, it can be used as a solution or dispersion, an emulsion, or if it is a gas, it can be used as it is. 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 commercial carrier dyeing auxiliaries can be preferably used. Also, 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 are diphenyl, ortho- or para-hydroxybiphenyl, other diphenyl derivatives, or
Sodium salicylate or derivatives thereof, halogenated aromatic compounds (for example, mono-, di- or trichlorobenzene), etc. For these, as an organic liquid solution using hexane, methanol, or the like as a solvent, an aqueous dispersion, or an emulsion using a surfactant. Can be used. Alternatively, an organic liquid having an affinity for a polymer material can be used as the impregnating agent. The guideline for selecting an organic liquid in this case is a single liquid or a mixture of liquids having similar solubility parameters (SP values) of the polymer material to be treated. It is preferable to treat with a solvent having a difference of about +2 or −2 depending on the solubility parameter of the polymer. Solvents having a difference within this range can be used if processed at a low temperature in a short time. Do not dissolve, just soak into the polymer surface. Even an organic solvent that is soluble at a high temperature can be used if it is processed in a short time at a low temperature that does not show solubility. As an example of the liquid impregnating agent, in the case of polypropylene, toluene, xylene, decalin, tetralin, cyclohexane, a mixture of 1 volume of dichloroethane and 4 volumes of ethanol, and polyethylene include toluene, xylene, α-chloronaphthalene, 1 volume of dichlorobenzene A mixture of 1 volume of toluene and 10 volumes of methanol can be used for polystyrene, and a mixture of 1 volume of phenol and 10 volumes of hexane can be used for polyethylene terephthalate.

Conditions such as temperature and time of the impregnation treatment are appropriately selected according to the shape of the material. For example, a fiber diameter of 5-1
In the case of a non-woven fabric made of polyolefin fibers of about 0 μm, the non-woven fabric is immersed in an impregnating agent (for example, toluene) at room temperature for 2 minutes and shaken off by a centrifugal dehydrator (500 to 2,000 revolutions / minute). When it is apparently dry, the process is terminated. In the case of a polyolefin film, plate or molded product (having a thickness of about 2 to 5 mm), it is immersed in an impregnating agent at room temperature to 70 ° C. for about 5 to 30 minutes, and then drained as described above. The impregnation weight ratio in these cases is about 1 to 10% by weight. In the case of wool, a mixture of aqueous sodium carbonate and methanol at room temperature
After soaking for 10 minutes, rinse with methanol and remove the liquid with a centrifuge. This impregnation is effective for a molded product having a large surface area, such as a film or a plate, or a material containing a large amount of an antioxidant or other additives.

(Activation Treatment Step) The step of activating the polymer material in the present invention means a treatment for introducing a carbonyl group to the surface of the material. In addition to the carbonyl group, introduction of a functional group containing oxygen or nitrogen, an unsaturated bond, or the like is also included. Preferred methods of the activation treatment include various treatments such as a plasma treatment, an ozone treatment, an ultraviolet irradiation treatment, a corona discharge treatment, and a 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 reforming, but in the present invention, the minimum activation treatment that can confirm the introduction of the carbonyl group is preferable. The conventionally proposed activation processing method is often an excessive processing for the purpose of the present invention. As a guide for the determination, 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 to the absorbance of the absorption based on the structure of the unchanged crystal part can be determined by a baseline method to determine the degree of oxidation. For example, the absorption based on the crystalline portion of methyl groups of the absorbance and unchanged around 1710 cm ^-1 based on the carbonyl groups introduced in the case of polypropylene 973 cm ^-1
Is preferably about 0.2 or less. A preferred method for setting the activation treatment conditions is to obtain the relationship between the treatment time and the carbonyl absorption for the target polymer material in advance, and based on this relational expression, activate the treatment to such an extent that the material strength is not reduced. Set conditions.
If the intensity is reduced even when the minimum carbonyl group that can be detected by infrared absorption spectroscopy is present,
Based on this relational expression, an appropriate processing time is obtained by interpolating the time corresponding to the absorbance that cannot be measured by infrared absorption. 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 bring the surface of a polymer material into contact with ozone molecules to carry out a reforming reaction mainly involving an oxidation reaction. Ozone treatment
This is done by exposing the polymeric material to ozone.
The exposure method can be performed by an appropriate method such as a method of maintaining the ozone in an atmosphere for a predetermined time or a method of exposing it to an ozone stream for a predetermined time. Ozone can be generated by supplying an oxygen-containing gas such as air, oxygen gas, or oxygenated air to an ozone generator. The obtained ozone-containing gas can be introduced into a container, a tank or the like holding the material to perform ozone treatment. The conditions of ozone concentration in ozone-containing gas, exposure time and exposure temperature are as follows:
It can be appropriately determined according to the type and shape of the polymer material and the purpose of the surface modification. Usually, an oxygen or air stream is used, and a flow rate of 20 ml to 10 L / min and a flow rate of 10 to 200
g / m ^{3 at} a concentration of 10-80.
The treatment can be carried out at a temperature of 1 ° C for 1 minute to 10 hours. For example, in the case of polypropylene or polyvinyl chloride fiber, treatment at an ozone concentration of 10 to 40 g / m ³ at room temperature for about 10 to 30 minutes is appropriate. In the case of a film, the ozone concentration is about 10 to 80 g / m ³ and the
A treatment of about 0 minutes to 3 hours is appropriate. The generated ozone concentration when air is used is about 50% of that when oxygen is used. Ozone treatment causes the surface of the polymer material to undergo hydroperoxy groups (--O-
OH) are introduced, and a part of them is presumed to change into a functional group such as a hydroxyl group or a carbonyl group.

(Plasma Treatment) In the plasma treatment, a polymer material is placed in a container containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen or air, exposed to plasma generated by glow discharge, and the surface of the material is exposed to oxygen. ,
The purpose is to introduce a functional group containing nitrogen or the like. When an inert gas such as argon or neon exists at low pressure, the surface of the polymer material is attacked by the generated plasma,
It is considered that radicals are generated on the surface. afterwards,
It is considered that the radical is bonded to oxygen by exposure 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. It is considered that the functional group is directly introduced by a plasma treatment in a trace amount of nitrogen, carbon dioxide, oxygen or air. Discharge types of plasma generation are classified into (1) DC discharge and low frequency discharge, (2) radio wave discharge, (3) microwave discharge, and the like.

(Ultraviolet irradiation treatment) The ultraviolet irradiation treatment is a method of irradiating the surface of a polymer material with ultraviolet light in the air. As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Before irradiation, the surface of the polymer material may be treated with an ultraviolet absorbing solvent. The wavelength of the ultraviolet light can be appropriately selected, but is preferably around 360 nm or less in order to reduce the deterioration of the material. When the polymer material is irradiated with ultraviolet light, the ultraviolet light is absorbed by a chemical structure such as a double bond in the surface region of the molded product, the chemical bond is cut by the absorbed energy, and oxygen in the air is generated by generated radicals. It is considered that they form a carbonyl group, a carboxyl group, etc. by bonding and passing through a peroxide structure in the middle.

(High-Pressure Discharge Treatment) In the high-pressure discharge treatment, a belt conveyor for moving a polymer material to be treated is installed in a tunnel-like treatment device, and the inside of the treatment device is moved while the polymer material is moved. This is a method in which a high voltage of several hundred thousand volts is applied between a large number of electrodes attached to a wall surface, and the electrodes are discharged in air for treatment. It is considered that the oxygen in the air and the surface of the object to be treated are activated by the discharge, and the oxygen is taken into the surface of the polymer material to generate a polar group.

(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 knife-shaped electrode placed at a distance of several mm from the metal roll. In this method, the polymer material to be processed passes between the electrode and the roll during the discharge. This method is suitable for processing films or thin materials.

