WO2013105539A1 - 樹脂複合材料及び樹脂複合材料の製造方法 - Google Patents
樹脂複合材料及び樹脂複合材料の製造方法 Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F10/06—Propene
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C08L101/00—Compositions of unspecified macromolecular compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the present invention relates to a resin composite material in which a silane compound is dispersed in a thermoplastic resin and a method for producing the resin composite material, and in particular, a resin composite in which the silane compound and the resin form an IPN structure or a semi-IPN structure.
- the present invention relates to a material and a method for producing a resin composite material.
- resin composite materials in which fillers and rubber-like components are blended in various resins are known.
- various fillers and rubber-like components By blending various fillers and rubber-like components into the thermoplastic resin, various physical properties can be imparted to the resin composite material, such as increasing the linear expansion coefficient of the resin composite material.
- Patent Document 1 discloses a resin composite material having a form in which a thermoplastic elastomer is dispersed in a network in a thermoplastic resin, and can reduce the linear expansion coefficient of the resin composite material. ing.
- thermoplastic elastomer has a problem that the glass transition temperature is low and the heat resistance is low. Therefore, the linear expansion coefficient of the resin composite material cannot be sufficiently lowered.
- An object of the present invention is to provide a resin composite material that realizes networking of a silane compound having high heat resistance in a resin and has a low linear expansion coefficient, and a method for producing the resin composite material.
- the resin composite material according to the present invention is a resin composite material containing a resin and a silane compound having the structure of formula (1), wherein the molecular chain of the resin and the molecular chain of the silane compound have an IPN structure. Alternatively, a semi-IPN structure is formed.
- Each R in the formula (1) is independently selected from the group consisting of hydrogen, halogen and any organic functional group, and at least one is a reactive organic functional group.
- x is 1 or 1.5.
- n is an integer of 100 or more and 10,000 or less.
- Another resin composite material according to the present invention is a resin composite material containing a resin and a silane compound having the structure of formula (1), wherein the resin composite material is at a temperature equal to or higher than the melting point of the resin composite material.
- the storage elastic modulus is always larger than the loss elastic modulus in the frequency range of 0.01 to 100 Hz
- the gel contained in the resin composite material contains a compound having a silicon atom
- the degree of swelling of the gel contained in the resin composite material is 500% or less.
- Each R in the formula (1) is independently selected from the group consisting of hydrogen, halogen and any organic functional group, and at least one is a reactive organic functional group.
- x is 1 or 1.5.
- n is an integer of 100 or more and 10,000 or less.
- each R in the formula (1) is hydrogen, chlorine, silyl, siloxy, alkoxy, vinyl, aryl, alkyl, alkylamine, ether, ester, amine, amide. , Thiol, methacrylic, acrylic, epoxy, ureido, mercapto, sulfide and isocyanate.
- each R in the formula (1) is vinyl, alkylamine, amine, methacryl, acrylic, epoxy, ureido, mercapto, sulfide, and isocyanate.
- a reactive organic functional group selected from the group consisting of
- a reactive organic functional group contained in the silane compound reacts to form a polymer of the reactive organic functional group. ing.
- the networking of the silane compound is promoted, the movement of the silane compound in the resin is further limited. Therefore, the linear expansion coefficient of the resin composite material can be further reduced.
- a reactive organic functional group contained in the silane compound reacts to form a chemical bond between the silane compound and the resin. is doing. In that case, since the silane compound and the resin are chemically bonded, there is an advantage that the silane compound and the resin are difficult to phase-separate.
- thermoplastic resin any of a crystalline resin and an amorphous resin can be used.
- the molecular chain constituting the amorphous part of the crystalline resin forms an IPN structure or a semi-IPN structure with the molecular chain of the silane compound.
- polyolefin is used as the thermoplastic resin.
- the cost of the resin composite material can be reduced, and the resin composite material can be easily molded.
- the method for producing a resin composite material of the present invention includes a step of obtaining a resin composition by mixing a resin and a silane compound having the structure of formula (2), and a plurality of the silane compounds contained in the resin composition An IPN structure forming step of condensing each other.
- Each R in the formula (2) is independently selected from the group consisting of hydrogen, halogen and any organic functional group, and at least one is a reactive organic functional group.
- x is 1 or 1.5.
- n is an integer of 1 or more and 100 or less.
- the resin composition in the IPN structure forming step, is placed in the presence of water at 80 ° C. or higher, whereby a plurality of the resin compositions are included.
- the silane compounds are condensed together. In that case, since sufficient temperature and water required for hydrolysis can be secured, the degree of condensation between the silane compounds can be increased.
- each R in the formula (1) is hydrogen, chlorine, silyl, siloxy, alkoxy, vinyl, aryl, alkyl, alkylamine, ether, ester. , Amine, amide, thiol, methacryl, acrylic, epoxy, ureido, mercapto, sulfide and isocyanate.
- each R in the formula (1) is vinyl, alkylamine, amine, methacryl, acrylic, epoxy, ureido, mercapto, sulfide.
- a reactive organic functional group selected from the group consisting of isocyanates.
- a reactive organic functional group contained in the silane compound reacts to form the reactive organic functional group.
- the method further includes the step of forming a polymer. In that case, since the networking of the silane compound is promoted, the movement of the silane compound in the resin is further limited. Therefore, the linear expansion coefficient of the resin composite material can be further reduced.
