Polymer composite and its manufacturing method

Abstract

To provide a method for producing a polymer composite having excellent mechanical strength and shape stability and to provide a method for producing the same.SOLUTION: There is provided a polymer composite which comprises a polymer containing a structural unit derived from an unsaturated monomer and a metal component dispersed in a matrix composed of the polymer, wherein the metal component is at least one selected from a zirconium component, an yttrium component, a cerium component and a neodymium component. The metal component preferably is a metal oxide or a metal ion. There is provided a polymer composite which can be produced by a method comprising: a mixing step of mixing a sol containing water and a metal oxide or an aqueous solution containing metal ions, an unsaturated monomer and a polymerization initiator; and a polymerization step of polymerizing the unsaturated monomer in order.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer composite having excellent mechanical strength, in which a metal component is dispersed in a polymer matrix, and to a method for producing the same. [Background technology]

[0002] Polymer gels are soft materials consisting of a polymer network and a large amount of liquid medium, and are widely used in the fields of food, environment, energy, medicine, sports, etc. One of the challenges required for such elastic materials is to improve their mechanical strength.

[0003] The following technologies are known as polymer gels that focus on mechanical strength. For example, Patent Document 1 discloses a topological gel in which crosslinking points move along the main chain. Patent Document 2 discloses a nanocomposite gel that uses hydrophilic clay as the crosslinking points. Patent Document 3 discloses a double network gel in which two types of network structures interpenetrate each other. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. WO 01 / 83566 [Patent Document 2] JP 2004-143212 A [Patent Document 3] International Publication No. WO 03 / 93337 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the technique of Patent Document 1 has problems in that the elastic modulus and breaking strength are insufficient and the manufacturing process is complicated. In addition, the technique of Patent Document 3 can produce an unprecedented gel that combines strength and flexibility, but the gel after polymerization must be immersed in another monomer for polymerization, and the manufacturing process is complicated.

[0006] An object of the present invention is to provide a polymer composite that has excellent mechanical strength, such as compressive modulus, tensile strength, and tensile elongation at break, and has a low volume expansion coefficient and excellent shape stability, as well as to provide a method for efficiently producing such a polymer composite. [Means for solving the problem]

[0007] The present inventors discovered that when a polymer composite in which fine metal-containing components such as zirconia are dispersed in a polymer matrix is ​​soaked in water or the like, the composite has excellent mechanical strength and shape stability, and have thus completed the present invention. The polymer composite of the present invention comprises a polymer including a structural unit derived from an unsaturated monomer and a metal component dispersed in a matrix made of the polymer, the metal component being at least one selected from a zirconium component, a yttrium component, a cerium component and a neodymium component. The polymer composite of the present invention may further contain water and / or an organic solvent. The method for producing a polymer composite in the present invention is characterized by comprising, in sequence, a mixing step of mixing a sol containing water and a metal oxide or an aqueous solution containing metal ions, an unsaturated monomer, and a polymerization initiator, and a polymerization step of polymerizing the unsaturated monomer. The method for producing a polymer composite of the present invention may further include a contacting step of contacting the reaction product obtained in the polymerization step with water and / or an organic solvent. Effect of the Invention

[0008] In the present invention, the polymer composite containing water and / or an organic solvent has excellent mechanical strength and shape stability, and therefore, by retaining the water and / or organic solvent, the durability of the product is expected to be improved. According to the method for producing a polymer composite of the present invention, a polymer composite having the above-mentioned effects can be efficiently produced by only using a sol containing water and a metal oxide or an aqueous solution containing a metal ion, an unsaturated monomer, and a polymerization initiator. In addition, the mechanical strength of the polymer composite can be easily controlled by appropriately changing conditions such as temperature and time to polymerize the unsaturated monomer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The polymer composite of the present invention comprises a polymer containing structural units derived from an unsaturated monomer, and a metal component (metal-containing component) dispersed in a matrix made of the polymer. The metal component is at least one selected from a zirconium component, a yttrium component, a cerium component, and a neodymium component.

[0010] The polymer composite of the present invention is preferably a soft material having elasticity and excellent mechanical strength and shape stability by containing (holding) water and / or an organic solvent. In the present invention, the reaction product obtained by the mixing step and polymerization step in the production method described below usually contains (holds) water, but since it is possible to subsequently distill off the water and solidify the reaction product, the polymer composite of the present invention does not necessarily contain water. The polymer composite obtained by subjecting the reaction product or solidified product to a contact step in which water and / or an organic solvent is brought into contact with the reaction product or solidified product contains water and / or an organic solvent, and therefore reliably exhibits the above-mentioned effects of the present invention. Hereinafter, the polymer composite of this embodiment will be described as a "highly elastic polymer composite".

[0011] In the highly elastic polymer composite of the present invention containing water and / or an organic solvent liquid, the organic solvent is preferably a compound having water solubility or hydrophilicity, and examples thereof include alcohols (methanol, ethanol, propanol, etc.), alkylene glycols (ethylene glycol, etc.), cyclic ethers (tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), dialkylformamides (dimethylformamide, etc.), dialkylacetamides (dimethylacetamide, etc.), dialkylsulfoxides (dimethylsulfoxide, etc.), alkylene glycol monoalkyl ethers, etc. When an organic solvent is contained, only one type may be contained, or two or more types may be contained. Since the effects of the present invention can be obtained by the highly elastic polymer composite, the lower limit of the content of the liquid is preferably 100 parts by mass, more preferably 200 parts by mass, based on 100 parts by mass of the polymer, and the upper limit is usually 2000 parts by mass, preferably 1000 parts by mass.