The method other than the ozone treatment activates the surface by irradiating the material, and it is necessary to devise a shadowed portion where the radiation is not applied. Therefore,
The ozone treatment is preferable for treating the entire fiber aggregate such as a nonwoven fabric or a material having a shadowed portion depending on the form of the material. In addition, ozone treatment is inexpensive and is preferable in terms of equipment costs.

(Monomer Grafting Step) The monomer to be grafted in the present invention is not limited as long as it can be grafted, but is a compound having at least one carbon-carbon double bond, for example, a vinyl compound. Or similar compounds are preferred. Among the monomers, hydrophilic monomers are preferred. As the hydrophilic monomer, acrylic acid, methacrylic acid, vinyl acetic acid, 2-butenoic acid, ethylene sulfonic acid,
At least one monomer selected from the group consisting of hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinylpyridine, vinylpyrrolidone, vinylcarbazole, maleic anhydride, and pyromellitic anhydride, or at least one selected from these groups And a mixture with a monomer of the formula (1). In the present invention, use of acrylic acid or methacrylic acid is particularly preferred from the viewpoint of chemical resistance and water absorption.

Further, vinyl monomers such as acrylic acid esters, methacrylic acid esters, vinyl acetate and styrene, which are monomers having a lower hydrophilicity than the hydrophilic monomers, can also be used. It is preferable to use only a hydrophilic monomer, but by using a mixture of a hydrophilic monomer and a poorly hydrophilic monomer, the grafting rate is increased, and the hydrophilicity contained in the graft polymer is increased. In some cases, monomers can impart hydrophilicity to the material.

The grafting of the monomer is carried out by (1) a method in the presence of a catalyst or an initiator (hereinafter collectively referred to as "initiator"), and (2) a method in the presence or absence of an initiator. Either a heating method or (3) a method of irradiating ultraviolet rays in the presence or absence of a catalyst or an initiator is preferable. Initiators include peroxides (benzoyl peroxide, t
-Butylhydroxyperoxide, di-t-butylhydroxyperoxide, etc.), ammonium dicerium nitrate (IV), persulfate (potassium persulfate, ammonium persulfate, etc.), a redox initiator (oxidizing agent: persulfate, persulfate, etc.) Combination of hydrogen oxide, hydroperoxide, etc. with inorganic reducing agent: copper salt, iron salt, sodium bisulfite, sodium thiosulfate, etc., or organic reducing agent: alcohol, amine, oxalic acid, etc., and oxidizing agent: hydroperoxide, etc. And inorganic reducing agents: copper salts, iron salts, sodium bisulfite, sodium thiosulfate, etc., or organic reducing agents: dialkyl peroxide, diacyl peroxide, etc. and reducing agents: tertiary amines, naphthenates, mercaptans, organometallic compounds (Combination with triethylaluminum, triethylboron, etc.) Such as known radical polymerization initiators. When acrylic acid is used as a monomer, a water-soluble polymerization initiator such as dicerium ammonium (IV) nitrate or potassium persulfate is preferably used,
Water-insoluble initiators such as benzoyl peroxide and N, N-azobisisobutyronitrile can be used by dissolving in methanol or acetone and mixing with water. In the case of ultraviolet irradiation, a photosensitizer such as benzophenone or hydrogen peroxide may be added as a catalyst in addition to these polymerization initiators.

For grafting of the monomer, a general grafting method can be used. Specific examples are shown below. In the case of a water-soluble initiator, dissolve the required amount in water. In the case of a water-insoluble initiator, the initiator is dissolved in an organic solvent (for example, acetone, methanol or the like) that mixes with water, such as alcohol or acetone, and then mixed with water so that the initiator does not precipitate.
A material which has been subjected to an activation treatment or a hydrophilic polymer treatment described below is added to the initiator solution, and a monomer is added thereto to perform grafting. The inside of the processing container is replaced with nitrogen as needed. 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 applied at an appropriate temperature and time. The ultraviolet lamp is not particularly limited, but a high-pressure mercury lamp (for example, trade name: H400P, manufactured by Toshiba Corporation) can be used. Ultraviolet light having a wavelength of about 360 nm may be extracted with a filter, or may be irradiated with 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 subjected to Hoffman rearrangement according to the method described in JP-A-8-109228 of the present inventors 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 easily soluble in water 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 and And 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 a hydrophilic polymer) When the activated polymer material is treated with a hydrophilic polymer,
It is preferably carried out in the presence of a catalyst or an initiator. As the catalyst and the initiator, those similar to those in the case of grafting with a monomer can be used. In the treatment step with a hydrophilic polymer, the hydrophilic polymer is preferably used in a solution state. Any water-soluble polymer can be used as an aqueous solution. If it is poor in water solubility, use it after dissolving it in an appropriate solvent. The case where a water-soluble polymer is used will be described below. In the case of performing the treatment with the water-soluble polymer in the absence of the initiator, the polymer material that has been subjected to the activation treatment is placed in an aqueous solution of a hydrophilic polymer, and the treatment is performed. 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, the initiator 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. The treatment is performed by adding the activated polymer material to the solution of the water-soluble polymer to which the initiator has been added. It is desirable that the inside of the processing vessel be replaced with nitrogen. However, for simplicity, practical treatment can be performed without nitrogen replacement. The temperature of the treatment with the water-soluble polymer and the initiator is not particularly limited, and is usually from 10 to 80 ° C, preferably from 60 to 90 ° C. In order to improve the durability of the hydrophilicity, the treatment may be performed at a high temperature for a long time (for example, about 12 hours).

(Uses) The polymer material modified by the method of the present invention has significantly improved hydrophilicity, water absorption, water retention, adhesiveness, etc., and excellent durability in its properties. Taking advantage of
It can be applied to various uses. In addition, because it has excellent adhesive properties, general adhesives, such as starch,
It can adhere to paper, wood, metal, etc. by polyvinyl acetate, polyvinyl alcohol, epoxy resin, polycyanoacrylate and the like. It can be applied to various materials that require adhesiveness. Furthermore, the modification method of the present invention can be applied to many polymer materials including polyolefins such as polypropylene and polyethylene, which are particularly difficult to modify. Polyolefin nonwoven fabrics, or mixed nonwoven fabrics composed of polyolefins and other polymers, can provide water absorption of about 7 to 10 times their own weight, and furthermore, have adhesiveness, alkali resistance, acid resistance, and oxidation resistance. Excellent. Each application will be described below, but the application of the present invention is not limited to the following.

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

(2) Water-absorbing material: A water-absorbing polymer material produced according to the present invention.

(3) Water retaining material: The hydrophilic polyolefin nonwoven fabric produced according to the present invention is useful as a water retaining material for supplying water to plants. The material shape as the water retention material for this purpose may be a woven fabric, a nonwoven fabric, a fiber having no fabric shape, or a cut fibrous waste. The diameter of the constituent fibers is preferably about 10 to 500 μm.

(4) Medical / Hygiene / Cosmetic Supplies: Various supplies of disposable specifications. Examples include diapers, sanitary products, bandages, gauze, sanitary napkins, disinfecting adhesive cloths and tapes, other medical supplies, various cleansing applications, face-wash packs,
And cosmetic articles such as pads. Disposable diapers or sanitary products contain a water-absorbing material made from pulp, starch, acrylic acid polymer, etc., and the outside,
It is covered with a water-repellent polyolefin nonwoven fabric so as not to transmit urine, moisture, blood and the like. Moisture released from the body passes through the inner hydrophilic nonwoven fabric and is absorbed by the inner water-absorbing material. As a material resistant to moisture and resistant to tearing, a hydrophilic polyolefin nonwoven fabric is the most desirable material. However, the hydrophilicity of the hydrophilized nonwoven fabric used on the inside is merely impregnated with a surfactant or a water-soluble treatment agent which easily falls off with water. For this reason, the hydrophilicity is not durable and is easily washed away with water. Also, the effect of surfactants on the skin is a problem. Therefore, an inexpensive, easy, and durable hydrophilization technique is desired. The water-absorbing and water-retaining polyolefin material obtained by the hydrophilicity-imparting technology of the present invention is an optimum material as a cloth for sewing inside a disposable diaper or sanitary article. The high-water-absorbing polymer material according to the present invention is also used as a water-absorbing material inside disposable diapers or sanitary products. It is lightweight, high-strength, safe, and able to withstand repeated use. Further, the hydrophilic or water-absorbing material obtained by the present invention is lightweight and high-strength, and can be impregnated with detergents, chemicals, adhesives, etc., so that gauze, a textile product for wiping, a cloth and tape for pasting and disinfecting, and the like can be used. Suitable for cosmetic products. When used as a disposable medical / hygiene / cosmetic product, the material shape is preferably a woven or nonwoven fabric, and the basis weight and thickness may be appropriately selected. However,
The diameter of the constituent fibers of the woven or nonwoven fabric is preferably about 1 to 500 μm.