- the step of forming the polymer of the reactive organic functional group is performed by irradiating the resin composition with radiation. In that case, compared with the method of adding a peroxide etc., there is little deterioration of the said resin.
- a reactive organic functional group contained in the silane compound reacts to form the silane compound and the resin. Further includes the step of forming a chemical bond. In that case, since the silane compound and the resin are chemically bonded, there is an advantage that the silane compound and the resin are difficult to phase-separate.
- the step of forming the chemical bond is performed by irradiating the resin composition with radiation.
- the step of forming the chemical bond is performed by irradiating the resin composition with radiation.
- the molecular chain constituting the amorphous part of the resin and the molecular chain of the silane compound having the structure of the formula (1) form an IPN structure or a semi-IPN structure.
- the silane compound is fixed to the amorphous part of the resin.
- the manufacturing method of the resin composite material which concerns on this invention in the resin composition obtained by mixing resin and the silane compound which has a structure of Formula (2), several said silane compounds are condensed. Therefore, in the resin composite material, an IPN structure or a semi-IPN structure is formed between the molecular chain constituting the amorphous part of the resin and the molecular chain of the silane compound. Therefore, the carbon material is uniformly dispersed in the composite resin molded body. Therefore, aggregation of the silane compound in the resin is suppressed. Therefore, the linear expansion coefficient of the resin composite material obtained by the production method of the present invention can be effectively reduced.
- FIG. 1 is a schematic diagram showing an IPN structure formed in a resin composite material according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram showing a process of forming an IPN structure in an embodiment of the manufacturing method of the present invention.
- the resin composite material of the present invention includes a resin and a silane compound having a structure of the formula (1).
- each R is independently selected from the group consisting of hydrogen, halogen and any organic functional group.
- each R consists of hydrogen, chlorine, silyl, siloxy, alkoxy, vinyl, aryl, alkyl, alkylamine, ether, ester, amine, amide, thiol, methacryl, acrylic, epoxy, ureido, mercapto, sulfide and isocyanate. Selected independently from the group.
- Each R may be the same or different.
- each R in the formula (1) is a reactive organic functional group.
- the reactive organic functional group is not particularly limited, and is selected from the group consisting of vinyl, alkylamine, amine, methacryl, acrylic, epoxy, ureido, mercapto, sulfide, and isocyanate.
- a plurality of R in the formula (1) may be reactive organic functional groups. In that case, the plurality of R reactive organic functional groups may be the same or different.
- x is 1 or 1.5.
- n is an integer of 100 or more and 10,000 or less. When n is smaller than 100, the strength of the silane compound is lowered, and even if an IPN structure or a semi-IPN structure described later is formed, the linear expansion coefficient of the resin composite material may not be sufficiently lowered. When n is larger than 10,000, the compatibility with the resin is deteriorated, phase separation occurs, and the IPN structure or semi-IPN structure described later may not be sufficiently formed.
- the compound having the structure of the formula (1) can be obtained, for example, by condensing alkoxysilane.
- a compound also includes a compound having a structure in which alkoxysilane is sterically bonded.
- an example of a compound in which x is 1.5 includes silsesquioxane.
- Silsesquioxane is obtained by hydrolyzing a trifunctional silane and is a network polymer having a structure of (RSiO 1.5 ) n .
- n is an integer of 100 or more and 1000 or less in the present invention as described above.
- Silsesquioxane has a so-called cage structure. Silsesquioxane, which has a size of about several nm, can be dispersed in a resin at the molecular level. Therefore, the strength can be increased while maintaining the workability and mechanical properties of the resin composite material. Furthermore, various physical properties can be expressed by selecting the functional group R.
- thermoplastic resin either a thermoplastic resin or a thermosetting resin can be used.
- thermoplastic resin any of a crystalline thermoplastic resin and an amorphous thermoplastic resin can be used.
- thermoplastic resin is not particularly limited, and various known thermoplastic resins can be used.
- the thermoplastic resin include polyethylene, polypropylene, ethylene vinyl acetate copolymer, acrylonitrile styrene copolymer, acrylonitrile butadiene styrene copolymer, polyvinyl chloride, acrylic resin, methacrylic resin, polystyrene, polytetrafluoroethylene, Polychlorotrifluoroethylene, polyvinylidene fluoride, ethylene vinyl alcohol copolymer, vinylidene chloride resin, chlorinated polyethylene, polydicyclopentadiene, methylpentene resin, polybutylene, polyphenylene ether, polyamide, polyphenylene ether, polyphenylene sulfide, polyether ether Ketone, polyallyl ether ketone, polyamideimide, polyimide, polyetherimide, polysulfone, polyether Sulfone, norbornene resins
- polyolefin such as polypropylene, polyethylene, ethylene-propylene copolymer, etc.
- polyolefin such as polypropylene, polyethylene, ethylene-propylene copolymer, etc.
- Polyolefin is inexpensive and easy to mold under heating. Therefore, by using polyolefin as the thermoplastic resin, the cost of the resin composite material can be reduced, and the resin composite material can be easily molded.
- thermoplastic resins examples include polyolefin and polyamide.
- the molecular chain of the amorphous part in the crystalline resin forms an IPN structure or a semi-IPN structure with the molecular chain of the silane compound.
- the amorphous resin examples include polystyrene and polycarbonate. In this case, the molecular chain of the amorphous resin forms an IPN structure or a semi-IPN structure with the molecular chain of the silane compound.
