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WO2007069765A1 - Matériau auto-réparateur - Google Patents

Matériau auto-réparateur Download PDF

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Publication number
WO2007069765A1
WO2007069765A1 PCT/JP2006/325149 JP2006325149W WO2007069765A1 WO 2007069765 A1 WO2007069765 A1 WO 2007069765A1 JP 2006325149 W JP2006325149 W JP 2006325149W WO 2007069765 A1 WO2007069765 A1 WO 2007069765A1
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WO
WIPO (PCT)
Prior art keywords
self
healing
compound
functional group
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/325149
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English (en)
Japanese (ja)
Inventor
Masayuki Yamaguchi
Minoru Terano
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Japan Advanced Institute of Science and Technology
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Japan Advanced Institute of Science and Technology
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Filing date
Publication date
Application filed by Japan Advanced Institute of Science and Technology filed Critical Japan Advanced Institute of Science and Technology
Priority to JP2007550261A priority Critical patent/JP5145564B2/ja
Publication of WO2007069765A1 publication Critical patent/WO2007069765A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52—Hydrogels or hydrocolloids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00—Compositions for creating shape memory

Definitions

  • the present invention relates to a self-healing material that naturally heals even if a scratch occurs on the surface.
  • the present invention relates to a crosslinked polymer in which a number of dangling chains are bonded to the crosslinked polymer structure, and has a material shape retaining action and a wound self-healing action.
  • a self-healing material that is compatible a method for producing the self-healing material, a self-healing structure in which the self-healing material is fixed to the base material soil, and the self-healing material or the self-healing structure described above And a biomedical material and an optical material.
  • self-healing materials that heal spontaneously and return to their original state even when scratches occur are characteristics that are not found in conventional artificial structures, and their self-healing is strongly desired.
  • Applications of self-healing materials include skin materials made of various materials such as materials used in places where repair work is difficult, such as outer space and the body, as well as the decline in commercial value due to surface scratches, optical materials, etc. Is the target.
  • self-healing materials microcapsules and hollow fillers containing chemical reactants are mixed with specific plastic materials, and the microcapsules hollow fillers break down at the same time as scratches occur, and the internal chemical reactants.
  • Self-healing materials based on the method of repairing damaged parts by spreading in the plastic have been proposed in, for example, the following documents 1 to 4.
  • Non-Patent Document 5 proposes a method of paying attention to polyphenylene ether and polycarbonate, and performing self-repair by mixing a catalyst that causes a reaction again after degradation and degradation.
  • the method of Non-Patent Document 5 is a method of re-bonding the main chain of a polymer using a chemical reaction in a specific type of polymer compound.
  • Non-Patent Document 6 K. lakeda, M. Tanahashi, H. Unno, bci. Techno ⁇ . Adv. Mater i als, vol. 4, pp. 435-444, (2003).
  • a method of repairing the generated scratch by raising the temperature above the glass transition temperature is proposed in, for example, Non-Patent Document 6 below, and a method of repairing the scratch by immersing in a specific solvent is: For example, it is proposed in the following non-patent document 7 ′.
  • Non-Patent Document 1 to Non-Patent Document 4 it is necessary to include chemical substances in microcapsules and hollow fillers, and they must be dispersed in plastic, so that they are inferior in cost performance and technical. It is also difficult. Furthermore, it is unlikely that repeated repair of scratches on the same part of the material is expected.
  • Non-Patent Document 1 to Non-Patent Document 5 are applied to specific polymers. There was a problem that it was limited to compounds.
  • Non-Patent Documents 6 and 7 the self-repairing action does not appear autonomously, and the material in which the scratch has occurred must be heated to a temperature higher than the glass transition temperature or immersed in a specific solvent. Therefore, it was practically difficult to apply.
  • the method of Non-Patent Document 6 performs self-healing by using diffusion of linear polymer chains in short, thus realizing practical self-healing speed and fluidization of material (deformation of self-healing material) There is a practically fatal problem that shape collapse is directly connected to the straight.
  • An object of the present invention is to provide such a self-healing material.
  • the first invention of the present application is a polymer crosslinked body in which a large number of dangling chains are bonded to the polymer crosslinked structure, and the amount of dangling chains bonded to the polymer crosslinked structure and the crosslinking point of the polymer crosslinked structure.
  • a self-healing material that exhibits the properties of a near-critical gel that achieves both the retention of the material shape due to the high molecular cross-linking structure and the self-healing effect due to the dangling chains by adjusting the intermolecular weight within a specific region. It is.
  • the material shape retention action and the self-healing action compatible In the self-healing material of the first invention, the material shape retention action and the self-healing action compatible.
  • a crosslinked polymer having such characteristics is referred to as “near critical gel”.
  • the holding action of the material shape is due to the above-described polymer cross-linked structure.