(5) Internal materials such as clothes, beds, futons, etc .: The hydrophilic or water-absorbing polymer material obtained by the present invention is lightweight and high-strength, controls water absorption, and is a textile product for clothing. Suitable for internal materials such as bed, futon and so on.

(6) Filtration material: A filtration material comprising a porous film made of a hydrophobic material such as polyolefin, polysulfone, polyester, etc. has a higher strength than a paper filtration material, but is poor in hydrophilicity. Therefore, it is not suitable for filtering aqueous solutions. At present, a surfactant or a water-soluble polymer is applied to cope with such a problem. However, these hydrophilized parts are eluted during filtration and lack durability. By performing the hydrophilization treatment of the present invention on a filter material made of such a hydrophobic material,
A durable, water-absorbing filter material is obtained.

(7) Material for microbial culture medium: The water-absorbing material obtained by the present invention is excellent in water absorption, strength and microorganism propagation, and is most suitable as a microbial culture medium material. The shape of the material for the microorganism medium may be a woven fabric, a nonwoven fabric, a fiber having no fabric shape, or a cut fibrous waste. The diameter of the constituent fibers is preferably about 10 to 500 μm.

(8) Orthodontic bracket: The treatment method according to the present invention can improve the adhesiveness of a polymer material. It can be used for various materials that require adhesiveness, composite materials, and reinforcing fibers to be added to fiber-reinforced plastic, so that the adhesiveness between the plastic orthodontic bracket and the teeth can be improved.

(9) Parts for medical equipment materials: artificial blood vessels,
It refers to artificial organs, artificial joints, tubular, thread-like, and plate-like polymeric material parts. The hydrophilicity of these materials can be improved to improve their suitability for medical use. For example, those used in contact with the human body or human body tissue (catheter, drainage device),
Examples include body fluid absorbing materials, contact lenses, bandages made of synthetic fibers, gauze infusion devices and the like.

(10) Composite material of polymer material: It can be used as a polymer material composite material having excellent strength by improving the adhesiveness of the reinforcing fiber to be mixed with the composite material and the fiber reinforced plastic.

(11) Synthetic paper: Synthetic paper made of a polymer material such as polyolefin or polyester such as polyethylene or polypropylene gives whiteness by adding bubbles or fillers.
Used as a paper substitute. According to the present invention, the surface can be made hydrophilic to improve the adhesiveness and printability.

(12) Materials with Improved Adhesion:
In addition to improving the adhesiveness of orthodontic brackets and reinforcing fibers for composite materials, it is also possible to improve the adhesiveness of various polymer films and molded articles to improve the adhesiveness with the same or different materials.

(13) 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 has excellent adhesion and is easily wetted by water.
An antifogging effect can be obtained by attaching it 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 a polymer material (1) The characteristics of the nonwoven fabric, woven fabric, fiber bundle, film, plate, and porous film used in Examples and Comparative Examples are shown in Table 1. In addition, PP: polypropylene, PE: polyethylene, PET: polyethylene terephthalate, PSU: polysulfone, P / E: a mixed sample of PP and PE.

[Table 1]

(2) Orthodontic bracket: size 2.
23 x 3.0 x 3.8 mm, weight about 31 mg / piece, polypropylene molded product reinforced with aluminum fittings.

(B) Reagents (1) Polyvinyl alcohol (PVA): manufactured by Wako Pure Chemical Industries, Ltd., product number 160-11485 (average degree of polymerization =
(1500-1800) (2) Sodium carboxymethylcellulose (CM
C): Wako Pure Chemical Co., Ltd., product number 039-01355 (3) Acrylic acid: Wako Pure Chemical Co., product number 011
-00776 (4) Methacrylic acid: manufactured by Wako Pure Chemical Industries, Ltd., product number 13
8-10805 (5) Methyl methacrylate: manufactured by Wako Pure Chemical Industries, Ltd., product number 139-02726 (6) Sodium persulfate (SPS): Wako Pure Chemical Industries, Ltd.
Product No. 195-04985 (7) Potassium persulfate (KPS): manufactured by Wako Pure Chemical Industries, Ltd.
Product number 162-04235 (8) 2,2'-azobisisobutyronitrile (AIB
N): Product number 019-04932, manufactured by Wako Pure Chemical Industries, Ltd. (9) Ammonium dicerium nitrate (IV) (CAN):
(10) Benzophenone: manufactured by Wako Pure Chemical Co., Ltd., product number 023-01072 (11) Methanol: manufactured by Wako Pure Chemical Co., product number 13
6-09475 (12) Sodium hydroxide: manufactured by Wako Pure Chemical Industries, Ltd., product number 194-02135 (13) Hydrochloric acid: manufactured by Wako Pure Chemical Industries, product number 080-0
1066 (14) Toluene: manufactured by Wako Pure Chemical Industries, Ltd., product number 204
-01866, this liquid itself was used (impregnating agent A). (15) Sodium dodecylbenzenesulfonate (DB
S): Tokyo Chemical Industry Co., Ltd., product number D1238, used as a surfactant. (16) Decahydronaphthalene (mixture of cis and trans): manufactured by Wako Pure Chemical Industries, Ltd., product number 048-006
6. This liquid itself was used (impregnating agent B). (17) Orthohydroxybiphenyl (OHB): manufactured by Wako Pure Chemical Industries, Ltd., product B No. 080-O1402, 1 g of orthohydroxybiphenyl and 0.2 g of sodium hydroxide
g of a surfactant (sodium dodecylbenzenesulfonate) in 200 ml of water and used as a solution (impregnating agent C). Alternatively, a solution obtained by dissolving 0.5 g of orthohydroxybiphenyl in 300 ml of methanol was used by dispersing it in water used as a carrier (carrier D). (18) 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 200 ml of water, and 1
A solution obtained by mixing 0.5 ml of 0% hydrochloric acid was used by dispersing it in water (impregnating agent E). (19) Diphenyl (DP): manufactured by Wako Pure Chemical Industries, Ltd., product number 040-18412. 2.5 g of diphenyl and surfactant (sodium dodecylbenzenesulfonate) 0.2
g was mixed with 200 ml of water to obtain a solution (impregnating agent F). (20) Carriert (trade name, manufactured by Toho Chemical Co., Ltd.):
Polyester synthetic fiber dye carrier, aromatic ether anion activator compound. It was used by dispersing in water (carrier 1). (21) Carrier TW200 (trade name, Nika Chemical Co., Ltd.)
Manufactured by: Polyester / wool blend spinning synthetic fiber dyeing carrier, methylnaphthalene and other blended products, dispersed in water and used (carrier 2).