- thermosetting resin may be used as the resin.
- the molecular chain of the thermosetting resin can form an IPN structure or a semi-IPN structure together with the molecular chain of the silane compound. Therefore, the linear expansion coefficient can be effectively lowered even in the case of a thermosetting resin.
- a thermosetting resin is not particularly limited, and examples thereof include an epoxy resin, a soft polyurethane, and a hard polyurethane. In particular, when a soft thermosetting resin such as soft soft polyurethane is used, the linear expansion coefficient can be effectively reduced.
- the content ratio of the resin and the silane compound in the resin composite material of the present invention is not particularly limited, but the silane compound is preferably contained in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the resin. .
- the linear expansion coefficient of a resin composite material can be lowered effectively. If the silane compound is less than 1 part by weight, the linear expansion coefficient of the resin material may not be sufficiently lowered. If the silane compound exceeds 50 parts by weight, phase separation with the resin may occur, and a resin composite material may not be produced.
- the molecular chain constituting the amorphous portion of the thermoplastic resin and the molecular chain of the silane compound having the structure of the formula (1) have an IPN structure ( An interpenetrating network structure) or a semi-IPN structure (semi-interpenetrating network structure) is formed.
- FIG. 1 is a schematic diagram showing an IPN structure in a resin composite material.
- the thermoplastic resin constituting the resin composite material includes a crystalline portion 13 and an amorphous portion 11.
- the amorphous part 11 exists in the gap between the crystals constituting the crystal part 13.
- the amorphous portion 11 has a molecular chain that constitutes the amorphous portion 11.
- One molecular chain of the thermoplastic resin is not necessarily entirely the crystal part 13 or the amorphous part 11, but a part of the molecular chain forms a crystal structure to form a crystal part 13. It may be an amorphous portion 11 that does not form a structure. In that case, one molecular chain of the thermoplastic resin constitutes a crystal part 13 forming a crystal structure and an amorphous part 11 not forming a crystal structure. That is, the crystal part 13 and the amorphous part 11 may be connected by one molecular chain.
- the silane compound 12 exists in the amorphous part 11 which is a gap between the crystal parts 13 of the thermoplastic resin.
- the molecular chain of the silane compound 12 forms an IPN structure or a semi-IPN structure with the molecular chain of the amorphous portion 11. That is, a network structure in which the molecular chain of the silane compound 12 and the molecular chain constituting the amorphous portion 11 of the thermoplastic resin are entangled with each other is formed. Since the molecular chains of the silane compound 12 and the amorphous part 11 are entangled with each other, the movement of the molecular chain of the amorphous part 11 in the thermoplastic resin is limited. Therefore, when the silane compound 12 forms an IPN structure or a semi-IPN structure in the thermoplastic resin, the linear expansion coefficient of the resin composite material can be effectively reduced.
- the IPN structure generally refers to a structure in which two polymer molecular chains both have a network structure in a network structure in which a plurality of polymer molecular chains intrude each other.
- the structure means a structure in which one polymer has a network structure and the other has a linear or branched structure.
- the resin composite material of the present invention it is only necessary to form a network structure in which the molecular chain of the silane compound 12 and the molecular chain constituting the amorphous part 11 of the thermoplastic resin are entangled with each other, as described above.
- the structure may be an IPN structure or a semi-IPN structure.
- an amorphous thermoplastic resin may be used as the resin.
- the molecular chain constituting the amorphous resin is the molecular chain of the silane compound.
- the IPN structure or the semi-IPN structure is formed.
- a thermosetting resin may be used as the resin.
- the molecular chain of the thermosetting resin, together with the molecular chain of the silane compound has an IPN structure or semi-IPN. A structure can be formed.
- the silane compound 12 is fixed to the amorphous portion 11 by the IPN structure or semi-IPN structure as described above, viscoelasticity measurement was performed at a temperature equal to or higher than the melting point of the resin composite material.
- the storage elastic modulus is always larger than the loss elastic modulus in the frequency range of 0.01 to 100 Hz.
- the portion where the IPN structure or the semi-IPN structure is formed as described above is a gel.
- the gel is composed of a network structure including an inorganic substance, that is, a network structure including the silane compound 12 as a compound having a silicon atom. For this reason, the degree of swelling of the gel is lower than the degree of swelling of the gel by a general crosslinked resin, and is 500% or less.
- whether the resin composite material has an IPN structure or a semi-IPN structure is measured by the above-described viscoelasticity measurement or a measurement that a compound having a silicon atom is contained in the gel. And by measuring the degree of swelling of the gel.
- the frequency of the resin composite material when the viscoelasticity measurement is performed at a temperature equal to or higher than the melting point of the resin composite material is always larger than the loss elastic modulus in the range of 0.01 to 100 Hz, and the gel contained in the resin composite material contains a compound containing a silicon atom, and the degree of swelling of the gel contained in the resin composite material Is 500% or less, the compound is recognized as the resin composite material of the present invention having an IPN structure or a semi-IPN structure.
- the gel contains a compound having a silicon atom, and when measuring the degree of swelling of the gel, it is preferable to take out the gel from the resin composite material and measure it.
- a method of taking out the gel for example, there is a method of immersing the resin composite material in a good solvent and taking out a component that has not been dissolved as a gel.
- the reactive organic functional group contained in the compound having the structure of the formula (1) may form a polymer.