  • the self-healing effect on the wound is due to the dangling chain.
  • the dangling chain means “a partial chain in which one end is connected to a crosslinked product and the other end is not connected to a crosslinked product”.
  • the mechanism of self-healing action by dangling chains is that when the self-healing material is damaged, dangling chains penetrate into each other in and between the molecules of the polymer cross-linked body, and the cohesive force due to entanglement According to topology interaction. Therefore, the time required for self-healing becomes shorter at higher temperatures.
  • the self-healing action is promoted by increasing the temperature, as long as the bonding amount of the dangling chain and the molecular weight between the crosslinking points of the polymer crosslinking structure are adjusted within a specific region, the shape of the material The holding action and the self-healing action are well balanced. This point is decisively different from the case of Non-Patent Document 6 described above.
  • the self-healing material of the first invention can be manufactured by a simple and low-cost process. Moreover, as long as it is a crosslinked polymer, its application target is not limited by the type of polymer compound. Secondly, the self-healing action is based on the above-described topological interaction, so it occurs repeatedly in the same part of the material. In addition, the self-repairing action is manifested autonomously and without shape collapse. That is, the self-healing material of the first invention can solve the above-described problems of the present invention.
  • FIG. 1 schematically shows the self-healing material of the first invention.
  • Fig. 1 (a) A single molecule of the polymer cross-linked product 1 is shown to be immobilized on the base material 3 by a chemical reaction at a fixing point 2 having a functional group.
  • the polymer cross-linked product 1 the polymer cross-linked structure is shown.
  • a number of dangling chains 4 are shown visually.
  • FIG. 1 (b) shows a state in which a plurality of molecules of the polymer crosslinked body 1 are densely fixed to the base material 3 at the fixing point 2 to form the coating layer 5.
  • Fig. 1 schematically shows the self-healing material of the first invention.
  • Fig. 1 (a) A single molecule of the polymer cross-linked product 1 is shown to be immobilized on the base material 3 by a chemical reaction at a fixing point 2 having a functional group.
  • the polymer cross-linked structure the polymer cross-linked structure is shown.
  • 1 is only a schematic illustration of a self-healing material, and specifically illustrates specific regions regarding the amount of dangling chains attached to the polymer cross-linked structure and the molecular weight between cross-linking points of the polymer cross-linked structure. It is not specified.
  • the “specific region” relating to the amount of dangling chain bonds and the molecular weight between crosslink points is the type of polymer, the type of monomer compound that forms the polymer, the polymer crosslink Because it varies depending on the contents of the structure, it is difficult or impossible to uniformly define these specific regions with numerical values. However, as will be described later in the second invention, it is possible to define a specific region that defines a near-critical gel in terms of the physical properties of the self-healing material.
  • the self-healing material according to the first invention satisfies one or more of the following conditions (a) to (d).
  • Loss tangent at a temperature 20 ° C higher than the glass transition temperature which is defined as the temperature at which the loss modulus is maximum in the measurement of dynamic viscoelasticity, is in the range of 0.6 to 10.0. .
  • a specific region as a near critical gel in the self-healing material according to the first invention is defined from the viewpoint of material properties and the like.
  • the gel fraction means [[weight after drying] / [weight before dipping] X 10 0 (%)].
  • the gel fraction is less than 30%, This means that there is a large amount of sol whose both ends are not connected to the frame, and in this case, the self-healing material becomes highly sticky on the surface and often causes inconvenience in handling.
  • the crosslinked polymer according to the first or second invention is a polyester resin, a polyamide resin, a polycarbonate resin, a polyurethane resin, a polyether resin, an epoxy resin, a polyimide resin, One or more of polyolefin resin, polystyrene resin, saturated rubber, unsaturated rubber, or other resin.
  • the resin species of the crosslinked polymer constituting the self-healing material is essentially limited. Although not specified, those listed in the third invention can be preferably exemplified.
  • the elastic modulus of the self-healing material varies depending on the selection of the resin type and the chemical structure of the polymer cross-linked body. Therefore, the elastic modulus of the surface of the self-healing material should be controlled to glass, leather, rubber, etc. Is possible.
  • a catalyst may be used to provide a certain first compound and a second compound or a certain first compound as defined in (1) to (3) below.
  • a self-healing material according to any one of the first to third inventions is produced by mixing and reacting a compound to a third compound at a predetermined reaction ratio.
  • a method for producing a self-healing material is produced by mixing and reacting a compound to a third compound at a predetermined reaction ratio.
  • a first compound having three or more functional groups A in one molecule and a second compound having two or more functional groups B that specifically bind to functional group A in one molecule are functional groups AZ.
  • the reaction ratio of the functional group B (the ratio of the number of moles of the functional group involved in the reaction: says the same shall apply hereinafter) is set to 0.3 to 0.7 and reacted.