(C) Ozone treatment: A test piece was placed in a hard glass container (with a gas inlet and an outlet) having a volume of 2 L or 10 L, and an ozone generator (OS-1 manufactured by Mitsubishi Electric Corporation) was used.
N), oxygen containing ozone having an ozone generation amount of 1 g / h and a concentration of 20 g / m ³ was supplied at a flow rate of 800 ml / min for 20 to 12 hours.
Blowed for 0 minutes. Next, 10% oxygen without ozone was added.
I blew for a minute. The ozone concentration was determined by iodine titration. The degree of oxidation was determined by shaving the surface member of the treated test piece, measuring the infrared absorption spectrum, and changing the absorbance at an absorption peak near 1710 cm ^-1 (absorption of a carbonyl group) and the ratio of this absorbance to the absorbance at 973 cm ^-1. Judged better.

(D) Plasma treatment: A test piece (cloth, film, etc.) was placed between electrodes in a reaction tank of a plasma treatment apparatus (Yamato PR500). The pressure inside the reaction tank is 0.
After reducing the pressure to 27 Pa, a mixture of argon gas and oxygen gas (1: 1 by volume) was introduced until the pressure reached 5.6 Pa. Glow discharge was performed at an oscillation frequency of 13.56 MHz, mainly for 30 seconds to 3 minutes, with the supplied power being a value between 40 W and 100 W. After the discharge, stop the gas introduction,
After the pressure was returned to normal pressure, the treated test piece was taken out. The degree of treatment was determined by the decrease in the contact angle of water with the film.

(E) Ultraviolet irradiation treatment: In the case of the activation treatment, the sample itself was directly irradiated with a high-pressure mercury lamp (Toshiba high-pressure mercury lamp H400P) from a distance of 10 cm. In the case of grafting, the reaction mixture is placed in a Pyrex (registered trademark) glass reaction vessel and heated at a temperature of 10 to 10.
70 ° C and a high pressure mercury lamp (Toshiba high pressure mercury lamp H40
0P) from a distance of 20 cm. The reaction tube revolved around the lamp while rotating so that the light was uniformly irradiated.

(F) Evaluation of water absorption: Measurement of water absorption of non-woven fabric, woven fabric, fiber bundle, film, plate, porous film: (1) Water absorption: A test piece (size 10 cm × 10 cm) is filled with water. And stir gently with a glass rod for about 1 minute. Next, the test piece is taken out and hung for 3 minutes (water drops do not drop). The weight of the dried test piece was subtracted from the weight of the water-absorbed test piece to determine the increased weight (water absorption).
The percentage with respect to the weight of the dried test piece was defined as the water absorption (%). Water absorption (%) = (water absorption / dry weight of test piece) × 10
0

(2) Water absorption rate: The lower end 1 cm of a test piece having a width of 1.5 cm was immersed in water, and the distance (unit: cm / min) at which water rose in one minute was measured. The water absorption rate of all the untreated samples used in this example was 0 cm / min. The water suction rate of all untreated samples used in this example was 0 cm.
/ Min.

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

(H) Washing resistance test: A test piece was placed in a 0.4% aqueous solution of a weakly alkaline fatty acid sodium soap (trade name: Lion powder soap manufactured by Lion Corporation) at a bath ratio of 1: 250 and stirred. Washing by boiling was performed for 5 minutes. Then, after sufficiently washing with water, it was dried. Water absorption rate, water suction rate,
And the tensile strength was measured and compared with that before washing.

(I) Tensile strength test: A test piece was 1.5 cm
It was cut into a rectangle of × 7 cm, and a portion 1 cm from both ends was fixed to a clamp of a tensile tester (SV55-0-20M manufactured by Imada Seisakusho Co., Ltd.).
It was pulled at 00 mm / min. The measurement was made in each direction of the vertical and horizontal eyes. In each embodiment, only the longitudinal direction is shown.

(J) Adhesive peel strength test: (1) In the case of a film: a test piece is 30 mm (longitudinal direction)
Cut into a size of 5 mm × 5 mm × 5 mm on one end of 0.1 g of adhesive is applied, and a plywood (thickness 2 mm, size 20 mm × 10 mm) or sticky paper ((0.2 mm thick)
m, size 20 mm × 10 mm), and put a 500 g weight on a polyethylene film for 12 hours. A 10 mm portion of the plywood that is not adhered and a 10 mm end of the film that is not adhered are sandwiched between clamps of a tensile tester (AGS-H manufactured by Shimadzu Corporation), and a pulling speed of 30 mm.
The film was pulled at a rate of mm / min to determine the energy required for peeling off the bonded portion (bonding peeling energy). In order to standardize the bonding conditions, relative values were determined by setting the bond peeling energy of the untreated material, which was similarly performed, to 1.0. The adhesive used was a polycyanoacrylate type (Aron Alpha: manufactured by Toagosei Co., Ltd.) for plywood and a sticky note for sticky paper.
A paper adhesive for stationery (trade name: KOKUYO Co., Ltd., split).

(2) In the case of a bracket: about 0.01 g of an adhesive is applied to the adhesive surface of the treated or untreated bracket,
Attach it to a ceramic plate (size 20 mm x 10 mm), hook a loop-shaped wire, and clamp the non-adhered portion of the ceramic plate to the lower clamp of a tensile tester (Shimadzu SV55-0-20M). And fix the wire to the upper clamp,
Pull at mm / min, and determine the load applied until the bonded part is peeled off. In order to standardize the bonding conditions, relative values were determined with the peel strength of the untreated material performed simultaneously as 1.0. Polymerizable methacrylic resin-based adhesive (using a mixture of methyl methacrylate monomer, polymer, polymerization catalyst, etc.): trade name Super Bond (Sun Medical Co., Ltd.) or a self-made product.

The processes corresponding to the first, second, and third aspects are referred to as inventions 1, 2, and 3, respectively, and examples of the processing of various nonwoven fabrics or woven fabrics made of polypropylene, polyester, and polyethylene are described below. As a result, the water absorption, the water absorption height, and the water absorption after washing of the obtained treated or untreated sample are shown in Table 2.
Shown in In all the examples, the operation of removing the antioxidant, the stabilizer and other additives contained in the polymer material was not performed.

Example 1 Hydrophilization of Polypropylene Nonwoven Fabric According to Invention 1 As a treatment with an impregnating agent, 100 ml of toluene was heated to 50 ° C., and then 1.0 g of PP nonwoven fabric 1 (size 20 cm × 20)
cm) for 15 minutes. Next, it was rinsed with methanol and then centrifuged (800 rpm) for 1 minute. The weight increase of the sample was about 4%. Next, as an activation treatment, ozone treatment was performed for 30 minutes (ozone generation rate:
1.0 g / h). By measuring the infrared absorption spectrum, 1
The ratio of the absorbance at the absorption peak near 710 cm ⁻¹ (absorption of the carbonyl group) was 0.02. Next, a processing material was put into a solution made by putting 200 ml of water, 20 mg of ceric ammonium nitrate (IV) and 0.6 ml of acrylic acid in a glass tube made of Pyrex. From, while keeping at 30 ℃
Irradiated for 120 minutes. After the treatment, the material was washed by boiling in a detergent aqueous solution at 60 ° C. for 10 minutes, then washed with water and dried. The water absorption of the treated sample in the water absorption test was 310%. The water absorption height was 2.0 cm / min. The untreated nonwoven fabric had a water absorption of 0% and a water absorption height of 0 cm / min.
In particular, it was excellent in water absorption and electrolyte solution retention. It has excellent alkali resistance, acid resistance, and oxidation resistance, and is effective as a method for producing a battery separator.

(Example 2) All processes were the same as in Example 1, except that decahydronaphthalene (impregnating agent B) was used as the impregnating agent treatment, plasma treatment was performed for 30 seconds as the activation treatment, and methacrylic acid was used as the monomer. is there.

Example 3 The procedure of Example 1 was the same as that of Example 1 except that an aqueous dispersion of orthohydroxybiphenyl (OHB) (impregnant C) was used for the treatment with the impregnating agent. (Example 4) Except for using a methanol solution of orthohydroxybiphenyl (impregnating agent D) as the impregnating agent treatment, all were the same as in Example 1.