- networking of the compound having the structure of the formula (1) is promoted, and a denser IPN structure or semi-IPN structure is formed. Therefore, the movement in the resin is further limited, and the linear expansion coefficient of the resin composite material can be further reduced.
- the reactive organic functional group contained in the compound having the structure of the formula (1) may form a chemical bond with the resin.
- the compound having the structure of the formula (1) and the resin are not only entangled with each other by the IPN structure or the semi-IPN structure, but also have a chemical bond, there is an advantage that it is difficult to separate from the resin. .
- Each R in Formula (2) is the same as each R in Formula (1) described above.
- x is 1 or 1.5.
- n of Formula (2) is an integer of 1 or more and 100 or less. When n is larger than 100, an IPN structure may not be formed in the resulting resin composite material.
- Examples of the compound having the structure of the formula (2) include vinyltriethoxysilane, 3-aminopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxysilane.
- n is about 10 to 100
- the amount of by-products generated during the condensation described later can be reduced. Therefore, a silane compound can be efficiently added to the obtained resin composite material.
- the mixing method is not particularly limited, and can be mixed by an appropriate method. Examples thereof include a melt kneading method performed by kneading under heating using a kneading apparatus such as a twin screw kneader such as a plast mill, a single screw extruder, a twin screw extruder, a Banbury mixer, and a roll. Further, a method in which the thermoplastic resin and the silane compound are dissolved or dispersed in a solvent and mixed can also be used.
- the blending ratio of the thermoplastic resin and the silane compound is not particularly limited, but the silane compound is preferably blended in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the resin. If the silane compound is less than 1 part by weight, the linear expansion coefficient of the resin material may not be sufficiently lowered. If the silane compound exceeds 50 parts by weight, phase separation may occur with the resin, and a composite material may not be prepared.
- a step of forming a polymer of the reactive organic functional group by polymerizing the reactive organic functional group of the silane compound in the obtained resin is performed. May be.
- the linear expansion coefficient of the resin composite material obtained by the production method of the present invention can be further reduced. Furthermore, when condensing the silane compounds described later, the silane compounds are less likely to aggregate, so that an IPN structure or a semi-IPN structure can be formed more effectively.
- the method for forming the chemical bond is not particularly limited.
- the method of irradiating the said resin composition with an electron beam is mentioned.
- a radical is generated in the reactive organic functional group by an electron beam.
- the reactive organic functional group can form a polymer.
- the step of forming the chemical bond is not an essential step in the method for producing the resin composite material of the present invention and may not be performed.
- the reactive organic functional group of the silane compound is reacted with the resin to form a chemical bond between the silane compound and the resin. You may perform the process of forming.
- phase separation of the resin composite material obtained by the production method of the present invention can be suppressed. Furthermore, when condensing the silane compounds described later, the silane compounds are less likely to aggregate, so that an IPN structure or a semi-IPN structure can be formed more effectively.
- the method for forming the chemical bond is not particularly limited.
- the method of irradiating the said resin composition with an electron beam is mentioned.
- a radical is generated in the reactive organic functional group by an electron beam.
- the radicals generated in the reactive organic functional group can graft the silane compound onto the resin.
- the reactive organic functional group is an amide group and the resin is a maleic acid-modified thermoplastic resin
- a chemical bond by an amide bond can be formed between the silane compound and the thermoplastic resin.
- the step of forming the chemical bond is not an essential step in the method for producing the resin composite material of the present invention and may not be performed.
- a step of condensing a plurality of the silane compounds contained in the resin composition is performed.
- the plurality of silane compounds contained in the resin composition are condensed to form an IPN structure or a semi-IPN structure with an amorphous part of the resin.
- the resin composite material of the present invention can be obtained.
- FIG. 2 is a schematic diagram illustrating an example of an embodiment when the resin is a thermoplastic resin as described above.
- FIG. 2 is a schematic view showing a process in which an IPN structure (right of FIG. 2) is formed by condensation of silane compounds from the thermoplastic resin composition before condensation (left of FIG. 2).
- the silane compound 12a is present in the amorphous portion 11.
- the silane compounds 12a contained in the said thermoplastic resin composition when the silane compounds 12a contained in the said thermoplastic resin composition are condensed, the silane compounds 12a will couple
- the resin composite material of the present invention in which a network structure in which the molecular chains of the amorphous portion 11 and the silane compound 12 are entangled with each other, that is, an IPN structure or a semi-IPN structure, can be obtained.
- the silane compound 12a is chemically bonded to the thermoplastic resin. Therefore, when the silane compounds 12a condense with each other, the movement of the silane compound 12a is restricted by the chemical bond, and therefore the condensation occurs without aggregation of the silane compound 12a. Therefore, an IPN structure or a semi-IPN structure in which the amorphous portion 11 and the silane compound 12 are entangled with each other by condensation can be more effectively formed.
- the resin is a thermoplastic resin
- a thermosetting resin may be used as the resin in the present invention.
- an IPN structure or a semi-IPN structure is formed by the molecular chain of the resin and the molecular chain of the silane compound.
- the condensation method is not particularly limited as long as the silane compound can be condensed, and examples thereof include a method of placing the thermoplastic resin composition in the presence of water at 80 ° C. or higher. In that case, although it depends on the silane compound to be used, the time for keeping in the presence of water at 80 ° C. or higher is preferably 24 hours or longer in order to sufficiently condense the silane compound.