  • a first compound having three or more functional groups A in one molecule a second compound having two or more functional groups B specifically binding to the functional group A, and a functional group A.
  • a third compound having two in one molecule is mixed and reacted at a functional group A / functional group B reaction ratio of 0.4 to 0.8.
  • the number of moles of functional group A derived from the first compound occupies 25% or more of the total number of moles of functional group A.
  • Functional group A includes a first compound having three or more functional groups A in one molecule and a second compound having three or more functional groups B that specifically bind to functional group A in one molecule.
  • / Reaction ratio of functional group B is 0.1 to 0.6 and mixed and reacted.
  • the self-healing material according to any one of the first invention to the third invention A simple and low cost manufacturing method is provided.
  • the self-healing material of the first invention which is a “near criticality gel”, as described above, it is difficult or impossible to uniformly define the specific region that defines this from the structural aspect. While it is possible to define from the viewpoint of material properties, etc. as in the second invention, it can also be defined by manufacturing conditions as in the fourth invention.
  • the first compound has a polyisocyanate having three or more isocyanate groups as a functional group A in one molecule.
  • the second compound is a polymer polyol having two or more hydroxyl groups in one molecule, and the self-healing material produced is a polyurethane resin, the reaction ratio of isocyanate group / hydroxyl group is 0.
  • the first compound and the second compound are mixed and reacted as 3 to 0.7.
  • the fifth invention provides an example of a particularly preferred embodiment of the polyurethane resin among the methods for producing the self-recovering material of the fourth invention.
  • As the reaction ratio of isocyanate group / hydroxy group a value of 0.5.5 or a value in the vicinity thereof is particularly preferred.
  • a sixth invention of the present application is a self-healing structure in which the self-healing material according to any one of the first to third inventions is immobilized on a base material.
  • the form of “immobilization” is not limited, but as a typical form, the molecular chain of the polymer crosslinked body constituting the self-healing material is located at one or a plurality of places. And a form chemically bonded to the substrate.
  • the usage form of the self-healing material according to the first to third inventions is not limited, but as a self-healing structure in which the self-healing material is fixed on the substrate as in the sixth invention The state is particularly useful.
  • the type of the substrate is not particularly limited as long as it has means capable of immobilizing the crosslinked polymer, but for example, a substrate made of a polymer material is preferably used.
  • a substrate made of a polymer material is preferably used.
  • the elastic modulus at the use temperature of the polymer crosslinked body constituting the self-healing material is 1/10 of the elastic modulus of the substrate.
  • the thickness of the crosslinked polymer is 0.1 mn! Within the range of ⁇ 10 mm.
  • the elastic modulus of the crosslinked polymer at the operating temperature exceeds 110 of the elastic modulus of the substrate, the mechanical properties of the substrate may be greatly impaired. If the thickness of the crosslinked polymer is less than 0 ⁇ 1 mm, there is a problem that the scratches that are received easily reach a substrate that does not have self-healing properties. When the thickness of the crosslinked polymer exceeds 10 mm, the mechanical properties of the base material are greatly impaired, and the self-healing material tends to be wasted.
  • the eighth invention of the present application is a self-healing structure in which the self-healing material according to the sixth invention or the seventh invention is used as the skin of the substrate.
  • base material skin is not limited.
  • the skin layer or coating layer of the base material which is an inorganic or organic material, the human body or other organisms, or the body tissue separated from them. Skin layer and the like.
  • Skin includes “outer skin” exposed to the outside world and “inner skin” existing in the internal space of biological or inanimate structures. '
  • a ninth invention of the present application is a self-healing material according to any one of the first invention to the third invention or a self-healing structure according to any of the sixth invention to the eighth invention, which is used as a biomedical material. It is a biomedical material.
  • Biomedical materials can be mentioned as a particularly useful application of the above self-healing material or self-healing structure.
  • Specific examples of biomedical materials include artificial blood vessel epidermis, artificial organ skin, and the like. (Invention 10)
  • the tenth invention of the present application is a self-healing material according to any one of the first to third inventions or a self-healing structure according to any of the sixth to eighth inventions, It is an optical material that is used.
  • FIG. 1 is a diagram schematically showing the structure of the self-healing material of the present invention.
  • FIG. 2 is a photograph showing the evaluation of the restorability of the self-healing material according to the example of the present invention.
  • FIG. 3 is a photograph showing the evaluation of the repairability of the self-healing material according to the example of the present invention.
  • FIG. 4 is a photograph showing the state of the repairability evaluation of the self-healing material according to the example of the present invention.
  • FIG. 1 is a diagram schematically showing the structure of the self-healing material of the present invention.
  • FIG. 2 is a photograph showing the evaluation of the restorability of the self-healing material according to the example of the present invention.
  • FIG. 3 is a photograph showing the evaluation of the repairability of the self-healing material according to the example of the present invention.
  • FIG. 4 is a photograph showing the state of the repairability evaluation of the self-healing material according to the example of the present invention.
  • FIG. 5 is a diagram showing a method for evaluating the repairability of a self-healing material according to an embodiment of the present invention.
  • FIG. 6 is a photograph showing a state of the repairability evaluation of the self-healing material according to the example of the present invention.
  • the self-healing material according to the present invention is a crosslinked polymer in which a number of dangling chains are bonded to the crosslinked polymer structure.
  • the amount of dangling chains attached to the polymer cross-linked structure and the molecular weight between cross-linking points of the polymer cross-linked structure are adjusted within a certain specific region, thereby exhibiting the properties of near-critical gels.
  • the characteristic of the near-critical gel means that the retention of the material shape and the self-healing action are compatible.
  • the self-healing material according to the present invention has the following (a ) ⁇ (D) can also be defined as satisfying one or more of the conditions.
  • Loss tangent at a temperature 20 ° C higher than the glass transition temperature which is defined as the temperature at which the loss modulus is maximum in the measurement of dynamic viscoelasticity, is in the range of 0.6 to 10.0. It is.
  • the above conditions (a) to (d) will be described in more detail as follows.
  • the crosslinked polymer used in the self-healing material has a loss tangent at a temperature 20 ° C. higher than the glass transition temperature in the range of 0.6 to 10.0, more preferably in the range of 0.65 to 5.0. Of these, more preferably in the range of 0.7 to 3.0. If the loss tangent at this temperature is less than 0.6, self-healing is not exhibited, and if it exceeds 10.0, it is difficult to maintain the shape.
  • the loss tangent at a temperature 50 ° C. higher than the glass transition temperature is in the range of 0.3 to 10.'0, more preferably in the range of 0.5 to 30. Further excellent self-repair. It is preferable to show the property.
  • the polymer cross-linked product has a higher temperature than the glass transition temperature and a large loss tangent at temperature. This means that one end is connected to the cross-linked product and the other end is not connected to the cross-linked product (dangling chain). Is called). Since the dangling strand shows entanglement and interaction with other adjacent dangling strands, once it is cleaved, it shows repair properties by entanglement interaction again.
  • the glass transition degree in the present invention means a temperature defined as a temperature at which the tensile loss elastic modulus is maximum in the measurement of dynamic viscoelasticity, and is measured by a commercially available forced vibration type dynamic viscoelasticity measuring device. It is possible to measure easily.
  • the crosslinked polymer used in the self-healing material of the present invention has a ratio between the storage elastic modulus (E20) at a temperature 20 ° C. higher than the glass transition temperature and the storage elastic modulus (E 80) at a temperature higher than 80 ° C.
  • E 20ZE 80 is in the range of 3 to: 100, more preferably Is in the range of 8 to 80. If E 2 0 / E 80 is less than 3, self-repairing properties are not exhibited, and if it exceeds 100, it is difficult to maintain the shape.
  • a large decrease in storage modulus at a temperature higher than the glass transition temperature means that there are many dangling chains.
  • the dangling strand exhibits a repair property to the wound due to the above-described action.
  • the storage elastic modulus decreases too much, the temperature dependence of the elastic modulus becomes excessive, which may cause practical problems.
  • the polymer frame used in the self-healing material of the present invention has a tensile elongation at break exceeding 300%. If the tensile elongation at break is 300% or less, self-healing is not exhibited.
  • High elongation of the polymer crosslinked body generally means that the molecular weight between crosslinks is large.
  • Cross-linked product with large molecular weight between cross-linking points The cross-linking density is low, and tangling interaction between the dangling chain and the cross-linked chain (partial chain where both ends are connected to the cross-linked product) also occurs. Therefore, self-healing properties are even better. '
  • the crosslinked polymer used in the self-healing material of the present invention has a gel fraction [[weight after drying] g [weight before dipping] X 10 0 (%)] of 30%, more preferably 5%. It is desirable to exceed 0%, more preferably 80%. When the gel fraction is less than 30%, the surface tackiness becomes violent, which often causes inconvenience in handling.
  • the low gel fraction of the polymer cross-linked product means that the amount of sol whose both ends are not connected to the cross-linked product increases.
  • the sol component causes surface stickiness, making it difficult to use as a material.
  • the crosslinked polymer used in the self-healing material of the present invention has an equilibrium swelling degree (([weight after swelling] ⁇ 1 [weight after drying]) of the gel contained in the crosslinked body in acetone. / [Weight after drying]) is 2 or more, preferably 5 or more at room temperature, which makes the self-repairing property remarkable.
  • the equilibrium swelling degree of the crosslinked polymer is large, the molecular weight between the crosslinking points becomes large. If the molecular weight between crosslinks is large, the crosslink density of the crosslinked product is low.
  • Self-repairability is excellent because entanglement and interaction occur with (a partial chain in which both ends are connected to a crosslinked product). .
  • the polymer crosslinked product used in the self-healing material of the present invention has a glass transition temperature defined as a temperature at which the tensile loss elastic modulus at a frequency of 10 Hz is maximized in the measurement of dynamic viscosity. It is desirable that the temperature is not higher than 20 ° C., which increases the repair speed. . ''
  • the self-healing behavior in the self-healing material of the present invention is due to entanglement interaction involving dangling chains.
  • the time until the entanglement interaction is formed depends on the diffusion rate of the molecule, and since the diffusion rate becomes extremely small below the glass transition temperature, self-healing properties are not shown in practice.
  • the resin type of the self-healing material is not limited as long as it can form a polymer cross-linked body, but since the control of the reaction is easy, polyester resin, polyamide resin, polycarbonate resin, polyurethane resin, poly It is preferably composed of one or more of ether resin, epoxy resin, polyimide resin, polyolefin resin, polystyrene resin, saturated rubber and unsaturated rubber. In addition, blend materials of these self-healing materials and other types of materials that are not self-healing materials (resin rubber) may be used.
  • the self-healing material of the present invention can be produced by the method of the fourth invention. That is, if necessary, using a catalyst, a certain first compound and second compound, or certain first compound to third compound, as defined in (1) to (3) below. Predetermined This is a method for producing the self-healing material described above by mixing and reacting at the reaction ratio (the ratio of the number of moles of functional groups involved in the reaction; the same shall apply hereinafter).
  • Functional group A includes a first compound having three or more functional groups A in one molecule and a second compound having two or more functional groups B that specifically bind to functional group A in one molecule.
  • / Reaction ratio of functional group B is 0.3 to 0.7 'and mixed and reacted.
  • a third compound having two in a molecule is mixed and reacted at a reaction ratio of functional group A and functional group B ′ of 0.4 to 0.8.
  • the number of moles of functional group A derived from the first compound occupies 25% or more of the total number of moles of functional group A.
  • a functional group AZ comprising a first compound having three or more functional groups A in one molecule and a second compound having three or more functional groups B specifically binding to the functional group A in one molecule.
  • the reaction ratio of functional group B! Mix and react as ⁇ 0.6.
  • the first compound to the third compound mean so-called monomers.
  • the functional group AZ functional group B can be combined with the isocyanate group Z hydroxyl group, isocyanate group Z amino group, carboxyl group / amino group, carboxyl group hydroxyl group, carboxyl group Z glycidyl group, carboxyl group oxazoline group, maleic anhydride Examples include oxazoline group, maleic anhydride nomino group, glycidyl group Z oxazoline group, isocyanate group Z oxazoline group and the like.
  • the “catalyst to be used when necessary” those well known in the polymerization reaction system of the first compound to the third compound may be appropriately selected and used.
  • polyurethane resin is particularly preferable because it is easy to handle.
  • a polyurethane-based resin obtained from a polyisocyanate compound having three or more isocyanate groups in one molecule and a polymer polyol having two or more hydroxyl groups in one molecule is provided.
  • the raw material has low toxicity and is preferable because of excellent handling.
  • isocyanate compounds having 3 or more isocyanate groups include 2, 4- and 2, 6-tolylene diisocyanate, m- and p-phenylene diisocyanate, , 4-Diisocyanate, 1,5-Naphtalene diisocyanate, Methylenebisphenylene 4,4'-Diisocyanate, m- and p-xylene diisocyanate, Hexamethylene diisocyanate, Lysine diisocyanate, 4, 4 , Monomethylene biscyclohexyl diisocyanate, isophorone diisocyanate, trisodium diisocyanate trimer such as trimethylhexamethylene diisocyanate, 1, 6, 11-undecane diisocyanate, lysine ester Rudriisocyanate, 4-isocyanate methyl-1,8-octamethinoresinisocyanate, etc. Toriisoshiane one DOO such or polyphenyl methane polyisobut
  • the above diisocyanates can be used in combination.
  • the number of N CO groups in the triisocyanate is 0.25 or more with respect to the number of N CO groups in all isocyanates. If it is less than 0.25, the shape may not be retained due to insufficient crosslinking density.
  • Polymer polyols having two or more hydroxyl groups in one molecule include polyester polyols, polyether polyols, polycarbonate polyols, Bran oil-based polyols, saponified EVA (ethylene vinyl acetate copolymer), polyvinyl alcohol, cellulose and cellulose derivatives are used, and one or more of these are used.
  • the molar ratio of the NCO group and hydroxyl group of the isocyanate compound to be used is within the range of 0.3 to 0.7, more preferably 0.4 to 0.6 when the number of hydroxyl groups in the polymer polyol is two. It is within the range. If this molar ratio is less than 0.3, even if triisocyanate alone is used as the isocyanate, the shape may not be retained due to insufficient crosslinking density, and if it exceeds 0.7, the self-repairing property may not be exhibited. '"[Self-healing structure]
  • the self-healing structure of the present invention is one in which any of the above self-healing materials is immobilized on a substrate.
  • the self-healing material can be preferably used, for example, as the skin of the substrate.
  • the type of the base material of the self-healing structure is not particularly limited as long as it has a means capable of immobilizing the crosslinked polymer constituting the self-healing material by chemical bonding or the like.
  • a polymer material substrate is preferably used.
  • the base material of the polymer material for example, polyester resins, polyamide resins, cellulose and cellulose derivatives, polyurethane resins, polycarbonate resins, polyether resins, polyimide resins, various rubbers and the like are preferably used.
  • the surface of the above plastic and rubber base materials subjected to corona discharge treatment for the purpose of increasing reactive functional groups on the surface and also the surface of polyolefin resin, polychlorinated bur resin, polystyrene resin, acrylic resin It is also possible to use one that has been subjected to corona discharge treatment.
  • the elastic modulus of the polymer crosslinked body at the operating temperature is 10% or less of the base material's raw material, and the thickness of the polymer crosslinked body is 0.1 mm to It is preferably within the range of 10 mm If the elastic modulus of the crosslinked polymer exceeds 1/10 of the elastic modulus of the base material, the mechanical properties of the base material may be greatly impaired.
  • the thickness of the molecular cross-linked body is less than 0.1 mm, scratches on the surface may reach the base material that does not exhibit self-healing properties. If exceeded, the chemical properties of the base material will be greatly impaired, and the material will be wasted and there is a strong risk of inferior cost performance.
  • the polymer cross-linked product before chemically bonding to the base tree or the self-repairing structure chemically bonded to the base material and the polymer cross-linked product is once immersed in an excess organic solvent and included in the polymer cross-linked product. It is also possible to dissolve the sol component in the solvent. By treating with an organic solvent, the surface tackiness can be reduced.
  • the self-healing material of the present invention can be preferably used, for example, as a high-grade skin material that dislikes surface scratches, an optical material, and a member that is not easily exchangeable, such as a biomedical material.
  • the self-healing material of the present invention has the following advantages: 1) The manufacturing process is excellent in cost performance and technically simple, and 2) The application target is essentially limited by the type of polymer compound. 3) Self-healing action is repeated even in the same part of the material, and 4) Self-healing action is exhibited autonomously and without shape collapse etc. Can do.
  • 1) The manufacturing process is excellent in cost performance and technically simple, and 2) The application target is essentially limited by the type of polymer compound. 3) Self-healing action is repeated even in the same part of the material, and 4) Self-healing action is exhibited autonomously and without shape collapse etc. Can do.
  • the storage elastic modulus and loss tangent of the polymer crosslinked body and the substrate were measured in a linear region using a forced vibration type dynamic viscoelasticity measuring apparatus (UBM, E-4000).
  • the measurement frequency was 10 Hz
  • the temperature increase rate was 2 ° C / min
  • a sine wave was applied to perform the measurement in tensile mode.
  • the glass transition temperature was a temperature at which the loss elastic modulus was maximum in the glass-rubber transition region.
  • the crosslinked polymer was stretched by a uniaxial tensile test.
  • the tensile speed was 5 OmmZ and the elongation at the breaking point was measured. .
  • the polymer cross-linked product whose weight was measured in advance was immersed in an excess of acetone and left at room temperature for 24 hours.
  • the weight of the swollen crosslinked product was measured, and then the solvent was removed by vacuum drying to measure the dry weight.
  • [Weight after drying] / [Weight before immersion] XI 0-0 (%) as the gel fraction, [([weight after swelling] 1 [weight after drying]) / [weight after drying] ] was determined as the degree of swelling.
  • the substrate was left for one week with the substrate facing upward and the crosslinked body facing downward, and the surface condition was visually observed.
  • the thickness of the crosslinked product was 1 mm. Self-healing properties were evaluated using the obtained samples.
  • the defoamed mixed sample was poured onto polytetrafluoroethylene and heated at 150 ° C. for 5 minutes to carry out a urethane reaction.
  • the obtained crosslinked product was peeled from polytetrafluoroethylene, and various physical properties were measured.
  • Crosslinked urethane on polyethylene terephthalate substrate in the same manner as in Example 1. After that, it was immersed in a large amount of acetone and allowed to stand at room temperature for 8 hours. Thereafter, the solvent was removed by vacuum drying to prepare a sample. Self-healing properties were evaluated using the obtained samples.