Example 5 The same procedure as in Example 1 was carried out except that an aqueous dispersion of sodium salicylate (impregnating agent E) was used as the impregnating agent treatment, and an ultraviolet irradiation treatment was performed for 60 minutes as the activation treatment. is there.

(Example 6) Except for using a diphenyl solution (impregnating agent F) as the impregnating agent treatment, the same as in Example 1 except that an ultraviolet irradiation treatment was performed for 60 minutes as the activation treatment. . (Comparative Examples 1 to 5) Comparative Example 1 is the result of using an untreated PP sample used in Example 1. Comparative Example 2 is the same as Example 1 except that the impregnating agent treatment step was omitted in the process of Example 1. Comparative Example 3 is the same as Example 1 except that the impregnating agent treatment step and the activation step were omitted in the step of Example 1. Comparative Example 4 is the same as Example 1 except that the impregnating agent treatment step and the grafting step were omitted in the step of Example 1. Comparative Example 5 is the same as Example 1 except that the activation treatment step was omitted from the process of Example 1.

(Example 7) A PP plain woven fabric was used as a PP sample, and an orthohydroxybiphenyl (OHB) solution (impregnating agent C) was used as an impregnating agent, and ultraviolet irradiation was performed for 2 hours as an activating process. Was. Other methods and procedures are the same as those in the first embodiment. Grafting Example 1
Was similar to

(Comparative Example 6) This is the result of an untreated PP plain woven fabric.

(Comparative Example 7) The same processing as in Example 2 was performed except that the impregnating agent treatment was omitted using PP plain woven fabric as a sample. From Example 3, the durability of the water absorption rate was slightly lowered.

Example 8 PET non-woven fabric (size 10 cm)
× 10 cm), using an aqueous dispersion of carrier 1 (trade name: Carantant) (5 g of reagent mixed in 200 ml of water), and using AIBN2 instead of CAN as an initiator.
The same procedure as in Example 1 was carried out using 0 mg.

Example 9 PET nonwoven fabric (size 10 cm)
× 10 cm), an aqueous dispersion of Carrier 2 (trade name: Carrier TW200) (5 g of reagent mixed with 200 ml of water) was used for activation, and for grafting, 20 mg of AIBN was used instead of CAN as an initiator. And thermal polymerization was carried out at 70 ° C. for 4 hours (the procedure was the same as in the examples, but no UV irradiation was applied). Performed in the same manner as in Example 1.

Example 10 PET nonwoven fabric (size 10)
cm × 10 cm) in the same manner as in Example 1.

(Comparative Examples 8 to 12) Regarding PET non-woven fabrics, Comparative Example 8 was untreated, Comparative Example 9 was without the impregnating agent treatment from Example 1, and Comparative Example 10 was the impregnating agent treatment and activation treatment from Example 1. Comparative Example 11 is a treatment in which the impregnating agent treatment and the grafting treatment are omitted from Example 4. In Comparative Example 12, the activation process is omitted from Example 1.

(Embodiments 11 to 12) Embodiment 11
Using nonwoven fabric 2 and an orthohydroxybiphenyl (OHB) solution (impregnating agent C), the same as in Example 1, and Example 12 using PP nonwoven fabric 2 and impregnating agent C, as in Example 2. .

(Comparative Examples 13 to 17) In all cases, PP nonwoven fabric 2 was used. Comparative Example 13 was the same as Example 1 except that the untreated PP nonwoven fabric 2 was omitted, and Comparative Example 14 was the same as Example 1 except that the impregnating agent treatment and activation treatment were omitted. Comparative Example 16 was the same as Example 1 except that only the ozone treatment as the activation treatment was performed, and Comparative Example 17 was that the activation treatment was omitted.

(Example 13) A P / E nonwoven fabric was used as a sample.
Ortho-hydroxybiphenyl (OH
The aqueous dispersion of B) (impregnating agent C) is used, activation is performed by ozone treatment, dicerium ammonium nitrate (IV) is used as an initiator, and thermal grafting is performed at 80 ° C. for 3 hours using methacrylic acid as a monomer. Was.

(Example 14) A P / E nonwoven fabric was used as a sample.
The procedure was performed in the same manner as in Example 2 except that potassium sulfate was used instead of ammonium ceric nitrate (IV).

(Comparative Example 18) This is the result of an untreated P / E nonwoven fabric.

Table 2 summarizes the results. The water absorption is
After treatment, the value after washing with detergent and drying, the water absorption after washing three times is the water absorption after washing and drying three times with a boiling detergent solution.

[0083]

[Table 2]

The following shows working examples of a polyethylene terephthalate film, an ultrahigh molecular weight polyethylene plate, and a polypropylene film, and comparative examples in which one or two steps are omitted from the untreated and the method of the present invention. The results are summarized in Table 3.

Example 15 Treatment of Polyethylene Terephthalate Film As an impregnant treatment, 100 ml of toluene (impregnating agent A) was heated to 80 ° C., and 1.62 g (size 15 cm × 15 cm) of a PET film was immersed for 15 minutes. Next, rinse with methanol, wipe off excess carrier with paper,
Dry for 5 minutes at room temperature. Next, as activation processing,
Ozone treatment was performed for 30 minutes (ozone generation rate: 1.0
g / h). Next, for the grafting, a treatment material was put into a solution made by putting 200 ml of water, 20 mg of AIBN, and 1.2 ml of acrylic acid in a glass tube made of Pyrex,
While maintaining the temperature at 80 ° C., it was left for 4 hours. After the treatment, the material was washed by boiling in a 60 ° C. aqueous detergent solution for 1 minute, then washed with water, and dried. The water absorption of the treated sample in the water absorption test was 90%, and the contact angle of water was 63 °. The adhesive peel strength of the sticky paper by the glue (stationary) for stationery was 4.0 when the untreated adhesive peel strength was 1.

Example 16 100 ml of an aqueous dispersion of orthohydroxybiphenyl (impregnating agent C) was heated to 70 ° C., and then 1.62 g of a PET film (size 15 cm × 1)
5 cm) for 15 minutes. Next, it was rinsed with methanol, wiped off with extra paper, and dried for 5 minutes at room temperature. Next, after the same ozone treatment as in Example 1, ultraviolet irradiation grafting was carried out using water 180 ml, potassium persulfate 2
0 mg and 1.2 ml of methacrylic acid were used.

Example 17 The same procedure as in Example 16 was carried out except that a methanol solution of orthohydroxybiphenyl (impregnating agent D) was used.

(Example 18) 1 g of sodium salicylate
Example 16 was repeated except that the aqueous dispersion (impregnating agent E) was used.

(Comparative Example 19) This is the result of an untreated PET film. (Comparative Example 20) The same process as in Example 16 except for the treatment with the impregnating agent was performed. (Comparative Example 21) A process was performed in which the impregnating agent treatment and the activation treatment were omitted from Example 16. (Comparative Example 22) The same process as in Example 16 except that the impregnating agent treatment and the grafting treatment were omitted. (Comparative Example 23) The same processing as in Example 16 except for the activation processing was performed.

Example 19 3.84 g (size 10 cm × 10 cm) of an ultra-high molecular weight polyethylene plate was treated with an impregnating agent and immersed in 100 ml of toluene (impregnating agent A) at 70 ° C. for 15 minutes. Then, after rinsing with methanol, excess impregnating agent was wiped off with paper and dried for 5 minutes at room temperature.
Next, for activation, ozone treatment was performed for 120 minutes. next,
The same ultraviolet irradiation grafting as in Example 2 was performed using 180 m of water.
1, 20 mg of diceric ammonium nitrate (IV) and 1.0 ml of acrylic acid.

Example 20 Example 19 was repeated except that decahydronaphthalene (impregnating agent B) was used as the impregnating agent treatment.
The same was done.