- Example 1 100 parts by weight of polypropylene (trade name “J-721GR” manufactured by Prime Polymer Co., Ltd., tensile modulus: 1.2 GPa, linear expansion coefficient: 11 ⁇ 10 ⁇ 5 / K) and 10 parts by weight of vinyltriethoxysilane It was melt-kneaded at 180 ° C. with a plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.), and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- a plast mill trade name “R-100” manufactured by Toyo Seiki Co., Ltd.
- the vinyl triethoxysilane was reacted by immersing the resin composition sheet in warm water at 80 ° C. for 24 hours to obtain a resin composite sheet having a thickness of 0.5 mm.
- Example 2 A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that 20 parts by weight of vinyltriethoxysilane was added.
- Example 3 A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that 40 parts by weight of vinyltriethoxysilane was added.
- Example 4 A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that methylmethoxysilane oligomer was used instead of vinyltriethoxysilane.
- Example 5 A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 1 except that silsesquioxane (product number “560391” manufactured by Sigma-Aldrich) was used instead of vinyltriethoxysilane.
- Example 6 100 parts by weight of polypropylene (trade name “J-721GR” manufactured by Prime Polymer Co., Ltd., tensile modulus: 1.2 GPa, linear expansion coefficient: 11 ⁇ 10 ⁇ 5 / K) and 10 parts by weight of 3-methacryloxypropyltrimethoxysilane Were melt-kneaded at 180 ° C. with a lab plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.) and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- a lab plast mill trade name “R-100” manufactured by Toyo Seiki Co., Ltd.
- the organic functional group portion of the 3-methacryloxypropyltrimethoxysilane was polymerized by irradiating the resin composition sheet with an electron beam.
- the resin composition sheet was immersed in warm water at 80 ° C. for 24 hours, whereby the 3-methacryloxypropyltrimethoxysilane was reacted to obtain a resin composite material sheet having a thickness of 0.5 mm.
- Example 7 100 parts by weight of polypropylene (trade name “J-721GR” manufactured by Prime Polymer Co., Ltd., tensile modulus: 1.2 GPa, linear expansion coefficient: 11 ⁇ 10 ⁇ 5 / K) and 10 parts by weight of vinyltriethoxysilane It was melt-kneaded at 180 ° C. with a plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.), and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- a plast mill trade name “R-100” manufactured by Toyo Seiki Co., Ltd.
- the polypropylene and the vinyltriethoxysilane were chemically bonded by irradiating the resin composition sheet with an electron beam.
- the resin composition sheet was immersed in warm water at 80 ° C. for 24 hours to cause the vinyltriethoxysilane to react to obtain a resin composite material sheet having a thickness of 0.5 mm.
- Example 8 Maleic anhydride-modified polypropylene (trade name “Admer QE800” manufactured by Mitsui Chemicals, Ltd., tensile elastic modulus: 1.5 GPa, linear expansion coefficient: 10 ⁇ 10 ⁇ 5 / K) and 3-aminopropyltriethoxysilane 10
- the parts by weight were melt-kneaded at 180 ° C. with a lab plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.) and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- the resin composition sheet was immersed in warm water at 80 ° C. for 24 hours, whereby the 3-aminopropyltriethoxysilane was subjected to a coupling reaction to obtain a resin composite material sheet having a thickness of 0.5 mm.
- Example 9 Laboplast mill 100 parts by weight of polyethylene (trade name “1300J” manufactured by Prime Polymer Co., Ltd., flexural modulus: 1.3 GPa, linear expansion coefficient: 11 ⁇ 10 ⁇ 5 / K) and 10 parts by weight of vinyltriethoxysilane (Product name “R-100” manufactured by Toyo Seiki Co., Ltd.) was melt-kneaded at 180 ° C. and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- the vinyl triethoxysilane was reacted by immersing the resin composition sheet in warm water at 80 ° C. for 24 hours to obtain a resin composite sheet having a thickness of 0.5 mm.
- Example 10 100 parts by weight of polyamide (trade name “1300S” manufactured by Asahi Kasei Co., Ltd., flexural modulus: 2.7 GPa, linear expansion coefficient: 8 ⁇ 10 ⁇ 5 / K) and 10 parts by weight of 3-glycidoxypropyltriethoxysilane Then, it was melt kneaded at 270 ° C. with a lab plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.), and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- a lab plast mill trade name “R-100” manufactured by Toyo Seiki Co., Ltd.
- the resin composition sheet was immersed in warm water at 80 ° C. for 24 hours, whereby the 3-glycidoxypropyltriethoxysilane was reacted to obtain a resin composite material sheet having a thickness of 0.5 mm.
- ABS (trade name “Toyolac 100” manufactured by Toray Industries, Inc., flexural modulus: 2.3 GPa, linear expansion coefficient: 7.4 ⁇ 10 ⁇ 5 / K) 100 parts by weight and 3-glycidoxypropyltriethoxysilane 10 parts by weight
- the parts were melt-kneaded at 200 ° C. with a lab plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.), and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- the resin composition sheet was immersed in warm water at 80 ° C. for 24 hours, whereby the 3-glycidoxypropyltriethoxysilane was reacted to obtain a resin composite material sheet having a thickness of 0.5 mm.
- Example 12 100 parts by weight of polycarbonate (trade name “H-4000”, manufactured by Mitsubishi Engineering Plastics Co., Ltd., tensile modulus: 2.4 GPa, linear expansion coefficient: 6.5 ⁇ 10 ⁇ 5 / K) and 3-glycidoxypropyltri 10 parts by weight of ethoxysilane was melt-kneaded at 270 ° C. with a lab plast mill (trade name “R-100” manufactured by Toyo Seiki Co., Ltd.) and formed into a sheet by pressing. Thereby, a resin composition sheet having a thickness of 0.5 mm was obtained.
- a lab plast mill trade name “R-100” manufactured by Toyo Seiki Co., Ltd.
- the resin composition sheet was immersed in warm water at 80 ° C. for 24 hours, whereby the 3-glycidoxypropyltriethoxysilane was reacted to obtain a resin composite material sheet having a thickness of 0.5 mm.
- Example 13 50 parts by weight of a bisphenol A type epoxy resin (trade name “828” manufactured by Mitsubishi Chemical Co., Ltd.), 50 parts by weight of a curing agent (trade name “Licacid TH” manufactured by Shin Nippon Chemical Co., Ltd.) 2MZ-A ”) 2 parts by weight and 10 parts by weight of vinyltriethoxysilane were mixed and stirred with a homodisper type stirrer. Subsequently, the mixture was applied to a release PET sheet and dried in an oven at 130 ° C. for 3 hours to obtain a resin composition sheet having a thickness of 0.5 mm.
- a bisphenol A type epoxy resin trade name “828” manufactured by Mitsubishi Chemical Co., Ltd.
- a curing agent trade name “Licacid TH” manufactured by Shin Nippon Chemical Co., Ltd.” 2MZ-A
- the vinyl triethoxysilane was reacted by immersing the resin composition sheet in warm water at 80 ° C. for 24 hours to obtain a resin composite sheet having a thickness of 0.5 mm.
- Example 3 A resin composite material sheet having a thickness of 0.5 mm was obtained in the same manner as in Example 3 except that 60 parts by weight of vinyltriethoxysilane was added.
- Viscoelasticity measurement The prepared sheet was cut into a disk shape having a diameter of 8 mm and a thickness of 0.5 mm. This sample was attached to a dynamic viscoelasticity measuring apparatus (TA Instruments, ARES) and measured under the conditions of shear mode, measurement frequency of 0.1 to 100 Hz, and strain of 1%. Tables 1 and 2 show the relationship between the measurement temperature and the storage elastic modulus Ga and the loss elastic modulus Gb.
- the resin composite material sheet has the IPN structure needs to satisfy the following points in the measurement results of a) to c).
- the gel contained in the resin composite material contains a compound having a silicon atom.
- the degree of swelling of the gel is 500% or less.
- thermosetting resin when the said requirements in evaluation of a) and b) were satisfy
- the resin composite material sheets obtained in Examples 1 to 13 have a lower linear expansion coefficient than the resin composite material sheets obtained in the corresponding Comparative Examples 1 to 13. This is considered due to the fact that the resin composite material sheet has an IPN structure.
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Abstract
Description
本発明の樹脂複合材料は、樹脂と、式(1)の構造を有するシラン化合物を含む。
本発明の樹脂複合材料の製造方法では、まず、上記樹脂と、式(2)の構造を有する上記シラン化合物とを混合することにより樹脂組成物を得る工程を行う。
ポリプロピレン(プライムポリマー社製 商品名「J-721GR」、引張弾性率:1.2GPa、線膨張率:11×10-5/K)100重量部と、ビニルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて180℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ビニルトリエトキシシランを20重量部添加したこと以外は実施例1と同様にして、厚み0.5mmの樹脂複合材料シートを得た。
ビニルトリエトキシシランを40重量部添加したこと以外は実施例1と同様にして、厚み0.5mmの樹脂複合材料シートを得た。
ビニルトリエトキシシランのかわりにメチルメトキシシランオリゴマーを用いたこと以外は実施例1と同様にして、厚み0.5mmの樹脂複合材料シートを得た。
ビニルトリエトキシシランのかわりにシルセスキオキサン(シグマアルドリッチ社製 商品番号「560391」)を用いたこと以外は実施例1と同様にして、厚み0.5mmの樹脂複合材料シートを得た。
ポリプロピレン(プライムポリマー社製 商品名「J-721GR」、引張弾性率:1.2GPa、線膨張率:11×10-5/K)100重量部と、3-メタクリロキシプロピルトリメトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて180℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ポリプロピレン(プライムポリマー社製 商品名「J-721GR」、引張弾性率:1.2GPa、線膨張率:11×10-5/K)100重量部と、ビニルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて180℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
無水マレイン酸変性ポリプロピレン(三井化学社製 商品名「アドマーQE800」、引張弾性率:1.5GPa、線膨張率:10×10-5/K)100重量部と、3-アミノプロピルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて180℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ポリエチレン(プライムポリマー社製 商品名「1300J」、曲げ弾性率:1.3GPa、線膨張率:11×10-5/K)100重量部と、ビニルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて180℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ポリアミド(旭化成社製 商品名「1300S」、曲げ弾性率:2.7GPa、線膨張係数:8×10-5/K)100重量部と、3‐グリシドキシプロピルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて270℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ABS(東レ社製 商品名「トヨラック100」、曲げ弾性率:2.3GPa、線膨張係数:7.4×10-5/K)100重量部と、3‐グリシドキシプロピルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて200℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ポリカーボネート(三菱エンジニアリングプラスチックス社製 商品名「H-4000」、引張弾性率:2.4GPa、線膨張係数:6.5×10-5/K)100重量部と、3‐グリシドキシプロピルトリエトキシシラン10重量部とを、ラボプラストミル(東洋精機社製 商品名「R-100」)にて270℃で溶融混練し、プレス加工によりシート状に成形した。それによって、厚み0.5mmの樹脂組成物シートを得た。
ビスフェノールA型エポキシ樹脂(三菱化学社製 商品名「828」)50重量部と、硬化剤(新日本理化社製 商品名「リカシッドTH」)50重量部、硬化促進剤(四国化成製 商品名「2MZ‐A」)2重量部、ビニルトリエトキシシラン10重量部とを配合し、ホモディスパー型撹拌機にて撹拌した。続けて離型PETシート状に混合物を塗工し、130℃のオーブンで3時間乾燥させることにより、厚み0.5mmの樹脂組成物シートを得た。
80℃の温水中に24時間浸漬しなかったこと以外は実施例1、2および4~13と同様にして、厚み0.5mmの樹脂複合材料シートを得た。
ビニルトリエトキシシランを60重量部添加したこと以外は実施例3と同様にして、厚み0.5mmの樹脂複合材料シートを得た。
上記のようにして得た実施例1~13及び比較例1~13の樹脂複合材料シートについて、IPN構造の有無及び線膨張率を、以下の要領でそれぞれ評価した。
実施例1~13及び比較例1~13により得られた樹脂複合材料シートについて、以下のa)~c)についてそれぞれ測定した。
作製したシートを直径8mm,厚さ0.5mmの円盤状にカットした.このサンプルを動的粘弾性測定装置(TAインスツルメンツ製,ARES)に取り付け,せん断モード,測定周波数0.1~100Hz,ひずみ1%の条件で測定した。測定温度及び貯蔵弾性率Gaと損失弾性率Gbとの関係を表1及び表2に示す。
試験管に作製したシートと溶媒を適量入れて未反応のシラン化合物を除去した。溶媒は表1に示す。8時間後にゲルを取り出し,120℃で3時間真空乾燥し、固形物を得た。その後核磁気共鳴装置(日本電子株式会社製、JNM-ECA)にてケイ素の有無を分析した。
試験管に作製したシートと溶媒を適量入れた。溶媒は表1に示す。8時間後にゲルを取り出し,電子天秤にて重量を測定した。続いてゲルを120℃で3時間真空乾燥し、電子天秤にて重量を測定した。得られた結果を次の計算式にあてはめて膨潤度を算出した。
実施例1~13及び比較例1~13により得られた樹脂複合材料シートの30~80℃における線膨張率を、JIS K7197に準拠して測定した。結果を下記の表1及び表2に示す。
12,12a…シラン化合物
13…結晶部分
Claims (18)
- 前記式(1)中の各Rが、水素、塩素、シリル、シロキシ、アルコキシ、ビニル、アリール、アルキル、アルキルアミン、エーテル、エステル、アミン、アミド、チオール、メタクリル、アクリル、エポキシ、ウレイド、メルカプト、スルフィド及びイソシアネートからなる群から独立して選択される、請求項1または2に記載の樹脂複合材料。
- 前記式(1)中の各Rのうち少なくとも1つが、ビニル、アルキルアミン、アミン、メタクリル、アクリル、エポキシ、ウレイド、メルカプト、スルフィド及びイソシアネートからなる群から選択される反応性有機官能基である、請求項1~3のいずれか1項に記載の樹脂複合材料。
- 前記樹脂複合材料において、前記シラン化合物に含まれる反応性有機官能基が反応することにより、反応性有機官能基の重合体が形成されている、請求項1~4のいずれか1項に記載の樹脂複合材料。
- 前記樹脂複合材料において、前記シラン化合物に含まれる反応性有機官能基が反応することにより、前記シラン化合物と前記樹脂とが化学結合を形成している、請求項1~5のいずれか1項に記載の樹脂複合材料。
- 前記樹脂が、熱可塑性樹脂である、請求項1~6のいずれか1項に記載の樹脂複合材料。
- 前記熱可塑性樹脂が結晶性樹脂であり、該結晶性樹脂の非晶部分を構成している分子鎖と、前記シラン化合物の分子鎖とが、前記IPN構造またはセミIPN構造を形成している、請求項7に記載の樹脂複合材料。
- 前記熱可塑性樹脂が、非晶性樹脂である、請求項7のいずれか1項に記載の樹脂複合材料。
- 前記樹脂が、熱硬化性樹脂である、請求項1~6のいずれか1項に記載の樹脂複合材料。
- 前記IPN構造形成工程において、前記樹脂組成物を80℃以上の水の存在下におくことにより、前記樹脂組成物に含まれる複数の前記シラン化合物同士を縮合させる、請求項11に記載の樹脂複合材料の製造方法。
- 前記式(1)中の各Rが、水素、塩素、シリル、シロキシ、アルコキシ、ビニル、アリール、アルキル、アルキルアミン、エーテル、エステル、アミン、アミド、チオール、メタクリル、アクリル、エポキシ、ウレイド、メルカプト、スルフィド及びイソシアネートからなる群から独立して選択される、請求項11または12に記載の樹脂複合材料の製造方法。
- 前記式(1)中の各Rのうち少なくとも1つが、ビニル、アルキルアミン、アミン、メタクリル、アクリル、エポキシ、ウレイド、メルカプト、スルフィド、及びイソシアネートからなる群から選択される反応性有機官能基である、請求項11~13のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記IPN構造形成工程の前に、前記シラン化合物に含まれる反応性有機官能基が反応して、反応性有機官能基の重合体を形成する工程をさらに備える、請求項11~14のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記反応性有機官能基の重合体を形成する工程が、樹脂組成物に放射線を照射することにより行われる、請求項15に記載の樹脂複合材料の製造方法。