  • the crosslinked product obtained by the same method as in Example 1 was peeled from polytetrafluoroethylene, immersed in a large amount of acetone and allowed to stand at room temperature for 8 hours, and then the solvent was removed by vacuum drying. Thus, a crosslinked product for measuring physical properties was obtained.
  • Shape holdability Can be used to hold the O ⁇ shape: Cannot be used because it flows without holding the X shape
  • a crosslinked product for measuring physical properties was obtained in the same manner as in Example 2 except that the reaction ratio of [NC 0] [OH] was 0 ⁇ 60. .
  • Polymer Polyolene [Nippon Polyurethane Co., Ltd., trade name-Zuporan 152, number average molecular weight 2000] 33.8 g and hexamethylene diisocyanate (Aldrich) 1. 46 g, dibutyltin dilaurate 10 O p
  • the new polymer polyol was obtained by mixing pm, mixing while maintaining at about 90 ° C. in a water bath and reacting for 20 minutes.
  • a crosslinked product for measuring physical properties was obtained in the same manner as in Example 2 except that the newly obtained polymer polyol and polyisocyanate were adjusted to a reaction ratio of [NCO] / [OH] of 0.50.
  • FIGS. Fig. 2 shows a state where a cut (completely cut state) has been given
  • Fig. 3 shows a state immediately after joining the cut portion (the cut remains)
  • Fig. 4 shows a condition for 24 hours at room temperature. This shows the state in which the cut after self-healing is completely self-healing.
  • Example 5 A film of self-healing material with a thickness of 2 mm and a width of 2 O mm was obtained under the same conditions and process as in Example 1 except that the reaction ratio of [NCO] / [OH] was 1.0. Sample (Sample A) was obtained. Further, under the same conditions and process as in Example 1 except that the reaction ratio of [NCO] / [OH] was 0.5, a film-like self-healing material having a thickness of 2 mm and a width of 2 O mm was used. A sample (Sample B) was obtained.
  • these 'film-like samples 1 are placed on a cylindrical column 2 with a diameter of 12 mm so that it bends and hangs under its own weight, and a laser blade is used along the chain line shown in the figure.
  • a cut with a width of 2 O mm and a depth of approximately 2 mm was made. After that, it was immediately removed from the cylindrical column, allowed to stand for 10 minutes without receiving external force at room temperature, and then returned to the mounting state shown in FIG.
  • the change over time of the cut of the film-like sample 1 in this state is shown in FIG. 6 by an enlarged photograph from the arrow “top view” direction and an enlarged photograph from the arrow “side view” direction shown in FIG.
  • top view and side view” in “A” in FIG. 6 are photographs immediately after the left side of the above sample A is returned to the mounting state shown in FIG. 5, and the right side is It is a photograph after 10 minutes have passed in that state.
  • photographs shown as “top vi6w” and “side view” in “BJ” in FIG. 6 are the photographs immediately after the left side of the sample B is returned to the mounting state shown in FIG. Yes, the photo on the right is 10 minutes after it has been in that condition.
  • a self-healing material having various advantages over the prior art and a self-healing structure using the material can be manufactured easily and at low cost.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Dispersion Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un matériau auto-réparateur qui se présente sous forme de polymère réticulé dans lequel un certain nombre de chaînes latérales sont liées à une structure polymère réticulée. Ledit matériau présente une propriété de gel proche d'un état critique, une propriété de rétention de forme due à la structure polymère réticulée ainsi qu'une propriété d'auto-réparation due aux chaînes latérales par régulation du degré de liaison desdites chaînes à la structure polymère réticulée et du poids moléculaire dans les points réticulés de la structure polymère réticulée de façon que le poids se situe dans une plage spécifique. Ledit matériau auto-réparateur peut être produit simplement et à faible coût, et présente une excellente propriété d'auto-réparation. L'invention concerne également une structure d'auto-réparation contenant ledit matériau auto-réparateur.
PCT/JP2006/325149 2005-12-16 2006-12-12 Matériau auto-réparateur Ceased WO2007069765A1 (fr)

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JP2010197579A (ja) * 2009-02-24 2010-09-09 Fuji Xerox Co Ltd 無端ベルト、画像定着装置、及び画像形成装置
WO2011136042A1 (fr) * 2010-04-27 2011-11-03 東レ株式会社 Film multicouche et article moulé
WO2012127418A1 (fr) 2011-03-21 2012-09-27 Arjowiggins Security Support d'information ou papier comportant un matériau auto-réparant
WO2012157500A1 (fr) * 2011-05-16 2012-11-22 東レ株式会社 Film stratifié et corps moulé
JP2015516994A (ja) * 2012-03-07 2015-06-18 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニアＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｃａｌｉｆｏｒｎｉａ 多機能性動的ナノコンポジットを得るためのバイオインスパイアード方法
CN108546407A (zh) * 2018-04-25 2018-09-18 哈尔滨工业大学 一种可自修复形状记忆聚酰亚胺及其制备方法
WO2020045439A1 (fr) * 2018-08-27 2020-03-05 国立大学法人名古屋工業大学 Résine/film de polyester réticulé mou présentant une propriété autoadhésive, une reformabilité et une propriété de réparation de défauts et procédé pour sa production
WO2020175321A1 (fr) 2019-02-28 2020-09-03 株式会社Adeka Nouveau composé, composition contenant ledit composé, et objet durci
KR20240001162A (ko) 2021-04-27 2024-01-03 가부시키가이샤 아데카 화합물, 경화성 조성물 및 경화물

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KR101872501B1 (ko) * 2014-02-18 2018-06-29 경북대학교 산학협력단 자가 복원 폴리우레탄 코팅제 제조방법
KR102709935B1 (ko) 2018-06-29 2024-09-24 삼성전자주식회사 자가 복원성 복합체 및 이를 포함하는 소자

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Cited By (23)

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JP2010197579A (ja) * 2009-02-24 2010-09-09 Fuji Xerox Co Ltd 無端ベルト、画像定着装置、及び画像形成装置
JP5799806B2 (ja) * 2010-04-27 2015-10-28 東レ株式会社 積層フィルムおよび成型体
WO2011136042A1 (fr) * 2010-04-27 2011-11-03 東レ株式会社 Film multicouche et article moulé
CN102844182A (zh) * 2010-04-27 2012-12-26 东丽株式会社 叠层膜和成型体
US8980432B2 (en) 2010-04-27 2015-03-17 Toray Industries, Inc. Multilayer film and molded body
CN102844182B (zh) * 2010-04-27 2015-03-25 东丽株式会社 叠层膜和成型体
WO2012127418A1 (fr) 2011-03-21 2012-09-27 Arjowiggins Security Support d'information ou papier comportant un matériau auto-réparant
JP5928334B2 (ja) * 2011-05-16 2016-06-01 東レ株式会社 積層フィルムおよび成型体
WO2012157500A1 (fr) * 2011-05-16 2012-11-22 東レ株式会社 Film stratifié et corps moulé
US9080053B2 (en) 2011-05-16 2015-07-14 Toray Industries, Inc. Laminated film and molded body
JP2015516994A (ja) * 2012-03-07 2015-06-18 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニアＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｃａｌｉｆｏｒｎｉａ 多機能性動的ナノコンポジットを得るためのバイオインスパイアード方法
US9938368B2 (en) 2012-03-07 2018-04-10 The Regents Of The University Of California Bio-inspired method to obtain multifunctional dynamic nanocomposites
CN108546407B (zh) * 2018-04-25 2020-10-02 哈尔滨工业大学 一种可自修复形状记忆聚酰亚胺及其制备方法
CN108546407A (zh) * 2018-04-25 2018-09-18 哈尔滨工业大学 一种可自修复形状记忆聚酰亚胺及其制备方法
WO2020045439A1 (fr) * 2018-08-27 2020-03-05 国立大学法人名古屋工業大学 Résine/film de polyester réticulé mou présentant une propriété autoadhésive, une reformabilité et une propriété de réparation de défauts et procédé pour sa production
WO2020175321A1 (fr) 2019-02-28 2020-09-03 株式会社Adeka Nouveau composé, composition contenant ledit composé, et objet durci
JPWO2020175321A1 (fr) * 2019-02-28 2020-09-03
CN113544120A (zh) * 2019-02-28 2021-10-22 株式会社Adeka 新化合物、含有该化合物的组合物及固化物
KR20210133236A (ko) 2019-02-28 2021-11-05 가부시키가이샤 아데카 신규 화합물, 그 화합물을 포함하는 조성물, 자기 수복 재료, 표면 코트제, 도료, 접착제, 전지용 재료 및 경화물
CN113544120B (zh) * 2019-02-28 2023-05-02 株式会社Adeka 新化合物、含有其的组合物、自修复材料、表面涂布剂、涂料、粘合剂、电池用材料及固化物
US11667609B2 (en) 2019-02-28 2023-06-06 Adeka Corporation Compound, composition containing said compound, self-healing material, surface coating agent, paint, adhesive, material for battery and cured product
JP7464957B2 (ja) 2019-02-28 2024-04-10 株式会社Adeka 化合物、該化合物を含む組成物、自己修復材料、表面コート剤、塗料、接着剤、電池用材料及び硬化物
KR20240001162A (ko) 2021-04-27 2024-01-03 가부시키가이샤 아데카 화합물, 경화성 조성물 및 경화물

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