Example 21 The same procedure was performed as in Example 19, except that orthohydroxybiphenyl (OHB) (impregnating agent C) was used, and no initiator was added during grafting.

(Comparative Example 24) This is the result of an untreated ultra high molecular weight polyethylene plate. (Comparative Example 25) The same process as in Example 19 except that the impregnating agent treatment was omitted was performed. (Comparative Example 26) The same process as in Example 19 except that the impregnating agent treatment and the activation treatment were omitted. (Comparative Example 27) The same treatment as in Example 19 except that the impregnating agent treatment and the grafting treatment were omitted. (Comparative Example 28) Processing in which the activation processing was omitted from Example 19 was performed.

Example 22 0.38 g (size 15 cm × 15 cm) of a polypropylene film was mixed with an aqueous dispersion of orthohydroxybiphenyl (impregnating agent C) at 70 ° C.
100 ml) for 10 minutes. Then, after rinsing with methanol, excess impregnating agent was wiped off with paper and dried for 5 minutes at room temperature. Next, for activation, ozone treatment was performed for 45 minutes. Next, the same ultraviolet irradiation grafting as in Example 1 was performed using water 180 ml, AIBN 20 mg, and acrylic acid 1.
Performed using 0 ml.

Example 23 The same procedure as in Example 17 was carried out except that a methanol solution of orthohydroxybiphenyl (impregnating agent D) was used.

(Example 24) Using sodium salicylate (impregnating agent E), plasma treatment was performed for 30 seconds as an activation treatment, and a mixture of acrylic acid and methacrylic acid was used as a monomer. is there.

(Comparative Example 29) This is the result of an untreated polypropylene film. (Comparative Example 30) The same treatment as in Example 22 except that the impregnating agent treatment was omitted. (Comparative Example 31) The same process as in Example 22 except that the impregnating agent treatment and the activation treatment were omitted. (Comparative Example 32) The same process as in Example 22 except that the impregnating agent treatment and the grafting treatment were omitted. (Comparative Example 33) A process was performed in which the activation process was omitted from Example 22. The above results are summarized in Table 3.

[Table 3]

(Example 25) Hydrophilization of carbon fiber and use of composite material: 6.0 g of carbon fiber
Was immersed in methanol at 50 ° C. for 30 minutes as an impregnating agent treatment. Next, it was centrifuged (800 rpm) for 1 minute. Next, as an activation treatment, the mixture was placed in a hard glass container having a thickness of 1.5 mm, and a flow rate of 100 ml /
Per minute of oxygen to generate ozone at a concentration of 40 mg / L, which was introduced into a container and blown for 30 minutes. Next, oxygen containing no ozone was blown for 10 minutes. Next, as the grafting, acrylic acid 1.2
ml, 200 ml of water and 5 ml of methanol were added, and the reaction vessel was set to a nitrogen atmosphere. The reaction vessel was irradiated with a high-pressure mercury lamp (Toshiba high-pressure mercury lamp H400P) from a distance of 15.5 cm to the reaction vessel for 3 hours. The temperature was 45 ° C. Next, the contents of the container were poured into a large amount of water. The carbon fiber to which the polymer was adhered was taken out, and washed by boiling with a detergent three times. The graft ratio was 15%. After the treatment, it was washed three times with an aqueous boiling detergent solution (one time, using 500 ml of water). After drying, the water absorption increased to 200% (120% for untreated).

(Comparative Example 34) When the activation treatment and the ultraviolet ray grafting were carried out except for the treatment with the impregnating agent, the graft ratio was 4.2%. (Comparative Example 35) When the impregnating agent treatment and the ultraviolet ray grafting treatment were performed, the graft ratio was 3.0%. (Comparative Example 36) When only the ultraviolet grafting was performed, the graft ratio was 1.0%.

(Example 26) The carbon fiber obtained in Example 25 was mixed with an epoxy resin adhesive, dried, and dried.
A rod of mm × 5 mm × 100 mm was made. For comparison, an epoxy resin rod mixed with untreated carbon fibers was prepared. The tensile strength of the hydrophilic carbon fiber reinforced epoxy resin rod was 40 times higher than that of the epoxy resin rod mixed with untreated carbon fiber.

(Example 27) Hydrophilization of wool fiber cloth: 1.02 g of wool fiber (woven cloth) was
As an impregnating agent treatment, 10 m of anhydrous sodium carbonate at 50 ° C.
g, 10 volumes of methanol and 90 volumes of water for 30 minutes. Next, it was centrifuged (800 rpm) for 1 minute. Next, as an activation treatment, oxygen at a flow rate of 100 ml / min was introduced into an ozone generator to generate ozone at a concentration of 40 mg / L, and this was introduced into a container and contacted for 30 minutes. Next, oxygen containing no ozone was blown for 10 minutes. Next, for grafting, 1.2 ml of acrylic acid, 200 ml of water and 5 ml of methanol were added to the treated fiber, and the reaction vessel was set to a nitrogen atmosphere. High pressure mercury lamp (Toshiba high pressure mercury lamp H400P) 20cm to the reaction vessel
Irradiation from a distance of 3 hours. The temperature was 45 ° C. Next, the contents of the container were poured into a large amount of water. The carbon fiber to which the polymer was adhered was taken out, and washed by boiling with a detergent three times. The graft ratio was 18%.

(Comparative Example 37) Except for the impregnating agent treatment, when the activation treatment and the ultraviolet ray grafting were performed, the graft ratio was 4.2%. (Comparative Example 38) When only the ultraviolet grafting was performed, the graft ratio was 1.5%. (Comparative Example 39) When the treatment with the impregnating agent and the ultraviolet ray grafting were performed, the graft ratio was 1.6%.

(Test of Water Absorption) The treated and untreated wool fiber cloths were floated in parallel to the water surface, and the time until water absorption and sinking was measured. The untreated wool cloth was 60 minutes, the treated wool cloth of Example 27 was 1 second, and Comparative Examples 37, 38 and 39 were 15 seconds, 28 seconds and 30 seconds, respectively.

Example 28 Hydrophilization of Synthetic Paper Made of Polypropylene: A porous polypropylene film for synthetic paper was treated in the same manner as in Example 2 to give hydrophilicity. The treated synthetic paper can be written with a water-soluble ink, and a water-soluble paste (starch,
CMC, PVA glue, etc.) to attach the sticky paper. The sticky paper could not be peeled off due to breakage.

Example 29 Hydrophilization of porous polyethylene film and use for filter: 0.3 g of porous polyethylene film (size 10)
cm × 10 cm), the same treatment as in Example 17 was performed. The treated film was washed with a boiling detergent aqueous solution and thoroughly washed with water. After drying, the water absorption was 200% (5% for untreated porous polyethylene film). The contact angle of water could not be measured due to water absorption (untreated porous polyethylene film, considered 0 °, 120
°). The weight increase of the sample due to the hydrophilic treatment was 2%. This hydrophilized porous polyethylene film had alkali resistance and acid resistance, and was effective for filtering components in an aqueous solution.

Example 30 A porous polyethylene film was treated with an impregnating agent (toluene at 70 ° C. for 15 minutes), activated (plasma treatment for 0.5 minutes), and UV-grafted (using methacrylic acid and potassium persulfate). ) Gave the same results as in Example 26.

(Example 31) Hydrophilization of porous polysulfone film and filter application: 0.5 g of porous polysulfone film (size 10)
cm × 10 cm) as an impregnating agent treatment, soaked in a 10% by volume aqueous solution of methanol at room temperature for 1 minute. Ozone treatment was performed for 5 minutes as an activation treatment. The same processing as in Example 17 was performed. The treated film was washed with a boiling detergent aqueous solution and thoroughly washed with water. After drying, the water absorption was 200% (5% for untreated porous polyethylene film). The contact angle of water could not be measured due to water absorption (120 ° for untreated porous polyethylene film). The increase in mass of the sample due to the hydrophilic treatment was 2%. This hydrophilized porous polyethylene film has alkali resistance and acid resistance,
It had heat resistance (heat treatment in an autoclave at 120 ° C. for 30 minutes was repeated three times), and was effective for filtering components in an aqueous solution.