[0012] The polymer according to the present invention contains at least one structural unit derived from an unsaturated monomer. The number of polymerizable unsaturated bonds contained in this unsaturated monomer is not particularly limited. When the compound has one polymerizable unsaturated bond, the polymer generally has a linear shape, but when the compound has two or more polymerizable unsaturated bonds, the polymer generally has a three-dimensional crosslinked structure. The polymer according to the present invention preferably has liquid absorption. The (total) absorption amount of water and / or organic solvent is preferably 1.0 g or more, more preferably 1.5 to 20 g, and even more preferably 2.0 to 10 g per 1.0 g of the polymer. This ratio also applies to the highly elastic polymer composite.

[0013] Among the above unsaturated monomers, examples of compounds having one polymerizable unsaturated bond include compounds having an amide group such as acrylamide, dimethylacrylamide, N-isopropylacrylamide, methacrylamide, dimethylmethacrylamide, N-isopropylmethacrylamide, and methacrylamidepropyltrimethylammonium chloride; compounds having a hydroxy group such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; compounds having a carboxylic acid group such as acrylic acid and methacrylic acid, or their salts; compounds having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid and p-styrenesulfonic acid, or their salts; compounds having a phosphoric acid group such as methacryloxyethyl trimeric acid, or their salts; acrylic acid alkyl esters, methacrylic acid alkyl esters, acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, and vinyl acetate. Of these, acrylamide and acrylic acid are preferred.

[0014] Among the above unsaturated monomers, compounds having two or more polymerizable unsaturated bonds (hereinafter referred to as "crosslinkable monomers") include N,N'-methylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)-bisacrylamide, monoethylene glycol diacrylate, monoethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, monopropylene glycol diacrylate, monopropylene glycol dimethacrylate, etc. Of these, N,N'-methylenebisacrylamide is preferred.

[0015] When the above polymer is composed of a structural unit derived from a compound having one polymerizable unsaturated bond and a structural unit derived from a crosslinkable monomer, the upper limit of the content of the structural unit derived from the crosslinkable monomer is preferably 1% by mass, and more preferably 0.1% by mass, when the total amount of the structural units constituting the above polymer is taken as 100% by mass, from the viewpoint of the mechanical strength and shape stability of the highly elastic polymer composite.

[0016] In the present invention, the metal component (metal-containing component) dispersed in the matrix made of the polymer is at least one selected from a zirconium component, a yttrium component, a cerium component, and a neodymium component, and examples of the metal components include ions, oxides, nitrides, carbides, sulfides, halides, hydroxides, nitrates, sulfates, phosphates, carbonates, organic acid metal salts, etc. The metal component contained in the polymer composite or highly elastic polymer composite of the present invention may be either an ion or a compound, or both. The metal components are preferably ions and oxides including zirconium, yttrium, cerium, or neodymium.

[0017] When the metal component is a compound, its shape and size are not particularly limited, but from the viewpoint of mechanical strength and shape stability in a highly elastic polymer composite containing a liquid of water and / or an organic solvent, the average particle size is preferably 100 nm or less, more preferably 1 to 50 nm.

[0018] In the present invention, the content of the above metal component is preferably 5 to 85 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 75 mass%, when the total of the above polymer and the above metal component is taken as 100 mass%, from the viewpoint of mechanical strength and shape stability in a highly elastic polymer composite containing a liquid of water and / or an organic solvent.

[0019] In the polymer composite of the present invention, ions or compounds of metals other than zirconium, yttrium, cerium and neodymium may be further dispersed as necessary. When these other dispersoids are contained, the upper limit of the content is usually 30 parts by mass, assuming that the content of the above metal components is 100 parts by mass.

[0020] Furthermore, the polymer composite of the present invention may further contain various fillers and additives for improving heat resistance, ultraviolet resistance, light resistance, oxidation resistance, flame retardancy, and the like, as required.

[0021] As described above, the polymer composite of the present invention can be a highly elastic polymer composite containing water and / or an organic solvent. In this highly elastic polymer composite, the compressive modulus is preferably 100 kPa to 30 MPa, more preferably 150 kPa to 25 MPa, and particularly preferably 200 kPa to 20 MPa. The tensile strength is preferably 100 kPa to 10 MPa, more preferably 200 kPa to 10 MPa, and particularly preferably 500 kPa to 10 MPa. The tensile breaking elongation is preferably 50 to 500%, more preferably 80 to 500%, and particularly preferably 100 to 500%. The volume expansion rate is preferably -30 to 100%, more preferably -20 to 80%, and particularly preferably -10 to 60%. These properties are superior to those of polymer gels that do not contain metal components in mechanical strength and shape stability. The compressive modulus, tensile strength, tensile breaking elongation, and volume expansion rate can be measured by the method described in [Examples].

[0022] Next, a method for producing the polymer composite of the present invention will be described. The method for producing a polymer composite of the present invention includes a mixing step of mixing a sol containing water and a metal oxide (at least one oxide selected from zirconium, yttrium, cerium, and neodymium) or an aqueous solution containing metal ions (at least one ion selected from zirconium, yttrium, cerium, and neodymium), an unsaturated monomer, and a polymerization initiator, and a polymerization step of polymerizing the unsaturated monomer.

[0023] In the mixing step, a sol containing water and a metal oxide (zirconium oxide, yttrium oxide, cerium oxide, or neodymium oxide), an aqueous solution containing metal ions, or a mixed liquid containing water, a metal compound, and metal ions can be used.

[0024] When a sol is used in the mixing step, the metal oxide may be either crystalline or amorphous, and the average particle size is preferably 100 nm or less, more preferably 1 to 50 nm, and even more preferably 5 to 30 nm. The concentration of the metal oxide in the sol is not particularly limited, but is preferably 1 to 50 mass%, more preferably 5 to 40 mass%, since a polymer composite is efficiently formed in the subsequent polymerization step.

[0025] When an aqueous solution containing metal ions is used in the mixing step, there is no particular limitation as long as it is an aqueous solution obtained by dissolving a water-soluble metal compound in water, an acidic aqueous solution, or a basic aqueous solution. The concentration of the metal ions is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, since a polymer composite is efficiently formed in the subsequent polymerization step.

[0026] The unsaturated monomers used in the mixing step are as exemplified above. In a preferred embodiment, all the unsaturated monomers are water-soluble, and the unsaturated monomers used contain at least 50% by mass of acrylamide or acrylic acid relative to the total amount. In a particularly preferred embodiment, acrylamide alone is used, and acrylamide is used in combination with a compound containing two or more polymerizable unsaturated bonds (such as N,N'-methylenebisacrylamide).

[0027] The polymerization initiator used in the mixing step is not particularly limited, and may be either an inorganic compound or an organic compound, or a combination of these. It may also be either water-soluble or oil-soluble. Specific examples of inorganic compounds include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate (ammonium peroxodisulfate). Specific examples of organic compounds include dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyric acid) dimethyl, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2, Examples of the polymerization initiator include azo compounds such as 2'-azobis[2-(2-imidazolin-2-yl)propane] or its dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and 1,1'-azobis(cyclohexane-1-carbonitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-tert-butyl peroxide, and cumene hydroperoxide. Note that, as a polymerization initiator combining an inorganic compound and an organic compound, for example, a redox polymerization initiator using sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, or the like as a reducing agent and potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroperoxide, or the like as an oxidizing agent has been known and can be used. In the present invention, the polymerization initiator may be any of a thermal polymerization initiator, a photopolymerization initiator, etc., and among these, a thermal polymerization initiator is preferred.

[0028] In the above mixing step, when a mixture is prepared by mixing a sol containing water and a metal oxide or an aqueous solution containing a metal ion with an unsaturated monomer and a polymerization initiator, in order to reliably obtain the effects of the present invention, the molar ratio of the metal oxide or metal ion to the unsaturated monomer is preferably 0.1 to 10, more preferably 0.2 to 2. The amount of the polymerization initiator used is not particularly limited. In addition, the temperature when these raw materials are mixed is preferably 30°C or less.

[0029] Next, the polymerization step is a step of polymerizing the unsaturated monomer after the mixing step, and the formed polymer usually constitutes a polymer composite while retaining water from the reaction system inside.

[0030] In the polymerization step, the mixture obtained in the mixing step may be used as it is, or may further contain the components described below, if necessary. The reaction system is prepared using a sol containing water and a metal oxide, or an aqueous solution containing metal ions, and the unsaturated monomer is preferably subjected to polymerization in a state of being dissolved in water.

[0031] In the above polymerization step, an organic solvent can be added to the reaction system as long as it does not inhibit the dispersion state of the metal oxide or metal ion or the polymerization reaction of the unsaturated monomer. Since an oil-soluble compound can also be used as the polymerization initiator, the solubility can be improved by adding an organic solvent. In addition, even when a water-insoluble unsaturated monomer is used in combination, it can be dissolved by the organic solvent, and as a result, the polymerization conversion rate of all unsaturated monomers can be improved. Examples of such organic solvents include alcohols (methanol, ethanol, propanol, etc.), alkylene glycols (ethylene glycol, etc.), cyclic ethers (tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), dialkylformamides (dimethylformamide, etc.), dialkylacetamides (dimethylacetamide, etc.), dialkylsulfoxides (dimethylsulfoxide, etc.), etc.

[0032] The reaction system may further contain various fillers and additives for improving heat resistance, UV resistance, light resistance, oxidation resistance, flame retardancy, and the like.

[0033] The reaction conditions in the polymerization step are not particularly limited. The polymerization reaction is preferably carried out under a sealed condition or in an inert gas atmosphere. When a thermal polymerization initiator is used as the polymerization initiator, the polymerization temperature is preferably 30°C to 100°C, more preferably 50°C to 100°C. The polymerization time is appropriately set depending on the composition of the reaction system, the total amount of raw materials, etc., and is usually 10 minutes or more. The upper limit of the polymerization time is usually 2 months, preferably 1 month.

[0034] In the above polymerization step, the polymerization reaction is carried out under sealed conditions, so that the polymer composite can be produced from the raw materials contained in the reaction vessel. Therefore, by using a reaction vessel having a cavity that reflects a specific shape, a polymer composite having a predetermined shape (fibrous, rod-like, plate-like, cylindrical, helical, spherical, etc.) can be directly produced. Needless to say, since the polymer composite of the present invention has excellent shape stability, it is also possible to produce a large polymer composite and then perform cutting or the like to give it a predetermined shape.

[0035] Furthermore, by adding a commonly used surfactant to the above reaction system, a polymer composite in the form of fine particles can be produced.

[0036] In the present invention, when the reaction system includes a mixture obtained by using a sol containing water and a metal oxide together with a thermal polymerization initiator, when this mixture is subjected to polymerization, the reaction solution is more likely to become highly viscous as the polymerization reaction proceeds than when an aqueous solution of metal ions is used, and the polymer composite made of the resulting reaction product is more likely to form a highly elastic polymer composite with excellent mechanical strength and shape stability. The inventors presume that the reason why the highly elastic polymer composite has such properties is that the obtained polymer composite has a structure in which the fine particles made of the metal oxide contained in the sol evenly fill the voids between the formed polymers.

[0037] As described above, the polymer composite formed by the polymerization process retains the water of the reaction system inside the polymer, but is usually capable of retaining further water and / or organic solvent, and the subsequent contacting process can reliably produce a highly elastic polymer composite with excellent mechanical strength and shape stability.

[0038] In the contact step, it is preferable to apply a method such as immersing the polymer composite in water and / or an organic solvent, or spraying water and / or an organic solvent onto the polymer composite. The organic solvent may be any of the compounds exemplified as organic solvents that can be used in the polymerization step, but the organic solvent may also be replaced in the contact step.

[0039] In particular, the highly elastic polymer composite obtained by the manufacturing method of the present invention has the above-mentioned properties (high compressive elastic modulus, high tensile properties, and low volume expansion coefficient) that are immeasurable from conventional techniques, and is useful as a medical material, a shock absorbing material, a soundproofing material, etc.

[0040] In the manufacturing method of the present invention, a solid polymer composite can be obtained by drying the reaction product, which is usually water-containing and obtained in the mixing step and the polymerization step. By subjecting this solid polymer composite to the contact step, water and / or an organic solvent can be retained, and a highly elastic polymer composite having the above-mentioned performance can be reversibly obtained. In addition, the solid polymer composite is usually porous, and can be used as a composite in which other polymer materials are impregnated therein. The polymer material is not particularly limited, but acrylic resins, epoxy resins, phenolic resins, nylon resins, ABS resins, polyesters (PET, PBT, etc.), polytetrafluoroethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyamide, polyimide, polycarbonate, polyacetal, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid esters, polymethacrylic acid esters, polyvinyl alcohol, melamine resins, silicone resins, epoxy resins, urethane resins, etc. can be used. These may be thermoplastic resins or thermosetting resins. However, in the case of a thermosetting resin, it is preferable to impregnate the solid polymer composite with the thermosetting resin and then cure it. EXAMPLES

[0041] The present invention will be described in more detail below with reference to examples. However, since these examples merely show some embodiments of the present invention, the present invention should not be interpreted as being limited to these examples.

[0042] 1. Methods for analyzing and evaluating highly elastic polymer composites In the examples and comparative examples described later, a polymer composite was first produced in which a zirconium component, a cerium component, a silicon component, or an aluminum component was dispersed in a matrix made of a polymer, and then this polymer composite was brought into contact with water or ethylene glycol (hereinafter also referred to as "EG") to produce a highly elastic polymer composite that had absorbed these liquids, which was then evaluated. The evaluation method for the highly elastic polymer composite is described below.

[0043] (1) Composition analysis of highly elastic polymer composites The highly elastic polymer composite was dried at 50°C under reduced pressure, and the amount of absorbed contact liquid (water or EG) was calculated by measuring the mass before and after the vacuum drying, and was calculated as the amount per 1g of polymer. The vacuum dried product was also subjected to thermogravimetric analysis to analyze the mass ratio of the polymer and metal components (zirconium component, cerium component, silicon component, or aluminum component), and the composition ratio of the highly elastic polymer composite was calculated from the ratio of the contact liquid obtained earlier. In addition, the thermogravimetric analysis was performed by heating up to 600°C at 10°C / min in an air atmosphere, and the weight loss from 150°C to 600°C was taken as the amount of polymer, and the residue at 600°C was taken as the amount of metal component. Tables 1, 2, and 3 show the ratios of the polymer and metal component when the total of the polymer, metal component, and absorbent component is 100% by mass (hereinafter, "% by mass" is written as "%), and the amount of the absorbent component constituting the highly elastic polymer composite was shown as the amount per 1g of polymer.

[0044] (2) Compressive modulus of highly elastic polymer composites In the examples and comparative examples described later, a mixture (vacuum degassed product) made of the manufacturing raw materials was placed in a container with a cylindrical spatial shape (inner diameter 8.8 mm) and heated at a predetermined temperature to obtain a cylindrical polymer composite. This polymer composite was then immersed in water or EG for 7 days to obtain a cylindrical highly elastic polymer composite. This was then cut to a thickness of 5 mm to obtain a test piece for measuring the compressive modulus. This test piece was set in a universal testing machine and a compression experiment was carried out at a compression speed of 3 mm / min. The compressive modulus was determined in the range of strain from 10% to 20%.

[0045] (3) Tensile strength and tensile elongation at break of highly elastic polymer composites In the examples and comparative examples described below, a mixture (vacuum degassed product) made of the manufacturing raw materials was heated at a predetermined temperature to obtain a sheet-shaped (1 to 3 mm thick) polymer composite. This polymer composite was then immersed in water for 7 days to obtain a highly elastic polymer composite. It was then cut to a predetermined size (JIS K 6251, tensile, No. 7 dumbbell shape) to obtain a test piece for a tensile test. This test piece was set in a tensile tester, and a tensile experiment was carried out at a tensile speed of 100 mm / min to measure the tensile strength and tensile elongation at break.

[0046] (4) Volume expansion rate of highly elastic polymer composites In the examples and comparative examples described below, a mixture (vacuum degassed product) made of the manufacturing raw materials was placed in a container with a cylindrical space shape (inner diameter 8.8 mm) and heated at a predetermined temperature to obtain a cylindrical polymer composite. Next, this polymer composite was cut into a disk shape and immersed in water for 7 days to obtain a disk-shaped highly elastic polymer composite. The diameter of this highly elastic polymer composite was measured, and the volume expansion coefficient was calculated according to the following formula. Volume expansion rate (%) = 100 x [diameter of high elastic polymer composite (mm) / 8.8 (mm)] 3 -100

[0047] 2. Manufacturing of polymer composites and highly elastic polymer composites Example 1 Acrylamide (hereinafter, also referred to as "AAm") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was dissolved in zirconia sol "ZSL-10T" (trade name, solid content 10.2 mass%, median diameter 13 nm) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. to prepare a 4 mol / L AAm zirconia aqueous solution (hereinafter, referred to as "AAm zirconia aqueous solution (1)"). Meanwhile, N,N'-methylenebisacrylamide (hereinafter, also referred to as "MBAA") manufactured by Tokyo Chemical Industry Co., Ltd. and ammonium peroxodisulfate (hereinafter, also referred to as "APS") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. were dissolved in water, respectively, to prepare a 0.2 mol / L MBAA aqueous solution and a 0.1 mol / L APS aqueous solution. Next, 5 mL of 4 mol / L AAm zirconia aqueous solution (1), 0.02 mL of 0.2 mol / L MBAA aqueous solution, 0.2 mL of 0.1 mol / L APS aqueous solution, and 4.78 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 50°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.40. Thereafter, the polymer composite was immersed in water at 25° C. for 7 days to obtain a highly elastic polymer composite. The highly elastic polymer composite thus obtained was subjected to various evaluations. The results are shown in Table 1.

[0048] Examples 2 to 5 Polymer composites and highly elastic polymer composites were produced and evaluated in the same manner as in Example 1, except that the heating temperature of the mixture was changed from 50° C. to 60° C., 70° C., 80° C., or 90° C. The results are shown in Table 1.

[0049] Examples 6 to 10 Except for changing the heating time of the mixture from 3 hours to 3 days (Example 6), 7 days (Example 7), 14 days (Example 8), 21 days (Example 9), or 28 days (Example 10), polymer composites and highly elastic polymer composites were produced and various evaluations were carried out in the same manner as in Example 3. The results are shown in Table 1. Moreover, the polymer composite of Example 6 was immersed in ethylene glycol for 7 days to produce a highly elastic polymer composite, and only the compressive modulus was measured (see Table 1).

[0050] Examples 11 to 13 and 15 to 21 As the zirconia sol, "ZSL-10T" (trade name, solid content 13.6 mass%, median diameter 15 nm) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., which has a different solid content from that used in Example 1, was used. Using this zirconia sol "ZSL-10T", a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (2)") was prepared in the same manner as in Example 1, and using these as production raw materials, a polymer composite and a highly elastic polymer composite were produced in the same manner as in Examples 1 to 10. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.56. After that, various evaluations were performed on the obtained highly elastic polymer composite. The results are shown in Table 1. In addition, the polymer composite of Example 17 was immersed in ethylene glycol for 7 days to produce a highly elastic polymer composite, and only the compressive modulus was measured (see Table 1).

[0051] Example 14 5 mL of 4 mol / L AAm zirconia aqueous solution (2), 0.2 mL of 0.1 mol / L APS aqueous solution, and 4.78 mL of the above zirconia sol "ZSL-10T" (trade name, solid content 13.6 mass%, median diameter 15 nm) were mixed. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.56. Thereafter, the polymer composite was immersed in water at 25° C. for 7 days to obtain a highly elastic polymer composite. The highly elastic polymer composite thus obtained was subjected to various evaluations. The results are shown in Table 1.

[0052] Examples 22 to 24 and 26 to 32 As the zirconia sol, zirconia sol "ZSL00120" (trade name, solid content 30.3 mass%, median diameter 14 nm) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. was used. Using this zirconia sol "ZSL00120", a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (3)") was prepared in the same manner as in Example 1, and using these as production raw materials, a polymer composite and a highly elastic polymer composite were produced in the same manner as in Examples 1 to 10. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.45. Thereafter, various evaluations were performed on the obtained highly elastic polymer composite. The results are shown in Table 2. Moreover, the polymer composite of Example 28 was immersed in ethylene glycol for 7 days to produce a highly elastic polymer composite, and only the compressive modulus was measured (see Table 2).

[0053] Example 25 5 mL of 4 mol / L AAm zirconia aqueous solution (3), 0.2 mL of 0.1 mol / L APS aqueous solution, and 4.78 mL of the above zirconia sol "ZSL00120" (product name, solid content 30.3 mass%, median diameter 14 nm) were mixed. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.40. Thereafter, the polymer composite was immersed in water at 25° C. for 7 days to obtain a highly elastic polymer composite. The highly elastic polymer composite thus obtained was subjected to various evaluations. The results are shown in Table 2.

[0054] Examples 33 to 42 As the zirconia sol, "ZSL00120" (trade name, solid content 34.9 mass%, median diameter 10 nm) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., which has a different solid content and median diameter from that used in Example 22, was used. This zirconia sol "ZSL00120" was used, and a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (4)") was used in the same manner as in Example 1 to 10, except that a polymer composite and a highly elastic polymer composite were produced. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.70. Thereafter, various evaluations were performed on the obtained highly elastic polymer composite. The results are shown in Table 2. Moreover, the polymer composite of Example 38 was immersed in ethylene glycol for 7 days to produce a highly elastic polymer composite, and only the compressive modulus was measured (see Table 2).

[0055] Example 43 Acrylamide (AAm) was dissolved in an aqueous solution of zirconium oxynitrate "Zircosol ZN" (trade name, solid content 25.4% by mass) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. to prepare a 4 mol / L aqueous solution of AAm zirconium oxynitrate. Next, 5 mL of 4 mol / L AAm oxyzirconium nitrate aqueous solution, 0.02 mL of 0.2 mol / L MBAA aqueous solution, 0.2 mL of 0.1 mol / L APS aqueous solution, and 4.78 mL of the above zirconium oxynitrate solution "Zircosol ZN" were mixed. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. Then, a highly elastic polymer composite was obtained in the same manner as in Example 1. The molar ratio of the metal ion (zirconium ion) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.36. The mass ratios of the polymer and metal component (zirconium ion) constituting the highly elastic polymer composite were 51.4 mass% and 48.6 mass%, respectively, and the liquid absorption was 2.69 g / g. After that, various evaluations were performed on the obtained highly elastic polymer composite. The results are shown in Table 3.

[0056] Example 44 Zirconia sol "ZSL-10T" (trade name, solid content 10.2 mass%, median diameter 13 nm) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. was diluted with water to prepare a zirconia sol aqueous solution with a solid content of 5.4 mass%. Acrylamide (AAm) was then dissolved in this zirconia sol aqueous solution to prepare a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (5)"). Meanwhile, the above-mentioned ammonium peroxodisulfate (APS) was dissolved in water to prepare a 0.1 mol / L APS aqueous solution. Next, 5 mL of the 4 mol / L AAm zirconia aqueous solution (5), 0.2 mL of the 0.1 mol / L APS aqueous solution, and 4.8 mL of the above-mentioned zirconia sol aqueous solution were mixed and bubbled with nitrogen. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.20. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were carried out. The results are shown in Table 3.

[0057] Example 45 As the zirconia sol, "ZSL-10T" (trade name, solid content 10.2 mass%, median diameter 13 nm) was used. This zirconia sol "ZSL-10T" and acrylamide (AAm) were used to prepare a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (6)"). Next, 7.5 mL of the 4 mol / L AAm zirconia aqueous solution (6), 0.2 mL of the 0.1 mol / L APS aqueous solution, and 2.3 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.24. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0058] Example 46 2.5 mL of the 4 mol / L AAm zirconia aqueous solution (6) prepared in Example 45, 0.2 mL of the 0.1 mol / L APS aqueous solution, and 7.3 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. The mixture was then placed in a reaction vessel and degassed under vacuum, and heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.85. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0059] Example 47 As the zirconia sol, zirconia sol "ZSL00120" (trade name, solid content 30.3 mass%, median diameter 14 nm) manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. was used. This zirconia sol "ZSL00120" and acrylamide (AAm) were used to prepare a 4 mol / L AAm zirconia aqueous solution (hereinafter referred to as "AAm zirconia aqueous solution (7)"). Next, 7.5 mL of the 4 mol / L AAm zirconia aqueous solution (7), 0.2 mL of the 0.1 mol / L APS aqueous solution, and 2.3 mL of the above zirconia sol "ZSL00120" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70 ° C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.83. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0060] Example 48 2.5 mL of the 4 mol / L AAm zirconia aqueous solution (7) prepared in Example 47, 0.2 mL of the 0.1 mol / L APS aqueous solution, and 7.3 mL of the above zirconia sol "ZSL00120" were mixed and bubbled with nitrogen. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 2.93. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0061] Example 49 The above-mentioned N,N'-methylenebisacrylamide (MBAA) and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (hereinafter also referred to as "AIYP") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. were dissolved in water and methanol, respectively, to prepare a 0.1 mol / L MBAA aqueous solution and a 0.1 mol / L AIYP solution. Next, 5 mL of the 4 mol / L AAm zirconia aqueous solution (6) prepared in Example 45, 0.04 mL of a 0.1 mol / L MBAA aqueous solution, 0.2 mL of a 0.1 mol / L AIYP solution, and 4.76 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 90 ° C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.39. Thereafter, a highly elastic polymer composite was produced and various evaluations were carried out in the same manner as in Example 1. The results are shown in Table 3.

[0062] Example 50 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (hereinafter also referred to as "AMHP") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was dissolved in water to prepare a 0.1 mol / L AMHP aqueous solution. Next, 5 mL of 4 mol / L AAm zirconia aqueous solution (6), 0.04 mL of 0.1 mol / L MBAA aqueous solution, 0.2 mL of 0.1 mol / L AMHP aqueous solution, and 4.76 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 90°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.39. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0063] Example 51 4,4'-azobis(4-cyanovaleric acid) (hereinafter also referred to as "ACA") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was dissolved in methanol to prepare a 0.1 mol / L ACA solution. Next, 5 mL of the 4 mol / L AAm zirconia aqueous solution (6) prepared in Example 45, 0.04 mL of a 0.1 mol / L MBAA aqueous solution, 0.2 mL of a 0.1 mol / L ACA solution, and 4.76 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 90°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.39. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0064] Example 52 5 mL of the 4 mol / L AAm zirconia aqueous solution (7) prepared in Example 47, 0.04 mL of a 0.1 mol / L MBAA aqueous solution, 0.2 mL of a 0.1 mol / L AIYP solution, and 4.76 mL of the above zirconia sol "ZSL00120" were mixed and bubbled with nitrogen. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 90°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.35. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0065] Example 53 As the zirconia sol, "ZSL-10T" (trade name, solid content 10.2 mass%, median diameter 13 nm) was used. In this zirconia sol, acrylic acid (hereinafter also referred to as "AAc") manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was dissolved to prepare a 4 mol / L AAc zirconia aqueous solution (hereinafter referred to as "AAc zirconia aqueous solution"). 5 mL of 4 mol / L AAc zirconia aqueous solution, 0.04 mL of 0.1 mol / L MBAA aqueous solution, 0.2 mL of 0.1 mol / L APS aqueous solution, and 4.76 mL of the above zirconia sol "ZSL-10T" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70 ° C for 24 hours to obtain a polymer composite. The molar ratio of the metal oxide (zirconia) to the water-soluble vinyl group-containing monomer (acrylic acid) was 0.39. Thereafter, a highly elastic polymer composite was produced and various evaluations were carried out in the same manner as in Example 1. The results are shown in Table 3.

[0066] Example 54 As the ceria sol, "CESL-30N" (trade name, solid content 30.2 mass%, median diameter 5 nm) was used. This ceria sol "CESL-30N" and acrylamide were used to prepare a 4 mol / L AAm ceria aqueous solution (hereinafter referred to as "AAm ceria aqueous solution"). Next, 5 mL of 4 mol / L AAm ceria aqueous solution, 0.04 mL of 0.1 mol / L MBAA aqueous solution, 0.2 mL of 0.1 mol / L AIYP solution, and 4.76 mL of the above ceria sol "CESL-30N" were mixed and bubbled with nitrogen. Then, the mixture was placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 70°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (ceria) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.03. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0067] Example 55 5 mL of the 4 mol / L AAm ceria aqueous solution prepared in Example 54, 0.04 mL of a 0.1 mol / L MBAA aqueous solution, 0.1 mL of a 0.1 mol / L AIYP solution, and 4.86 mL of the above-mentioned zeriasol "CESL-30N" were mixed and bubbled with nitrogen. The mixture was then placed in a reaction vessel and degassed under vacuum, and then heated in an oven at 90°C for 3 hours to obtain a polymer composite. The molar ratio of the metal oxide (ceria) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.03. Thereafter, a highly elastic polymer composite was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3.

[0068] Comparative Examples 1 to 10 Except for using water instead of zirconia sol, polymer composites and highly elastic polymer composites were produced in the same manner as in Examples 1 to 10. Thereafter, various evaluations were carried out on the highly elastic polymer composites obtained in Comparative Examples 1 and 2, and the results are shown in Table 4. In Comparative Examples 3 to 10 and 13, evaluations could not be carried out because a solid was not obtained by polymerization through heating, or a solid was obtained but absorbed too much water when immersed in water and was unable to maintain its shape.

[0069] Comparative Examples 11 to 14 Polymer composites and highly elastic polymer composites were produced in the same manner as in Examples 3 to 6, except that a 4 mol / L AAm silica aqueous solution prepared using a silica sol "Snowtex O" (trade name, solid content 20.6 mass%, particle size 12 nm) manufactured by Nissan Chemical Industries, Ltd. was used instead of the AAm zirconia aqueous solution (1). The molar ratio of the metal oxide (silica) to the water-soluble vinyl group-containing monomer (acrylamide) was 1.68. Thereafter, the compressive modulus and volume expansion coefficient were measured for the highly elastic polymer composites obtained in Comparative Examples 11 and 12, and the results are shown in Table 4. In Comparative Example 14, although a solid was obtained, it was not possible to perform evaluation because it absorbed too much water when immersed in water and could not maintain its shape.

[0070] Comparative Examples 15 to 18 Polymer composites and highly elastic polymer composites were produced in the same manner as in Examples 3 to 6, except that a 4 mol / L AAm alumina aqueous solution prepared using an alumina sol "Aluminosol-10A" (product name, solid content 10 mass%, short diameter 10 nm, long diameter 50 nm) manufactured by Kawaken Fine Chemical Co., Ltd. was used instead of the AAm zirconia aqueous solution (1). The molar ratio of the metal oxide (alumina) to the water-soluble vinyl group-containing monomer (acrylamide) was 0.47. Thereafter, the compressive modulus and volume expansion coefficient of the obtained highly elastic polymer composite were measured, and the results are shown in Table 4.

[0071] [Table 1]

[0072] [Table 2]

[0073] [Table 3]

[0074] [Table 4]

[0075] Examples 1 to 55 are examples of highly elastic polymer composites according to the present invention, and it was found that, compared with highly elastic polymer composites not containing metal components and highly elastic polymer composites containing silica or alumina, they have higher compressive modulus and tensile strength, excellent mechanical strength, a lower volume expansion coefficient, and excellent shape stability. [Industrial Applicability]

[0076] The highly elastic polymer composite of the present invention has excellent mechanical strength and high shape stability, and is therefore useful as a medical material, a shock absorbing material, a soundproofing material, etc.

Claims

1. A method for producing a composite material comprising the steps of: a polymer including a structural unit derived from an unsaturated monomer; a metal component dispersed in a matrix of the polymer; and water and / or an organic solvent, the metal component being at least one selected from a zirconium component, a yttrium component, and a neodymium component; the content of the metal component is 5 to 85% by mass, where the total content of the polymer and the metal component is 100% by mass; the organic solvent is a water-soluble or hydrophilic compound, A highly elastic polymer composite having a compressive elastic modulus of 100 kPa to 30 MPa as measured by the following method. (Method of measuring compressive elastic modulus) A highly elastic polymer composite having a thickness of 5 mm is subjected to a compression experiment at a compression speed of 3 mm / min, and the compressive elastic modulus is determined in the range of strain from 10% to 20%.

2. 2. The highly elastic polymer composite according to claim 1, wherein the unsaturated monomer comprises at least one of acrylamide and acrylic acid.

3. 3. The highly elastic polymer composite according to claim 1, wherein the metal component is a metal oxide or a metal ion.

4. 4. The highly elastic polymer composite according to claim 1, having a tensile strength of 100 kPa to 10 MPa as measured by the following method. (Method of measuring tensile strength) The tensile strength is obtained by a tensile test in accordance with JIS K 6251 (tensile, No. 7 dumbbell shape) at a tensile speed of 100 mm / min.

5. 5. The highly elastic polymer composite according to claim 1, wherein the tensile elongation at break measured by the following method is 50 to 500%. (Method of measuring tensile elongation at break) The tensile elongation at break is obtained by a tensile test in accordance with JIS K 6251 (tensile, No. 7 dumbbell shape) at a tensile speed of 100 mm / min.

6. 6. The highly elastic polymer composite according to claim 1, which has a volume expansion coefficient of −30 to 100% as measured by the following method. (Method of measuring volume expansion rate) A mixture (vacuum degassed product) consisting of the raw materials for producing a highly elastic polymer composite was placed in a container with a cylindrical spatial shape (inner diameter 8.8 mm) and heated to produce a cylindrical polymer composite. The sample was then cut into a disk shape and immersed in water for 7 days. The diameter of the resulting disk-shaped highly elastic polymer composite was measured, and the volume expansion coefficient was calculated using the following formula. Volume expansion rate (%) = 100 x [diameter of highly elastic polymer composite (mm) / 8.8 (mm)] ３ -100

7. A method for producing a highly elastic polymer composite according to any one of claims 1 to 6, characterized in that the method comprises, in sequence, a mixing step of mixing a sol containing water and a metal oxide or an aqueous solution containing metal ions with an unsaturated monomer and a polymerization initiator, and a polymerization step of polymerizing the unsaturated monomer.

8. The method for producing a highly elastic polymer composite according to claim 7, further comprising a contacting step of contacting the reaction product obtained in the polymerization step with water and / or an organic solvent.

9. 9. The method for producing a highly elastic polymer composite according to claim 7, wherein the unsaturated monomer comprises at least one of acrylamide and acrylic acid.

10. The method for producing a highly elastic polymer composite according to any one of claims 7 to 9, wherein the unsaturated monomer further contains a compound having two or more polymerizable unsaturated bonds.

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