- 前記IPN構造形成工程の前に、前記シラン化合物に含まれる反応性有機官能基が反応して、前記シラン化合物と前記樹脂とが化学結合を形成する工程をさらに備える、請求項11~16のいずれか1項に記載の樹脂複合材料の製造方法。
- 前記化学結合を形成する工程が、樹脂組成物に放射線を照射することにより行われる、請求項17に記載の樹脂複合材料の製造方法。
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US14/124,676 US20140113988A1 (en) | 2012-01-12 | 2013-01-08 | Resin composite material and method for producing resin composite material |
KR1020137032859A KR20140123405A (ko) | 2012-01-12 | 2013-01-08 | 수지 복합 재료 및 수지 복합 재료의 제조 방법 |
CN201380003129.1A CN103827224A (zh) | 2012-01-12 | 2013-01-08 | 树脂复合材料及树脂复合材料的制造方法 |
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US (1) | US20140113988A1 (ja) |
EP (1) | EP2803703A4 (ja) |
JP (2) | JP5374665B1 (ja) |
KR (1) | KR20140123405A (ja) |
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SG11201610665YA (en) * | 2014-06-20 | 2017-01-27 | Agency Science Tech & Res | Anti-scratch coating |
CN109651693A (zh) * | 2018-12-26 | 2019-04-19 | 无锡杰科塑业有限公司 | 微互穿网络交联型低烟无卤阻燃电缆料及其制备方法 |
JP7031614B2 (ja) | 2019-01-07 | 2022-03-08 | 信越化学工業株式会社 | オルガノポリシロキサン架橋物と(メタ)アクリル重合体からなる相互侵入網目重合体及びその製造方法 |
CN113072752B (zh) * | 2021-04-01 | 2022-11-22 | 西南科技大学 | 一种兼具优异核防护和柔韧性的橡胶复合材料及制备方法 |
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JP2004303567A (ja) * | 2003-03-31 | 2004-10-28 | Shirouma Science Co Ltd | ポリシロキサン系ゲル電解質組成物およびその製造法 |
JP2005285377A (ja) * | 2004-03-26 | 2005-10-13 | Shirouma Science Co Ltd | ポリシロキサンおよびポリオレフィン複合ゲル電解質およびそれを用いたリチウム電池 |
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US4500688A (en) * | 1982-04-20 | 1985-02-19 | Petrarch Systems Inc. | Curable silicone containing compositions and methods of making same |
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JP2002332354A (ja) * | 2001-05-08 | 2002-11-22 | Jsr Corp | 水系分散体とその製造方法および塗装体 |
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2013
- 2013-01-08 CN CN201380003129.1A patent/CN103827224A/zh active Pending
- 2013-01-08 US US14/124,676 patent/US20140113988A1/en not_active Abandoned
- 2013-01-08 KR KR1020137032859A patent/KR20140123405A/ko not_active Application Discontinuation
- 2013-01-08 JP JP2013501966A patent/JP5374665B1/ja not_active Expired - Fee Related
- 2013-01-08 WO PCT/JP2013/050068 patent/WO2013105539A1/ja active Application Filing
- 2013-01-08 EP EP13735987.3A patent/EP2803703A4/en not_active Withdrawn
- 2013-03-28 JP JP2013069572A patent/JP2014028919A/ja active Pending
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JPH10506956A (ja) * | 1995-04-21 | 1998-07-07 | アメロン インターナショナル コーポレイション | 改良された耐衝撃性を有するフェノール樹脂組成物 |
JP2004303567A (ja) * | 2003-03-31 | 2004-10-28 | Shirouma Science Co Ltd | ポリシロキサン系ゲル電解質組成物およびその製造法 |
JP2005285377A (ja) * | 2004-03-26 | 2005-10-13 | Shirouma Science Co Ltd | ポリシロキサンおよびポリオレフィン複合ゲル電解質およびそれを用いたリチウム電池 |
JP2008115292A (ja) * | 2006-11-06 | 2008-05-22 | Toyohashi Univ Of Technology | ポリイミド/シロキサン組成物 |
JP2008163055A (ja) * | 2006-12-26 | 2008-07-17 | Hokkaido Univ | 高強度ゲルおよびそのゲルの製造方法 |
JP2011527377A (ja) * | 2008-07-07 | 2011-10-27 | バイオミメディカ インコーポレイテッド | 疎水性ポリマーに由来する親水性相互貫入ポリマーネットワーク |
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Also Published As
Publication number | Publication date |
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US20140113988A1 (en) | 2014-04-24 |
EP2803703A4 (en) | 2015-07-15 |
JPWO2013105539A1 (ja) | 2015-05-11 |
EP2803703A1 (en) | 2014-11-19 |
CN103827224A (zh) | 2014-05-28 |
KR20140123405A (ko) | 2014-10-22 |
JP5374665B1 (ja) | 2013-12-25 |
JP2014028919A (ja) | 2014-02-13 |
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