Example 32 Hydrophilization of Polypropylene Nonwoven Fabric 2 (Using Polyvinyl Alcohol): Impregnation of 1.0 g of polypropylene nonwoven fabric 2 (size: about 15 cm × 15 cm) was performed with 2.5 g of diphenyl and a surfactant (dodecyl). It was immersed in a solution obtained by mixing 0.2 g of sodium benzenesulfonate) in 200 ml of water at 50 ° C. for 5 minutes. Next, the liquid was removed using a centrifugal separator (at 1,000 revolutions / minute). When the weight increase was 4%, ozone treatment was performed at 20 ° C. for 30 minutes as an activation treatment. Next, as a polymer treatment, the treated nonwoven fabric was put into a reaction vessel, a mixture of 200 ml of water, 60 mg of potassium persulfate, 0.3 g of polyvinyl alcohol, and 6 ml of methanol was added, and the mixture was treated at 80 ° C. for 2 hours. After the treatment, it was washed with water and washed with detergent. Water absorption from 800 to 1,100% deli, increase or decrease in the mass of the sample by hydrophilic treatment could not be measured with an accuracy of 0.1 mg. Table 1 shows the results. Water absorption of 810% or more was maintained even after six detergent washings. This treated sample was most suitable as a material for water absorption use.

(Example 33) Treatment of polypropylene nonwoven fabric 2 according to Invention 2 (using sodium carboxymethylcellulose): Treatment of polypropylene nonwoven fabric 2 was performed in the same manner as in Example 32, except that sodium carboxymethylcellulose was used instead of polyvinyl alcohol. The water absorption was 600 to 900%, indicating durability.

Example 34 Use of Microorganism Medium: The water-absorbent nonwoven fabric produced according to Example 32 was cut into 2 cm × 2 cm pieces each of two sheets.
They were arranged so as not to overlap a petri dish having a diameter of 8 cm and a depth of 2 cm. 1% by weight meat extract, 1% by weight polypeptone,
After making 100 ml of a bouillon agar solution consisting of an aqueous solution containing 0.5% by weight of sodium chloride and 1.5% by weight of agar and melting the agar with a microwave oven, 50 ml of this bouillon agar solution was impregnated into the nonwoven fabric, Return to room temperature.
The thus obtained nonwoven fabric impregnated with the bouillon agar solution (hereinafter referred to as a medium nonwoven fabric) was placed in a test tube which was autoclaved at 120 ° C. for 15 minutes. After keeping the temperature at 37 ° C. overnight with the tester in the upright position and checking the sterility on the next day, the microorganism strain to be cultured (E. coli K-12 strain, Salmonella tyhimurium LT-2 strain, Bacillus subtilis Marburg strain, etc.) ) Was inoculated, and this was allowed to stand still at 30 to 37 ° C. overnight in an incubator. When the growth state of the planted various bacteria was observed with a microscope, the various bacteria were growing smoothly.

(Comparative Example 40) The polypropylene nonwoven fabric 2 was subjected to the process of Example 32 except for the impregnation process. The water absorbency of the treated sample was determined to be 7 after washing the detergent three times.
It decreased from 80% to 400%.

(Example 35) Use of the cloth for hydrophilizing and wiping and cleaning the sample 6 according to the invention 3: The sample 6 is a nonwoven fabric of a core-sheath fiber having a polyester core and a polyethylene sheath. 2.4 g of a nonwoven fabric of a polyethylene / polyester core-in-sheath type composite fiber was impregnated at room temperature with 10 ml of 0.5 g of orthohydroxybiphenyl in methanol 30
The solution (impregnant D) obtained by dissolving in 0 ml
Soaked for a minute. Next, it was applied to a centrifugal dehydrator (rotation speed: 1000 / min), and the surface was apparently dried. The mass increase was about 4%. Next, ozone treatment was performed for 30 minutes. Next, the ozone-treated nonwoven fabric was placed in an Erlenmeyer flask, and 5 ml of methanol, 100 ml of water, 0.5 g of polyvinyl alcohol, and 0.1 g of potassium persulfate were added.
Treated at 2 ° C. for 2 hours. After the treatment, it was sufficiently washed with water at 60 ° C. The water of the treated nonwoven fabric was squeezed (to a water absorption of about 300%), placed in a container, and added with 400 ml of water, 100 mg of diceric ammonium nitrate (IV), and 5 ml of acrylic acid, and left as a nitrogen atmosphere at 80 ° C. for 2 hours. After the treatment, the treated nonwoven fabric was washed three times with a detergent solution at 60 ° C. (1
Times, using 500 ml of water). After drying, the water absorption (according to water absorption test 1) was 2310%, and the untreated nonwoven fabric was 350%. The weight increase of the sample due to the hydrophilic treatment was 4%. Further than the method of Invention 1,
Water absorption is high. (When treated by the method of Invention 1, water absorption is 1
It was excellent in water absorption speed and water absorption durability, and was most suitable as a wiper (a substitute for a rag) for wiping and cleaning. The hydrophilic nonwoven fabric was made to absorb water (water absorption rate: about 2,000%), and ten sheets were stacked, attached to a cleaning mop, and used for wiping a wooden floor. After use, it was rinsed with water and used 10 or more times.

(Example 36) Materials for hydrophilized polypropylene nonwoven fabric 2 and disposable hygiene articles: Use of hydrophilized polypropylene nonwoven fabric 2 obtained by the method of Example 11 as an inner cloth, and a water retaining agent (water-absorbing polymer: pulp) , Modified starch or polyacrylic acid)
And a model of a disposable diaper using an untreated external polypropylene nonwoven fabric. That is, an untreated water-repellent polypropylene nonwoven fabric was placed at the bottom, a water-absorbing polymer was laid thereon, and the water-absorbent polyolefin nonwoven fabric of the present invention was further placed thereon. When water was applied from above, the water quickly permeated the water-absorbent polyolefin nonwoven fabric and was absorbed by the moisture retaining agent. Thus, the water-absorbent nonwoven fabric according to the present invention is most suitable as a material for disposable diapers and sanitary and sanitary products.

(Example 37) Improvement of adhesiveness of orthodontic polypropylene bracket:
20 brackets made of polypropylene for orthodontics (0.6
For 22 g), methyl methacrylate was grafted in the same manner as in Example 14. The polymerization inhibitor for methyl methacrylate was omitted. The treated product had improved adhesiveness to ceramic dental materials with a polymerizable acrylic resin adhesive, and a tensile test resulted in material destruction of orthodontic polypropylene brackets.

(Comparative Example 41) Polypropylene / polyethylene nonwoven fabric hydrophilized with a known surfactant (a product obtained by impregnating a surfactant into Nippon Vilene Co., Ltd .: The basis weight is the same as that of Sample 4 in Table 1) Was prepared, and the same evaluation as in Example 1 was performed. The results were as follows. 1) Alkali resistance test: After drying, the water absorption was reduced to 5% of the original value. 2) Sulfuric acid resistance test: After sufficiently washing with water and drying, the water absorption was reduced to 5% of the original value. 3) Oxidation resistance test: After drying, the water absorption decreased to the original 5%.

(Comparative Example 42) Grafting of acrylic acid onto nonwoven fabric 1 by known ultraviolet irradiation: 1.2 g of nonwoven fabric 1 shown in Table 1 made of polypropylene (size 7.7 c
mx 10 cm) in a reaction solution having a composition of 20.0% of acrylic acid monomer, 78.8% of water, 0.2% of benzophenone and 1.0% of methanol (both by weight) to obtain 400 watts. The high-pressure mercury lamp was irradiated from a distance of 12 cm for 120 minutes. After the reaction, the nonwoven fabric was solidified with a polymer, but after boiling and washing for 10 minutes in an aqueous solution of fatty acid sodium soap (concentration: 2% by weight, bath ratio: 1/20), the polymer was dissolved and separated as a result of washing with water. The water absorption of the obtained nonwoven fabric was 100% (48% for the untreated nonwoven fabric).
The graft ratio was 1%. That is, grafting by ultraviolet irradiation is difficult in the case of the present nonwoven fabric. By boiling washing with a detergent, it was considered that the produced homopolymer composed of only acrylic acid was dissolved and came off the nonwoven fabric. The acidity and alkali treatment reduced the hydrophilicity.

[0117]

As described above, various polymer materials obtained by the method for modifying a polymer material of the present invention have excellent properties such as excellent water absorption and adhesiveness with an adhesive without a decrease in strength. The improvement effect was shown. Properties imparted by the modification are excellent in durability. In addition, the filtration of aqueous solutions has been developed due to the hydrophilicity of polyolefin filter media. It can impart water absorbency to synthetic paper, improve adhesiveness, and improve printing performance. Since the adhesiveness of many polymer materials including carbon fibers by an adhesive is improved, a hydrophilically treated product useful as a reinforcing fiber of a composite material is provided. The hydrophilicity of various polymer moldings can also be improved, and the absorption of water-soluble ink and the like can be improved for polyolefin writing implement parts that were not possible before. It can be used for various medical, hygiene and cosmetic products and textiles for clothing, improves the adhesiveness of orthodontic polypropylene brackets, and improves the water wettability of polymeric medical materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61L 15/00 A61L 27/00 W 4G066 27/00 B01J 19/08 C 4G075 E 4L031 B01J 19/08 19 / 12 4L033 20/26 D 19/12 C12N 1/00 F 20/26 D06M 10/00 K C12N 1/00 13/07 D06M 10/00 14/28 11/32 C08L 101: 00 13/07 A61F 13/18 307B 14/28 D06M 7/02 A // C08L 101: 00 F term (reference) 4B065 BC41 4C003 AA12 AA16 AA19 4C081 AA02 AB05 AB12 AB13 AB31 BA03 CA02 CA05 CA08 CD02 CD03 CD11 DA02 DA04 DA05 DB07 4C083 AD041 AD091 AD051 AD051 AD241 AD261 AD301 AD411 AD451 CC07 DD12 EE03 4F073 AA01 AA24 AA32 BA03 BA06 BA13 BA14 BA17 BA18 BA19 BA23 BA26 BA28 BA29 BB01 BB02 CA01 CA21 CA45 CA62 EA01 EA25 FA01 FA03 FA04 FA08 FA09 FA11 FA13 HA04 HA09 HA10 4G066 AC01B AC02B AC03B AC13C AC17B AC17C AC21B AC23C AE06B BA02 BA03 BA16 CA43 DA12 DA13 EA05 4G075 AA32 BA05 CA18 CA33 CA47 CA54 CA57 4L031 AA14 AA18 AAB AAB AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AAB AA AA AAB AA AA AAB AA AA AAB AA AA AA AAB AA AA AAB AA AA AAB AA AA AA AB AA AA AA AA AA AA AA AB AA AA AA AA AA AA AA AA AA AB AA AA AA AA AA AA AA B AA07 AA08 AA10 AB01 AB05 AB07 AC07 AC15 BA04 CA18 CA23 CA28 CA29

Claims (24)

[Claims] (1) contacting a surface of a polymer material with (1) a compound having an impregnating property with respect to the polymer material;
(Impregnation in the range of (to the polymer material), an impregnation step in which the shape of the material is not substantially changed, (2) an activation step of introducing a carbonyl group, and (3) a step of grafting a monomer The polymer material is modified in this order. 2. Contacting the surface of a polymer material with (1) a compound impregnating the polymer material, so that the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40% by weight.
(With respect to a polymer material), an impregnating step of substantially not changing the shape of the material, (2) an activation step of introducing a carbonyl group, and (3) a step of treating with a hydrophilic polymer. A method of modifying a polymer material, wherein the treatment is performed in this order. 3. The surface of a polymer material is brought into contact with (1) a compound having an impregnating property with respect to the polymer material so that the impregnation amount within a depth of 100 microns from the surface is 0.1 to 40% by weight.
(With respect to a polymer material), an impregnation step of substantially not changing the shape of the material, (2) an activation step of introducing a carbonyl group, (3) a step of treating with a hydrophilic polymer, And (4) a method for modifying a polymer material, wherein the treatment is performed in this order by a step of grafting a monomer. 4. The method according to claim 1, wherein the polymer material is a fiber, a woven fabric, a knitted fabric,
2. A molded material selected from the group consisting of a nonwoven fabric, a plate, a rod, a film, a sheet, a porous film and a sheet, a member or a product molded into a predetermined shape, or a composite material with another material. 4. The method for modifying a polymer material according to any one of items 1 to 3. 5. The method for modifying a polymer material according to claim 1, wherein the polymer material contains at least one of an antioxidant and a stabilizer. 6. The method for modifying a polymer material according to claim 1, wherein the impregnation is performed at a temperature equal to or lower than a melting point or a softening point of the polymer material. 7. The method according to claim 1, wherein the activation treatment is at least one treatment selected from the group consisting of ozone treatment, plasma treatment, ultraviolet irradiation treatment, corona discharge treatment, and high-pressure discharge treatment. 4. The method for modifying a polymer material according to any one of 3. 8. The method according to claim 1, wherein the monomer is a compound having a carbon-carbon double bond. 9. The method according to claim 9, wherein the monomer is acrylic acid, methacrylic acid, vinyl acetic acid, 2-butenoic acid, ethylene sulfonic acid,
At least one monomer selected from the group consisting of hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinylpyridine, vinylpyrrolidone, vinylcarbazole, maleic anhydride, and pyromellitic anhydride, or at least one monomer selected from these groups 4. The method for modifying a surface of a polymer material according to claim 1, wherein the mixture is a mixture of a kind monomer and another vinyl monomer. 10. The hydrophilic polymer is polyvinyl alcohol, carboxymethyl cellulose, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyalkylene glycol, starch, glucomannan. , Fibroin, sericin, agar,
4. The method for modifying the surface of a polymer material according to claim 2, wherein the method is at least one polymer compound selected from the group consisting of protein in egg white and sodium alginate. 11. The method of the step of grafting a monomer, wherein (1) a method of performing the step in the presence of a catalyst or an initiator,
(2) a method of heating in the presence or absence of a catalyst or an initiator, and (3) a method of irradiating ultraviolet rays in the presence or absence of a catalyst, an initiator, or a photosensitizer. 3. The method for modifying a polymer material according to claim 1, wherein the method is performed by a plurality of methods. 12. The method according to claim 2, wherein in the step of treating with the hydrophilic polymer, these steps are carried out in the presence of a catalyst or an initiator. Surface modification method. 13. The initiator is at least one compound selected from the group consisting of peroxide, ceric ammonium nitrate (IV), persulfate, redox initiator and other radical polymerization initiator. The method for modifying a polymer material according to claim 11, wherein: 14. A polymer material modified by the method for modifying a polymer material according to claim 1. Description: 15. A material for wiping and cleaning comprising a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 16. A filter medium comprising a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 17. A water-absorbing material comprising a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 18. A water retention material containing a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 19. A writing instrument member using a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 20. A material for a microorganism culture medium comprising a polymer material modified by the method for modifying a polymer material according to any one of claims 1 to 13. 21. A medical / hygiene / cosmetic article comprising the polymer material modified by the method for modifying a polymer material according to claim 1. 22. Synthetic paper comprising a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 23. An orthodontic bracket including a polymer material modified by the method for modifying a polymer material according to claim 1. Description: 24. A medical device material comprising a polymer material modified by the method for modifying a polymer material according to claim 1. Description: