JP7428985B2 - Laminates and composites containing carbon materials - Google Patents

Description

The present invention relates to adhesives for carbon materials, carbon material laminates laminated via the adhesive, laminates of carbon materials and ceramics, laminates of carbon materials and metals, composites of carbon layer materials and resins, and molded products such as resin bonds and saw wires containing these laminates and composites.

Carbon materials generally refer to materials composed of carbon atoms, and exhibit various forms and functions depending on the bonding and aggregation modes of carbon atoms. Among them, carbon materials include graphite, fullerene, carbon nanotubes, carbon nanohorns, carbon nanobrushes, graphene, and carbon. Fibers (carbon fiber), activated carbon, diamond-like carbon, carbon black, etc. have been attracting attention for a long time, and are used as reinforcing materials (aircraft, automobiles, sporting goods, tires), catalyst carriers, electrode materials (dry batteries, fuel cells), molecular sieve membranes, and water purification. It is widely used as adsorbents, deodorants, cosmetics, shampoos, face masks, surface coatings, electromagnetic shielding materials, heat dissipation materials, and pharmaceuticals (adsorbents).

Carbon materials consist of a 6-membered ring structure of carbon atoms and have no polarity, so they have poor wettability and dispersibility in general-purpose materials, and have insufficient adhesion with matrix resins. We have carried out surface hydrophilic treatment using conventional methods. For example, it has been reported that fluffing of carbon fibers can be prevented by attaching epoxy resin and 1,3-phenylenebis-2-oxazoline as sizing agents to the surface (Patent Document 1); A fiber sizing agent containing an acrylic resin and an aqueous medium has been reported (Patent Document 2). Diamond powder and fine particles can be stably dispersed in general-purpose solvents such as water and alcohol by introducing oxygen-containing functional groups such as hydroxyl groups onto the surface of diamond powders and fine particles through strong acid treatment at high temperatures or UV irradiation in the presence of hydrogen peroxide. A method for manufacturing diamond has been disclosed (Patent Documents 3 and 4).

On the other hand, carbon nanotubes (CNTs) are a typical nano-sized carbon material with excellent electrical, thermal, and mechanical properties, but they have a fibrous structure with a diameter of several to several tens of nanometers and a length of several to several hundred micrometers. , the aspect ratio was very large and the problem was that it was very easy to get tangled. In addition, CNTs have poor wettability, adhesion, and adhesion not only to general-purpose resins, metals, and inorganic matrices, but also to similar carbon-based matrices. In the development of composite materials, research is actively being conducted on physical and chemical treatments of CNT surfaces, and dispersion adjustment using dispersants.

Patent Document 5 discloses a CNT dispersant made of a polymer having an oxazoline group in a side chain, the dispersant, CNTs and A dispersion of CNT prepared from a solvent was reported. Patent Document 6 discloses a CNT dispersion promoter and an adhesion improver made of a polymer of an oxazoline monomer and a nitrogen-containing heterocyclic monomer, and a CNT prepared from the dispersion promoter, CNTs, and a dispersant such as water or alcohol. reported on dispersion liquids, etc. Further, Patent Document 7 discloses a CNT dispersion accelerator and adhesion improver made of a polymer of an oxazoline monomer and a vinyl monomer having a glass transition temperature of 70°C or less, a sizing agent for fibrous carbon materials, and the dispersion. A CNT dispersion prepared from a promoter, CNT, and a dispersant such as water or an organic solvent was reported. In all of these prior arts, the starting point is to prepare a CNT dispersion using an oxazoline polymer, and then, in Patent Document 5, the obtained CNT dispersion is coated on a current collecting substrate and heated. It was dried to form a conductive binding layer interposed between the current collecting substrate and the active material layer. In Patent Documents 6 and 7, CNTs surface-modified with an oxazoline polymer were produced by heating the obtained CNT dispersion and removing the dispersant.

However, in these conventional techniques, since the CNT and the polymer modified on its surface are integrated, they must be used as an integrated unit in various fields. Of course, the amount and uniformity of the modified polymer depends on many factors such as the number and density of carboxyl groups and phenolic groups on the CNT surface, the molecular weight of the modifying polymer, and the equivalent weight of the functional group. Even if dispersion was possible, there was a drawback that it was difficult to make the surface condition of the CNTs uniform. In particular, the higher the reactivity of the functional groups in the polymer and the higher the molecular weight of the polymer, the thicker the modification film on the CNT surface tends to become, leading to the problem that the CNT's original properties such as electrical conductivity and thermal conductivity cannot be exhibited. there were.

From this perspective, we are developing an adhesive for carbon materials that can easily bond carbon materials such as CNTs to various organic and inorganic materials such as metal materials, carbon materials, and resin materials without any particular surface treatment or surface modification. Development is desired.

Japanese Patent Application Publication No. 5-132874 Japanese Patent Application Publication No. 2014-152428 Japanese Patent Application Publication No. 9-025110 JP2012-046378A WO2015/029949 publication JP2018-24788A WO2018/168867 publication

The present invention enables carbon materials such as CNTs to be easily bonded to various organic materials and inorganic materials simply by using an adhesive, without requiring special surface treatment and without impairing the original properties of carbon materials. It is an object of the present invention to provide an adhesive for carbon materials, and also to provide a laminate or a composite having carbon materials obtained by bonding via the adhesive. Furthermore, it is an object of the present invention to provide an industrial method for manufacturing laminates and composites having carbon materials using the adhesive.

As a result of intensive studies to solve these problems, the present inventors found that a polymer obtained by polymerizing a vinyl monomer having a functional group that reacts with active hydrogen can be used as a carbon material, various organic materials, and inorganic materials. It has been found that it has excellent adhesion and strong adhesion. In addition, by bonding the carbon material and various organic and inorganic materials using the adhesive, it was possible to obtain a laminate and a composite containing the carbon material. Furthermore, we were able to find a method for easily producing a laminate or composite of carbon materials using the adhesive, and the above problems were solved, leading to the present invention.

That is, the present invention
(1) A reactive adhesive (D) used for bonding a carbon material (C), containing a polymer (B) obtained by polymerizing a vinyl monomer (A) having a functional group that reacts with active hydrogen;
(2) The adhesive according to (1) above, wherein the functional group of the vinyl monomer (A) is one or more functional groups selected from an oxazoline group, a glycidyl group, an isocyanate group, and a carbodiimide group. (D),
(3) The adhesive (D) according to (1) or (2) above, wherein the constituent units derived from the vinyl monomer (A) constituting the polymer (B) are 10 mol% or more;
(4) The adhesive (D) according to any one of (1) to (3) above, wherein the polymer (B) has a glass transition temperature of 80° C. or higher;
(5) The polymer (B) according to any one of (1) to (4) above, wherein the structural unit derived from the vinyl monomer (A) having an oxazoline group exceeds 90 mol%. Adhesive (D),
(6) Carbon materials (C) include carbon fiber (CF), graphite, diamond (DM), diamond-like carbon (DLC), carbon black (CB), nanocarbon fiber (CNF), carbon nanotube (CNT), graphene, The adhesive (D) according to any one of (1) to (5) above, characterized in that it is one or more materials selected from fullerenes,
(7) a carbon material laminate (E) in which carbon materials (C) are laminated via the adhesive (D) according to any one of (1) to (6);
(8) A carbon/ceramic laminate (F) formed by laminating a carbon material (C) and ceramics via the adhesive (D) according to any one of (1) to (6) above;
(9) A carbon/metal laminate (G) formed by laminating a carbon material (C) and a metal via the adhesive (D) according to any one of (1) to (6) above,
(10) A carbon/resin composite (H) formed by combining a carbon material (C) and a resin material via the adhesive (D) according to any one of (1) to (6) above,
(11) In the carbon material laminate (E) described in (7) above, carbon fibers (CF), carbon nanofibers (CNF) and/or carbon nanotubes (CNT) are bonded together via an adhesive (D). (CNF, CNT)/CF carbon material laminate obtained by laminating the carbon material laminate, characterized in that the coverage of CNF and/or CNT on the CF surface is 10% or more. (E1),
(12) The carbon material laminate (E) described in (7) above is a carbon material laminate (E) in which diamond particles and carbon nanofibers (CNF) and/or carbon nanotubes (CNT) are laminated via an adhesive (D). (CNF, CNT)/diamond carbon material laminate (E2), characterized in that the CNT coverage rate on the surface of the diamond particles is 10% or more;
(13) The carbon/ceramic laminate (F) described in (8) above is a structure in which ceramics and carbon nanofibers (CNF) and/or carbon nanotubes (CNT) are laminated via an adhesive (D). A carbon/ceramic laminate obtained by a carbon/ceramic laminate, characterized in that the CNT coverage on the ceramic surface is 10% or more,
(14) The carbon/metal laminate (G) described in (9) above is a carbon/metal laminate (G) in which a metal and carbon nanofibers (CNF) and/or carbon nanotubes (CNT) are laminated via an adhesive (D). a carbon/metal laminate obtained by a carbon/metal laminate, the carbon/metal laminate having a CNT coverage rate of 10% or more on the metal surface;
(15) A resin bonded grindstone containing the (CNF, CNT)/diamond laminate (E2) described in (12) above;
(16) A saw wire containing the (CNF, CNT)/diamond laminate (E2) according to (12) above;
(17) Bringing the adhesive (D) according to any one of the above (1) to (5) into contact with the surface of the carbon material (C) that is the base material to form a chemical bond between the base material and the adhesive. A method for producing a carbon material laminate (E), characterized in that after forming an adhesive layer, the same or different carbon material is brought into contact with the adhesive layer and bonded by chemical bonding,
(18) The base material is one or more materials selected from carbon fiber (CF), diamond (DM), diamond-like carbon (DLC), and carbon nanofiber (CNF), and the carbon material to be bonded is carbon nanotube. (CNT), carbon nanofiber (CNF), the method for producing a carbon material laminate (E) according to (17) above,
(19) The adhesive (D) according to any one of (1) to (5) above is brought into contact with the surface of the ceramic base material, and an adhesive layer is formed between the base material and the adhesive by chemical bonding. A method for producing a carbon/ceramic laminate (F), which comprises forming the carbon material (C), then bringing the carbon material (C) into contact with the adhesive layer and adhering it by chemical bonding;
(20) The carbon/ceramic laminate according to (19) above, wherein the base material is ceramic, and the carbon material to be bonded is carbon nanofiber (CNF) and/or carbon nanotube (CNT). F) manufacturing method,
(21) A carbon/resin composite characterized in that the adhesive (D) according to any one of the above (1) to (5) is mixed into a resin material and then composited with a carbon material (C). method for producing body (H);
(22) The carbon/resin described in (21) above, wherein the carbon material is one or more materials selected from carbon fibers (CF), carbon nanofibers (CNF), and carbon nanotubes (CNT). A method for producing composite (H) is provided.

The adhesive (D) of the present invention contains a polymer (B) obtained by polymerizing a vinyl monomer (A) having a functional group that reacts with active hydrogen, and has a reactive property used for adhesion of a carbon material (C). An adhesive for obtaining molded products such as composites and laminates by bonding carbon materials to each other, carbon materials to organic materials such as resins, and inorganic materials such as ceramics and metals through the adhesive. be able to. In addition, since it is possible to form a thin adhesive layer, it is possible to easily create high-performance laminates and composites without impairing the inherent properties of carbon materials such as mechanical strength, thermal conductivity, and electrical conductivity. can be manufactured.

The present invention will be explained in detail below.
The vinyl monomer (A) used in the present invention is a vinyl monomer having a functional group that reacts with active hydrogen. The active hydrogen referred to in the present invention refers to the active hydrogen of a carboxyl group or phenolic hydroxyl group that is present on the surface of a carbon material. Further, the functional group that the vinyl monomer (A) has is not particularly limited as long as it is a functional group that can react with these active hydrogens under normal reaction conditions such as temperature, pressure, and presence of a catalyst. Examples include amine groups, alcohol groups, acid anhydrides, glycidyl groups, isocyanate groups, oxozoline groups, and carbodiimide groups. Among these, a glycidyl group, an isocyanate group, a carbodiimide group, and an oxozoline group are preferred because they have high reactivity with active hydrogen. Among these, oxazoline groups are particularly preferred because they have the highest reactivity and addition reactions with active hydrogen do not generate by-products.

Examples of the vinyl monomer (A1) having a glycidyl group include glycidyl (meth)acrylate, (meth)acrylate monomers having a glycidyl group such as 4−hydroxybutyl (meth)acrylate glycidyl ether, and N-glycidyl (meth)acrylamide. , N−methyl−N−glycidyl (meth)acrylamide, N−ethyl−N−(meth)glycidyl acrylamide, and other (meth)acrylamide-based monomers having a glycidyl group. , allylglycidyl ether, trialkoxysilyl monoglycidyl ether, tricyclodecane dimethanol monoallyl ether monoglycidyl ether, tricyclodecane dimethanol trialkoxysilyl monoglycidyl ether, and other monomers having a glycidyl group and an allyl group. It will be done. Among these, glycidyl methacrylate and glycidyl acrylate are preferred from the viewpoint of easy availability of industrial products and good copolymerizability. These glycidyl group-containing vinyl monomers are not limited to one type, and a plurality of types may be used in combination.

As the vinyl monomer (A2) having an isocyanate group, 2-isocyanate ethyl (meth)acrylate, 3-isocyanate propyl (meth)acrylate, 2-isocyanate 1-methylethyl (meth)acrylate, 3-(meth)acryloyloxyphenyl Isocyanate, 3-isocyanate 2-methylbutyl (meth)acrylate, 4-(meth)acryloyloxyphenyl isocyanate, 3-(meth)acryloyloxyphenyl isocyanate, 2-(meth)acryloyloxyphenyl isocyanate, 3,5-bis(meth) ) acryloyloxyethyl) phenyl isocyanate, 2,4-bis((meth)acryloyloxy) phenyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, 1,1-bis((meth)acryloyloxy) Examples include methyl)ethyl isocyanate and (meth)acryloyl isocyanate. Among these, 2-isocyanate ethyl acrylate and 2-isocyanate ethyl methacrylate are preferred from the viewpoint of easy availability of industrial products and good copolymerizability. These isocyanate group-containing vinyl monomers are not limited to one type, and a plurality of types may be used in combination.

Examples of the vinyl monomer (A3) having an oxazoline group include 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2- Vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5- Dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl- 2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, Examples include 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, and 4,5-diethyl-2-isopropenyl-2-oxazoline. Among these, from the viewpoint of having high reactivity with carboxyl groups and phenolic hydroxyl groups, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4 -dimethyl-2-vinyl-2-oxazoline is preferred, and 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline are particularly preferred. These vinyl monomers having an oxazoline group are not limited to one type, and a plurality of types may be used in combination.

These vinyl monomers (A) may be used alone or in combination of two or more types having different functional groups.

The polymer (B) used in the present invention preferably contains 10 mol % or more of constitutional units derived from the vinyl monomer (A). If the content of (A) is 10 mol% or more, the obtained polymer (B) has sufficient functional groups that can react with carbon materials and other organic materials and inorganic materials, and the polymer ( The adhesive (D) of the present invention containing B) is preferred because it can strongly bond these materials.

The polymer (B) used in the present invention preferably contains more than 90 mol% of constitutional units derived from the vinyl monomer (A3) having an oxazoline group. If A3 is contained in an amount exceeding 90 mol%, the density of oxazoline groups contained in the polymer (B) is high, and it becomes possible to reduce the molecular weight of B, thereby making it possible to reduce the molecular weight of the adhesive (D) of the present invention. A thin and strong adhesive layer can be formed. Moreover, from the same viewpoint, the content of A3 is more preferably 95 mol% or more, and the content of A3 is particularly preferably 100 mol% (homopolymer).

The polymer (B) used in the present invention preferably has a glass transition temperature (Tg) of 80°C or higher. When Tg is 80°C or higher, the adhesive (D) of the present invention containing the polymer (B) can form a thin and uniform adhesive layer on the surface of carbon materials and other organic and inorganic materials. A specific effect was confirmed. Although it is not clear whether the Tg of the polymer (B) has a causal relationship with the specific effect, the polymer (B) of the present invention can interact with carboxyl groups or phenol groups on the surface of carbon materials, organic materials, or inorganic materials. It has been confirmed that the reaction proceeds quickly when the temperature is 80°C or higher, and if the Tg of the polymer (B) is 80°C or higher, it has appropriate flexibility during the reaction, so the group The adhesive layer is uniformly distributed on the surface of the material, and after the reaction is completed, the adhesive layer is fixed in a uniformly distributed state on the surface of the base material as soon as the base material is cooled, thereby obtaining a thin and uniform adhesive layer. The inventors speculate that this is because it is possible to On the other hand, in the case of a polymer having a Tg of less than 80° C., when the substrate is cooled after the completion of the reaction, there is a possibility that the adhesive layer will aggregate into a lump or lump shape depending on the number of functional groups.

The method for polymerizing the polymer (B) used in the present invention is not particularly limited, and it can be synthesized by a known radical polymerization method. Examples include solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization in organic solvents such as alcohol and ethyl acetate, or in water. When a solution polymerization method in an organic solvent is employed, the polymerization solvent may be toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol, etc. alone or in combination.

Examples of the polymerization initiator used in the polymerization of the polymer (B) include commonly known polymerization initiators such as azo type, organic peroxide type, inorganic peroxide type, and redox type. The amount of the polymerization initiator used is usually about 0.001 to 10 mol% based on the total amount of polymerizable monomer components. Further, ordinary radical polymerization techniques such as adjustment of molecular weight using a chain transfer agent can be applied.

The vinyl monomer (A) alone may be used as the monomer constituting the polymer (B), but other copolymerizable vinyl monomers may also be used. Other copolymerizable vinyl monomers include (meth)acrylates having alkyl groups with 1 to 12 carbon chains, N-alkyl (meth)acrylamides having alkyl groups with 1 to 12 carbon chains, the same or different N,N-dialkyl (meth)acrylamides with two carbon chain 1-12 alkyl groups, (meth)acrylates or (meth)acrylamides with aromatic substituents, hydroxyalkyl (C1-12) (meth)acrylates or Examples include (meth)acrylamide, (meth)acrylonitrile, (meth)acrylic acid, and the like. These copolymerizable vinyl monomers may be used alone or in combination of two or more.

The weight average molecular weight of the polymer (B) used in the present invention is 500 to 200,000. Further, it is preferably 1,000 to 100,000, more preferably 2,000 to 60,000. If the weight average molecular weight is less than 500, there will be a large amount of unpolymerized monomer (residual monomer), and when it is blended into the adhesive (D), it may not be possible to obtain sufficient adhesive strength, which is undesirable. . On the other hand, if the weight average molecular weight exceeds 200,000, an adhesive layer may be formed on the surface of the carbon material, organic material, or inorganic material, depending on the amount of the polymer (B) in the adhesive (D). This is not desirable as it may become thick or uneven.

The adhesive (D) of the present invention preferably contains 10% by mass or more of the polymer (B) as an essential component. If the polymer (B) is less than 10% by mass, the resulting adhesive (E) may have insufficient adhesive strength depending on the amount and type of functional groups contained in B, which is not preferable.

The carbon material (C) used in the present invention is a material (carbon material) mainly composed of only carbon, and specifically includes carbon fiber (CF), graphite, diamond (DM), diamond-like carbon ( DLC), carbon black (CB), nanocarbon fiber (CNF), carbon nanotube (CNT), graphene, and fullerene. Carbon fibers (CF) include polyacrylonitrile (PAN), pitch, rayon, and plant-based materials, and carbon nanotubes (CNT) include single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (SWCNT), Examples include wall carbon nanotubes (DWCNTs), multiwall carbon nanotubes (MWCNTs), and cup stacked carbon nanotubes (CSCNTs). Among these, PAN-based carbon fibers are more preferable as fibrous carbon materials because they have excellent strength and elastic modulus per unit weight and can be produced in large quantities, while CNTs can control the structure at the nanometer level and are inexpensive as new functional materials. Since it can now be manufactured at an industrial level, it is preferred as a nano-based carbon material. Further, these carbon materials may be used as they are as commercially available products, or may be used after being subjected to a treatment such as oxidation to arrange many carboxyl groups or phenolic hydroxyl groups on the surface.

The carbon material (C) used in the present invention may be used alone or in combination of two or more types depending on the purpose. In addition, although these carbon materials can be used as ordinary commercially available products, they may be washed with water or a solvent, or may be subjected to physical dispersion treatment such as bead mill dispersion treatment or ultrasonic dispersion treatment to disentangle the CNTs. It is more preferable to use it after carrying out.

Various laminates (E, F, G,) using carbon materials of the present invention are carbon material laminates (E) formed of the same carbon material or different carbon materials, carbon material laminates (E) formed of carbon materials and ceramics, /Ceramics laminate (F), carbon/metal laminate (G) formed of carbon material and inorganic material such as metal, carbon/inorganic material laminate, carbon formed of carbon material and organic material other than carbon material /organic material laminate, etc. In addition, the carbon material laminate (E) includes carbon fiber (CF), graphite, diamond (DM), diamond-like carbon (DLC), carbon black (CB), nanocarbon fiber (CNF), carbon nanotube (CNT), It can be formed by laminating two or more materials arbitrarily selected from graphene and fullerene. Among these, carbon material laminates formed from carbon fibers and carbon nanofibers, carbon fibers and nanodiamond particles, carbon fibers and carbon nanotubes, carbon nanofibers and carbon nanotubes, diamond particles and carbon nanotubes, etc. have different sizes. This combination of carbon materials is more preferable because defects in physical properties can be repaired, characteristics can be maintained or further enhanced, and unique effects not seen before can be expected due to the interaction of different types of carbon materials.

Various laminates using the carbon material of the present invention are formed using an adhesive (D). The lamination method is not particularly limited, and can generally be carried out by applying an adhesive to the surfaces of both or one of the laminated materials and adhering them. Since the shape of the laminated material (adhesive) may differ or the surface area may differ greatly, the adhesive is brought into contact with the surface of the base material and an adhesive layer is formed between the base material and the adhesive through chemical bonding. A preferred manufacturing method is to further contact the laminated material and bond the laminated material and the adhesive in the adhesive layer by chemical bonding.

The base material used in the present invention is a carbon material, an inorganic material, a metal material, or the like. Further, it is preferable to have active hydrogen on the surface of the base material, and it is particularly preferable that the active hydrogen is a carboxyl group or a phenolic hydroxyl group. The required minimum amount of functional groups on the surface of the base material varies depending on the material of the base material, the shape of the surface, etc., but the total amount of carboxyl groups and phenolic hydroxyl groups should be 0.1 μmol/g or more. preferable. Moreover, it is more preferable that it is 0.5 micromol/g or more, and it is most preferable that it is 1.0 micromol/g or more. The base material used in the present invention is not limited to one type, and multiple types can be used in combination. In addition, it may be used as a commercially available product, or it may be used after being subjected to a treatment such as oxidation to arrange many carboxyl groups or phenolic hydroxyl groups on the surface.

The laminate material used in the present invention is a carbon material, and in order to introduce the properties of nano-sized carbon materials such as excellent electrical conductivity, thermal conductivity and mechanical strength into the laminate material, the laminate material is made of nano-sized carbon material. It is preferable that it is a carbon material. Specific examples include nano-sized diamonds, diamond-like carbon, carbon nanofibers, carbon nanotubes, graphene, and fullerene. Among these, carbon nanofibers and carbon nanotubes with a large aspect ratio are particularly preferable because they have soft and strong mechanical properties. It is preferable that the surface of the laminate also contains active hydrogen, and the active hydrogen is particularly preferably a carboxyl group or a phenolic hydroxyl group. The required minimum amount of functional groups on the surface of the laminated material varies depending on the material of the laminated material, the shape of the surface, etc., but the total amount of carboxyl groups and phenolic hydroxyl groups should be 0.1 μmol/g or more. preferable. Moreover, it is more preferable that it is 0.5 micromol/g or more, and it is most preferable that it is 1.0 micromol/g or more. The laminated material used in the present invention is not limited to one type, and a plurality of types can be used in combination. In addition, it may be used as a commercially available product, or it may be used after being subjected to a treatment such as oxidation to arrange many carboxyl groups or phenolic hydroxyl groups on the surface.

When the laminated material is carbon nanotubes or the like having a very large aspect ratio, it is very easy to get entangled, so it is preferable to use the material after dispersing it in water or an organic solvent. As a dispersant for carbon materials such as carbon nanotubes, organic solvents that are liquid at room temperature (25° C.) and water are preferable. Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone, esters such as ethyl acetate, propyl acetate, butyl acetate, and ethylene glycol. Ethers such as monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether, tetrahydrofuran (THF), toluene, xylene, chloroform, N-methylpyrrolidone (NMP), N-methylformamide (NMF), N,N-dimethylformamide (DMF), N-methylacetamide, dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), cyclohexane, alkoxy-N,N-dialkylpropanamide, polyhydric alcohol, silicone oil, A wide variety of surfactants can be used, including cationic, anionic, amphoteric or nonionic surfactants. Further, any one of these solvents may be used alone, a plurality of solvents may be combined, or a mixture of a water-soluble organic solvent and water in an arbitrary blending ratio may be used.

In particular, dispersants for the above solvents include NMP, NMF, DMF, DMSO, "KJCMPA" (3-methoxy-N,N-dimethylpropanamide, "KJCMPA" is a registered trademark of KJ Chemicals Co., Ltd.), etc. Hydrophilic solvents that have nitrogen or sulfur atoms in their molecules have a strong interaction with the functional groups on the surface of carbon materials, which has the effect of preventing re-aggregation of carbon materials such as CNTs, making them stable. This is preferable because it facilitates the formation of a dispersion liquid. Furthermore, when water is used as a dispersant, there is no organic solvent to be disposed of, which has the advantage of being environmentally friendly.

The method for manufacturing a laminate containing a carbon layer material of the present invention involves contacting the surface of a base material with an adhesive, forming an adhesive layer between the base material and the adhesive by chemical bonding, and then further contacting the laminate material. In this method, the laminated material and the adhesive in the adhesive layer are bonded by chemical bonding. The method of bringing the surface of the base material into contact with the adhesive varies depending on the molecular weight and condition of the adhesive. If the adhesive is liquid at the working temperature, there are two methods: applying a thin layer of the adhesive to the surface of the substrate, passing a fibrous carbon material through a liquid or waxy adhesive, and dipping particulate carbon material into the adhesive. One example is how to do it. Furthermore, whether the adhesive is solid or liquid, it is preferable to prepare and use a solution of the adhesive. An adhesive in a solution state is preferable because it can form a thin adhesive layer by contacting the surface of the substrate at an extremely low concentration.

The reaction between the base material and the adhesive does not vary greatly depending on the material of the base material, but an appropriate reaction method can be selected depending on the shape and size of the base material. Reaction methods can be broadly divided into two types: one is to heat the adhesive while it is in contact with the surface of the base material in a liquid medium, and the other is to heat the adhesive while it is in contact with the surface of the base material in a liquid medium. This is a method in which the material is brought into contact with the surface of the material and then heated. in particular,
(1) Dissolve the adhesive in water or an organic solvent to prepare an adhesive solution. The obtained solution is heated to a predetermined temperature, and the fibrous base material is passed through the adhesive solution at a predetermined speed, and the active hydrogen contained in the functional groups such as carboxyl groups on the surface of the base material is combined with the oxazoline etc. of the adhesive. The functional groups are reacted to form a thin and uniform adhesive layer on the surface of the substrate. In addition, by adding a particulate base material to an adhesive solution heated to a predetermined temperature, or by pouring a heated adhesive solution onto a particulate base material, it is possible to add functional groups such as carboxyl groups on the surface of the base material. Active hydrogen reacts with functional groups such as oxazoline in the adhesive to form a thin and uniform adhesive layer on the surface of the base material.
(2) Perform the operation in (1) above at room temperature or low temperature to bring the adhesive into contact with the surface of the base material. Thereafter, while heating to a predetermined temperature and removing the solvent, the active hydrogen contained in the functional groups such as carboxyl groups on the surface of the base material is reacted with the functional groups such as oxazoline of the adhesive, and a thin and uniform coating is applied to the surface of the base material. Form an adhesive layer.

In the manufacturing method of (1) above, a solvent that has a high boiling point and high thermal stability, can dissolve the adhesive, and does not have reactivity with the adhesive can be used. The reaction temperature varies depending on the type of substrate and the composition and structure of the adhesive, but is preferably 40 to 200°C, more preferably 60 to 180°C. If the temperature is lower than 40°C, the reaction time may be longer or the reaction may not proceed sufficiently, while if the temperature is higher than 200°C, it may be necessary to use a solvent with a fairly high boiling point, and the There is a problem that the solvent cannot be easily removed.

In the manufacturing method (2) above, water, a low boiling point solvent, a thermally unstable solvent, or a solvent that reacts with the adhesive is used as the solvent. The contact treatment temperature is preferably -20 to 40°C, and the subsequent reaction temperature is 40 to 240°C, preferably 60 to 220°C, and more preferably 80 to 200°C. If the reaction temperature is less than 40°C, there is a possibility that less reactive substances may not react sufficiently depending on the structure of the adhesive, and if the reaction temperature exceeds 240°C, thermal decomposition or oxidation of the adhesive may occur. There are problems that are likely to occur and are not desirable.

The reaction between the laminated material of the present invention and the adhesive layer adhered to the surface of the base material is achieved by bringing the surface of the laminated material into contact with the adhesive layer, and creating a chemical bond between the laminated material and the adhesive in the adhesive layer. This is the way to do it. The method of bringing the surface of the laminated material into contact with the adhesive layer depends on the type, shape, and size of the base material that has the adhesive layer on the surface of the laminated material, the type, shape, and size of the laminated material, as well as the molecular weight, number of functional groups, etc. of the adhesive. However, it is preferable to prepare the laminate in the form of a dispersion wax and then bring it into contact with the adhesive layer on the base material, from the viewpoint of obtaining a uniform laminate.

The laminate material used in the present invention is more preferably in the form of a dispersion liquid dispersed in water or an organic solvent. As long as a dispersion liquid can be prepared, there are no particular restrictions on the dispersion method, equipment used for dispersion, and processing conditions such as dispersion temperature and dispersion time. In particular, in nano-sized laminate materials, from the viewpoint of preventing breakage during dispersion treatment, it is preferable to use a stirring device, an ultrasonic cleaner, a bead mill disperser, or the like as the device.

For the reaction between the laminate and the adhesive, an appropriate reaction method can be selected depending on the shape and size of the laminate and the base material. The reaction method can be broadly divided into two types: one is to prepare the laminate in the form of a dispersion or wax, and heat it while bringing it into contact with the adhesive layer on the surface of the base material; This is a method in which the adhesive is prepared in the form of a dispersion or wax, brought into contact with the adhesive layer on the surface of the base material, and then heated. in particular,
(1) The laminate material is dispersed in water or an organic solvent to prepare a dispersion liquid or wax of the laminate material. Further, in order to obtain a uniform laminate, a laminate material dispersion liquid with a low concentration is preferable. The obtained laminate material dispersion is heated to a predetermined temperature, and a fibrous base material having an adhesive layer on the surface is passed through the laminate material dispersion at a predetermined speed to form functional groups such as carboxyl groups on the surface of the laminate. The adhesive is reacted with a functional group such as oxazoline, and the laminate material is adhered to the surface of the base material via the adhesive layer, thereby forming a laminate consisting of the base material/adhesive layer/laminate material. In addition, a particulate base material having an adhesive layer on the surface may be added to a dispersion of a laminate material heated to a predetermined temperature, or a particulate base material having an adhesive layer on the surface may be heated with a dispersion of a laminate material. The functional groups such as carboxyl groups on the surface of the laminate react with the functional groups such as oxazoline of the adhesive by pouring water onto the surface of the laminate, and the laminate is adhered to the surface of the base material via the adhesive layer, forming the base material/adhesive layer/laminated material. A laminate of materials is formed.
(2) After carrying out the work in (1) above at room temperature or low temperature to bring the adhesive into contact with the surface of the laminate, heat it to a predetermined temperature and remove water and solvent while removing the carboxyl groups on the surface of the laminate. The functional group of the adhesive is reacted with the functional group of the adhesive such as oxazoline, and the laminate material is adhered to the surface of the base material via the adhesive layer, thereby forming a laminate consisting of the base material/adhesive layer/laminate material.

In the manufacturing method of (1) above, the solvent may be a solvent that has good dispersibility in the laminate, has a high boiling point and high thermal stability, and does not react with the laminate, the base material, or the adhesive. . The reaction temperature varies depending on the substrate, the type of laminate, the composition and structure of the adhesive, but is preferably 40 to 200°C, more preferably 60 to 180°C. If the temperature is lower than 40°C, the reaction time may be longer or the reaction may not proceed sufficiently, while if the temperature is higher than 200°C, it may be necessary to use a solvent with a fairly high boiling point, and the There is a problem that the solvent cannot be easily removed.

In the manufacturing method (2) above, the solvent may be water, a low boiling point solvent, a thermally unstable solvent, or a solvent that reacts with the laminate, the base material, and the adhesive. The contact treatment temperature is preferably -20 to 40°C, and the subsequent reaction temperature is 40 to 240°C, preferably 60 to 220°C, and more preferably 80 to 200°C. If the reaction temperature is less than 40°C, there is a possibility that less reactive substances may not react sufficiently depending on the structure of the adhesive, and if the reaction temperature exceeds 240°C, thermal decomposition or oxidation of the adhesive may occur. There are problems that are likely to occur and are not desirable.

As the dispersant for the base material and the laminate material used in the present invention, organic solvents and water that are liquid at room temperature (25° C.) are preferable. Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone, esters such as ethyl acetate, propyl acetate, butyl acetate, and ethylene glycol. Ethers such as monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether, tetrahydrofuran (THF), toluene, xylene, chloroform, N-methylpyrrolidone (NMP), N-methylformamide (NMF), N,N-dimethylformamide (DMF), N-methylacetamide, dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), cyclohexane, alkoxy-N,N-dialkylpropanamide, polyhydric alcohol, silicone oil, A wide variety of surfactants such as cationic, anionic, amphoteric or nonionic surfactants can be used. Further, any one of these solvents may be used alone, a plurality of solvents may be combined, or a mixture of a water-soluble organic solvent and water in an arbitrary blending ratio may be used.

In dispersants for the above solvents, molecules such as NMP, NMF, DMF, DMSO, and "KJCMPA" (3-methoxy-N,N-dimethylpropanamide, "KJCMPA" is a registered trademark of KJ Chemicals Co., Ltd.) are particularly useful. The hydrophilic solvent having a nitrogen atom or a sulfur atom has a strong interaction between the base material and the laminated material used in the present invention, and thereby has the effect of preventing re-aggregation of nano-sized laminated materials such as CNTs. However, it is preferable because a stable dispersion can be easily formed. Furthermore, when water is used as a dispersant, there is no organic solvent to be disposed of, which has the advantage of being environmentally friendly. At this time, known dispersion promoters, N-vinylpyrrolidone polymers, and the like may be added.

The concentration of the laminate material dispersion varies greatly depending on the shape and size of the laminate, the presence or absence of pretreatment and the treatment method, the type of dispersion, the presence or absence of a dispersion accelerator, and the amount of these, but It is preferably 0.01 to 20% by mass based on the dispersing agent, and in the case of laminated materials such as CNTs that are difficult to disperse and have large aspect ratios, it is preferably 0.01 to 10% by mass based on the dispersing agent. More preferably, the content is particularly preferably from 0.05 to 5% by mass from the viewpoint of forming a laminate that is uniform, thin, and has a high coverage.

The laminate of the present invention is manufactured by laminating a laminate material on a base material via an adhesive, and the number of laminations is not particularly limited, but the laminate material is adhered onto the surface of the base material. The coverage rate, which indicates the amount of laminated material, is preferably 10% or more, more preferably 20% or more in one lamination process. Furthermore, by increasing the number of lamination operations, a laminate with a coverage of 100% can be easily obtained. Furthermore, in a laminate with 100% coverage, continuous lamination is possible by reacting functional groups such as carboxyl groups on the surface of the laminate with functional groups such as oxazoline in the adhesive. A laminated material of carbon materials whose thickness can be suitably adjusted can be easily manufactured, and can be suitably used in various applications and fields.

The composite of the present invention is made by combining a carbon material and a resin material with an adhesive. Examples of resin materials used in the composite include thermoplastic resins and moldable low molecular weight thermosetting resins. These resin materials may be used alone or in combination. The blending ratio with the composite carbon material varies depending on the type, structure, physical properties, and purpose of the resin material, but for example, it can be used to reinforce thermoplastic resins or low-molecular-weight thermosetting resins, impart antistatic properties, improve heat resistance, etc. Depending on the intended use, carbon material can be blended in an amount of 0.01% to 20% by mass, preferably 0.05% to 10% by mass, based on the thermoplastic resin. Furthermore, it is preferable to dilute and use a highly concentrated carbon material as a masterbatch because it makes it easier to obtain a uniform carbon/resin composite material. On the other hand, for applications such as surface coating, surface modification, and surface modification of resin materials, the carbon material is 0.001% to 10% by mass, preferably 0.005% to 5% by mass, based on the surface layer of the resin material. It is preferable to mix the resin material, and a molding method such as applying a dispersion of the carbon material to the surface of the resin material can be used.

Thermoplastic resins include polyolefins such as polyethylene (PE) and polypropylene (PP), polyamides such as nylon 6 (PA6) and nylon 66 (PA66), and polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Examples include thermoplastic resins such as polyurethanes, acrylic resins, ABS (acrylonitrile butadiene styrene) resins, polystyrene (PS), polycarbonates, and carboxylic acid or maleic anhydride modified resins of these general-purpose resins. Examples of molecular weight thermosetting resins include phenol resins, epoxy resins, polyimide resins, melamine resins, urea resins, unsaturated polyester resins, diallyl phthalate resins, polyurethane resins, and silicone resins.These resins are not limited to one type. , multiple types can be used in combination.

The carbon materials used for the carbon/resin composite (H) include, in principle, the various carbon materials described above. Among these, carbon fibers (CF), carbon nanotubes (CNT), carbon nanofibers (CNF), natural or synthetic diamonds, and the like are preferred because they are easily available as inexpensive commercial products. These carbon materials are not limited to one type, and a plurality of types can be used in combination. Further, these carbon materials may be used as commercially available products, or may be used after being subjected to treatment such as oxidation to arrange many carboxyl groups or phenolic hydroxyl groups on the surface.

The obtained carbon/resin composite consists of a thermoplastic resin-based carbon/resin composite containing a thermoplastic resin as a main component, a thermosetting resin-based carbon/resin composite containing a thermosetting resin as a main component, and a carbon/resin composite containing a thermosetting resin as a main component. It can be classified into carbon-based carbon/resin composites whose main components are carbon-based materials, and by further subjecting these carbon/resin composites to complex reactions, various required physical properties such as strength, elongation, and toughness can be met. New types of carbon/resin composites can be produced. From the perspective of ensuring sufficient workability and moldability of the new carbon/resin composite material, the blending ratio of carbon material in the thermosetting resin carbon/resin composite material is 1. It is preferably more than 10% by mass, more preferably more than 10% by mass.

Methods for producing carbon/resin composites (H) can be broadly divided into solution immersion methods, melt-kneading methods, and solution reaction methods, depending on the structure of the main component and the use of the resulting composite. In the dipping method, a dispersion of the carbon material (C) is prepared in the same manner as the dispersion of the laminate described above, and then a certain amount of the resin material modified with the adhesive (D) of the present invention is added to the dispersion. The adhesive on the surface of the resin material is brought into contact with the surface of the carbon material by immersion for a residence time, and the resin material and the carbon material form a composite via the adhesive by heating at the same time or after the contact. be done. In addition, modification processing of a resin material with the adhesive (D) of the present invention can be carried out by dissolving both the adhesive and the resin material in a solvent and reacting in the solution, or by melt-kneading or extrusion of the adhesive and the resin material using an extruder. It can be carried out by a known method such as. The obtained carbon/resin composite is suitably used mainly for surface modification such as reinforcing thermosetting resins, imparting antistatic properties, and improving heat resistance. Further, the reaction between the carbon material and the adhesive on the surface of the resin material can be carried out under the same conditions (reaction temperature, reaction time, etc.) as described above.

In the method of producing a carbon/resin composite (H) by melt kneading, a thermoplastic resin, a low molecular weight thermosetting resin, an adhesive, and other additives, if solid at room temperature, are dried at a predetermined blending ratio. After blending, the reaction can be carried out by melt kneading while heating using a melt extruder or the like. Furthermore, when the material is liquid at room temperature, the reaction can be carried out by adding the material in a fixed amount while pressurizing it through the liquid inlet of the kneading extruder and similarly melting and kneading it. The melt-kneading temperature varies greatly depending on the type of resin, but if it is within the range of 80 to 240°C, it will melt the functional groups such as carboxyl groups on the terminal or side chains of the resin material and the oxazoline groups on the adhesive. The reaction can be fully completed in a kneading process of 0.1 to 30 minutes, and neither the adhesive nor the resin material decomposes thermally, and it can be converted into adhesives at various composition ratios depending on the purpose. A quality resin material can be suitably prepared. The obtained modified resin material can be further dry-blended with a carbon material at a predetermined blending ratio, and then reacted by melt-kneading while heating using a melt extruder or the like. If the melt-kneading temperature is within the range of 100 to 280°C, both the melting of the modified resin and the reaction with the carbon material will proceed sufficiently, and the molding material of the produced carbon/resin composite will remain stable. This is preferred because thermal decomposition can be prevented. Similarly, the residence time in the extruder is preferably 0.1 to 30 minutes from the viewpoint of balancing reactivity and suppression of decomposition. Furthermore, in the production of carbon/resin composites (H) by melt kneading, resin materials such as thermoplastic resins and low molecular weight thermosetting resins, adhesives, carbon The materials can be blended at a predetermined mixing ratio and melt-kneaded using an extruder at a predetermined temperature. In this case, the kneading temperature is preferably within the range of 100 to 240°C, taking into consideration the reaction rate and dispersion effect of the resin material, adhesive, and carbon material.

Thermoplastic resins used for thermal processing and processing such as melt kneading include polyolefins such as polyethylene (PE) and polypropylene (PP), polyamides such as nylon 6 (PA6) and nylon 66 (PA66), and polyethylene terephthalate ( PET), polyesters such as polybutylene terephthalate (PBT), polyurethanes, acrylic resins, ABS (acrylonitrile butadiene styrene) resins, polystyrene (PS), polycarbonates, and carboxylic acid and maleic anhydride modified resins of these general-purpose resins. PP, modified PP, polyamide, polyester, polycarbonate, etc. are preferred from the viewpoint of fully utilizing the characteristics of carbon materials such as high strength, high flexibility, heat resistance, and conductivity. Preferably.These resins are not limited to one type, and a plurality of types can be used in combination.

Furthermore, from the viewpoint of operational convenience, it is preferable to use a highly concentrated masterbatch. In this case, a masterbatch of an adhesive and a resin material and/or a masterbatch of a carbon material and a resin material may be prepared and pelletized in advance, and then various resin materials and carbon materials may be further kneaded.

Examples of the melt-kneading machine used in the melt-kneading step include known melt-kneading machines, such as a Banbury mixer, plastomill, Brabender plastograph, single-screw extruder, and twin-screw extruder. From the viewpoint of dispersing the filler well and improving the heat resistance and rigidity of the thermoplastic resin composition, melt-kneading is preferably performed using a single-screw extruder or a twin-screw extruder, and a twin-screw extruder is particularly preferred.

A method for producing a carbon/resin composite (H) using a solution reaction method involves dissolving or dispersing a thermoplastic resin, a low molecular weight thermosetting resin, an adhesive, and other additives in a solvent in a predetermined ratio; This is a method of reacting the resulting mixed solution or dispersion while heating it to a predetermined temperature. Since the reaction temperature and reaction time mainly depend on the structure of the resin material, solubility in a solvent, etc., there are no particular limitations as long as the reaction can be carried out sufficiently.

In the production of the carbon/resin composite (H), known additives that are generally added to thermoplastic resins, such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, pigments, and antistatic agents, are added as necessary. A flame retardant, a neutralizing agent, a blowing agent, a plasticizer, an antifoaming agent, etc. can be added as appropriate.

The carbon material laminate (E), carbon/ceramics laminate (F), carbon/metal laminate (G), and carbon/resin composite (H) of the present invention are used to provide thermal conductivity and electrical conductivity. It can be suitably used in a variety of fields such as application, mechanical strength improvement, heat resistance, conductivity, secondary battery electrodes, antistatic properties, and durability improvement. When natural or synthetic diamond particles and/or CNT are used as the carbon material, and polyphenol is used as the resin material, high-performance resin bonded grindstones and saw wires can be easily manufactured. In addition, carbon/resin composites produced by melt extrusion are used as injection molding materials, extrusion molding materials, press molding materials, blow molding materials, film molding materials, etc. It can be suitably used as an automobile material or a home appliance material that requires impact resistance.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. In the following, parts and % indicate parts by mass and % by mass, respectively.

The materials used in Examples and Comparative Examples are as follows. In addition, products that do not specify the manufacturer, purification method, etc. are commercially available products.
(1) Vinyl monomer having a glycidyl group (A1)
GMA: Glycidyl methacrylate MGAM: N−methyl−N−glycidyl acrylamide (manufactured by KJ Chemicals Co., Ltd., the registered trademark is "Kohsylmer").
(2) Vinyl monomer having isocyanate group (A2)
MOI: 2-Isocyanate ethyl methacrylate (3) Vinyl monomer with oxazoline group (A3)
VOZO: 2-vinyl-2-oxazoline IPOZO: 2-isopropenyl-2-oxazoline (These monomers are manufactured by KJ Chemicals Co., Ltd. and the registered trademark is "Kohsylmer".)
(4) Vinyl monomer “ACMO” used for copolymerization: Acryloylmorpholine (a product of KJ Chemicals Co., Ltd. The registered trademarks are “ACMO” and “Kohsylmer”).
AM-90G: Methoxypolyethylene glycol 400 acrylate (EO 9mol) (manufactured by Shin Nakamura Chemical)
NVP: N-vinylpyrrolidone SA: stearyl acrylate (5) Carbon material CF: Carbon fiber (manufactured by Toray Industries, Inc., PAN-based CF, trade name "Torayka Yarn T700 12K", diameter 7 μm) Washed with acetone and dried . Amount of functional groups on the surface = 4×10 ⁻⁶ (mol/m ² )
CNT: Carbon nanotube (manufactured by Nanocyl, NC7000, diameter 11 nm, washed with chloroform and dried. Amount of functional groups on the surface = 7 × 10 ^-6 (mol/m ² )
BCNT: Bead mill treated CNT (bead mill treatment: 39.8 g of N-methylpyrrolidone, 0.8 g of CNT and 160 g of beads (zirconia Φ0.5 mm) were added to the vessel of a wet bead mill device (RMB-08 manufactured by Imex), and the mixture was heated at 1000 rpm. Bead milling was performed by stirring for 1.5 hours.Then, the solution was placed in a 1L beaker, including all the beads, and ion-exchanged water was added, shaken lightly, and the supernatant was taken out to remove the carbon suspended in the supernatant. The nanotubes and the zirconia beads settling at the bottom were separated. After repeating this operation many times to completely separate the carbon nanotubes and zirconia beads, the supernatant was filtered, vacuum dried at 80°C for 4 hours, and bead milled as a black powder. Carbon nanotubes (BCNT) were obtained.)
CSCNT: Cup stack carbon nanotube (manufactured by GSI Creos Co., Ltd., washed with chloroform and dried. Amount of functional groups on the surface = 1 × 10 ^-5 (mol/m ² ))
DM75: Diamond, average diameter 75 μm (TMD manufactured by Trustwell, untreated)
DM50: Diamond, average diameter 50 μm (IRV-3 manufactured by Tomei Diamond Co., Ltd., untreated, amount of functional groups on the surface = 9×10 ⁻⁶ (mol/m ² )).
DM10: Diamond, average diameter 10 μm (IRM-16 manufactured by Tomei Diamond, untreated)
BN: Ceramics (plate-like boron nitride, untreated)
SCBN: Ceramics (cubic boron nitride manufactured by Trustwell, untreated)
NMC: Active material (ternary positive electrode active material Li(NiMnCo)O2)
LCO: Active material (layered structure of lithium cobalt dioxide)
Al plate: Aluminum foil (thickness 20μm)
(6) General-purpose resin PP: Polypropylene resin (manufactured by Japan Polypropylene Co., Ltd., MA3)
PMP: Maleic anhydride modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Umex 1010)
PA: Polymethylpentene resin (manufactured by Mitsui Chemicals, Inc., TPX MX002)
PMA: Acid-modified polymethylpentene resin (manufactured by Mitsui Chemicals, Inc., TPX MM-101B)
PF: Polyphenol resin (powder)
(7) Other AIBN: Azobisbutyronitrile (Wako Pure Chemical, reagent)
NMP: N-methylpyrrolidone EtOH: Ethyl alcohol DMF: N,N-dimethylformamide "KJCMPA": 3-methoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals, registered trademark "KJCMPA")

Measurement methods and evaluation methods for various physical properties in Examples and Comparative Examples are as follows.
(1) SEM measurement:
The surfaces of various base materials and the surface of the laminate were observed using a SEM device (JEOL). Observation conditions: applied voltage 10 kV, emission current 10 μA, SEM observation after platinum deposition.
(2) How to calculate coverage rate SEM image is converted to black and white, and areas covered with carbon material are shown in white and areas not covered are shown in black.Coverage rate (%) = (number of white pixels) )/(number of pixels in the entire measurement area).

Synthesis of Polymer (B) Synthesis Example 1 (Synthesis of Polymer (B1))
VOZO 9.7 g (100 mmol), "ACMO" 113.0 g (850 mmol), AM-90G 22.7 g (50 mmol), Azo 1.6 g (10 mmol) of bisisobutyronitrile (AIBN) and 220 mL of ethyl acetate were charged, and the reaction solution was stirred at 30°C for 60 minutes under a stream of dry nitrogen, and then a polymerization reaction was carried out at 70°C for 12 hours. After the reaction was completed, the temperature was returned to room temperature, and the viscous reaction solution was poured into hexane (about 1 L) to obtain a white precipitate. Thereafter, the supernatant was discarded, and the precipitate was washed twice with hexane, followed by vacuum drying at 40° C. for 3 hours to obtain 132.5 g of a white powder product (yield: 91.1%).
The infrared absorption spectrum (IR) of the product revealed that it had an absorption characteristic of the oxazoline group derived from VOZO (1660 cm ^-1 ), an absorption characteristic of the amide group derived from "ACMO" (1640 cm ^-1 ), and an absorption characteristic of the amide group derived from AM-90G. Absorption (1730 cm ^-1 ) characteristic of ester groups was detected, and absorption (1620 cm ^-1 ) of vinyl groups derived from these monomers was not detected, confirming the production of polymer (B1). The Tg of the polymer (B1) was measured by DSC (DSC-60Plus manufactured by Shimadzu Corporation, temperature increase rate 10°C/min) and was 83°C. The weight average molecular weight (Mw) of the polymer was analyzed by GPC method (Prominence-I LC-2030C manufactured by Shimadzu Corporation, standard polystyrene) and was confirmed to be 18,000.

Synthesis Examples 2 to 6 (Polymers B2 to B6) and Synthesis Comparative Example 1-2 (Polymers P1 to P2)
As in Synthesis Example 1, a vinyl monomer having a glycidyl group (A1), a vinyl monomer having an isocyanate group (A2), a vinyl monomer having an oxazoline group (A3), other copolymerizable vinyl monomers, and AIBN in the predetermined amounts shown in Table 1, polymerizations were carried out in Synthesis Examples 2 to 6 and Synthesis Comparative Examples 1 to 2, and the obtained polymers were purified in the same manner as in Synthesis Example 1. The combined products (B2-B6 and P1-P2) were obtained as a white or pale yellow powdered product. Next, in the same manner as in Synthesis Example 1, polymers B2 to B6 and P1 to P2 were identified (IR), Tg measurement, and molecular weight measurement (GPC), and the results are shown in Table 1 along with the yields.

Preparation of carbon material (C) dispersion The carbon material and dispersant were mixed in the proportions shown in Table 2, and treated at 30°C for 30 minutes using a bath-type ultrasonic device (manufactured by ELMA, S30) to form a dispersion. 1 to 11 were obtained.

Manufacturing Example 1 of carbon material laminate (E)
A 10% ethanol solution was prepared using the adhesive (D1) containing 100% of the polymer (B2) of the present invention, and while heating it to maintain the temperature at 60°C, The fiber (C1) was passed through the adhesive (D1) solution bath at a speed of 1 mm/sec. Thereafter, the carbon fibers were passed through an ethanol bath at the same speed (washing) and dried with hot air at 80° C. for 3 minutes to obtain carbon fibers having an adhesive layer on the surface. Thereafter, the obtained carbon fiber having the adhesive layer was passed through a bath of dispersion liquid 1 (KJCMPA dispersion liquid of BCNT) heated to 100° C. at the same speed as described above. Thereafter, it was similarly washed with ethanol and dried with hot air at 160°C for 3 minutes to obtain a CF and CNT laminate (E1). A SEM photograph of the BCNT/CF laminate is shown in FIG. The coverage of the laminate E1 was 24.8%.

Production Example 2 and Comparative Example 2 of carbon material laminate (G)
A 10% ethanol solution was prepared using an adhesive (D2) containing 100% of the polymer (B3) of the present invention. 25 μL of the solution was dropped onto an Al plate, spin-coated at 1500 rpm for 4 minutes, and then heated on a hot plate at 120° C. for 10 minutes. The Al plate coated with the adhesive was placed in a beaker containing ethanol, stirred for 10 minutes at 200 rpm using a lab shaker to clean it, and then heated on a hot plate at 80° C. for 10 minutes to remove the ethanol (drying). After drying, 25 μL of dispersion 2 (aqueous CNT dispersion) was dropped onto the Al plate, spin-coated in the same manner, and heated on a hot plate at 120° C. for 10 minutes. Thereafter, washing with ethanol and drying on a hot plate were performed in the same manner to obtain a CNT and metal laminate (G1). Furthermore, the CNT coverage was measured in the laminate G1 before and after the final ethanol washing (Table 3).

A CNT and metal laminate was produced in the same manner as in Example 2, using the polymer (P1) (100%) obtained in Synthesis Comparative Example 1 instead of the adhesive (D2) in Example 2. However, the Al plate coated with the polymer (P1) was not washed with ethanol. CNT coverage was measured in the laminate before and after the final ethanol cleaning (Table 3).

Examples 3 to 12 and Comparative Examples 3 to 4
Carbon material laminate (E), carbon/ceramic laminate by the above-mentioned simultaneous heating method or post-heating method using carbon fiber, diamond, ceramics, metal, etc. as the base material and carbon nanotube, diamond, etc. as the adhesive and laminate material. A carbon/metal laminate (G) and a carbon/resin composite (H) were manufactured. Table 3 summarizes the raw materials, manufacturing conditions, product composition, coverage rate, etc. Further, SEM photographs of the base material and the laminate are shown in FIGS. 2 to 10.

From the results in FIGS. 1 to 10, a carbon laminate formed via an adhesive (D) containing the polymer (B) of the present invention, (E), a carbon/ceramic laminate (F), a carbon/metal It is clear that in the laminate (G) and carbon/resin composite (H), the surfaces of CF, DM, BN, SCBN, NMC, LCO, and Al are tightly coated with CNTs and CSSNTs. Various carbon laminates and carbon/resin composites of the present invention can be produced by various methods such as simultaneous heating and post-heating. In addition, the oxazoline group contained in the polymer (B) is highly reactive and the chemical bonds formed are strong, and it will adhere to carbon materials such as CNTs and CFs just by contacting them at room temperature, and furthermore, strong chemical bonds can be formed by heating. Even when the CNTs were formed and were washed, only the portions attached to the surface were removed, confirming that the CNTs were uniformly fixed to the surface of the CF by chemical bonding. Furthermore, an adhesive containing a polymer having a glass transition temperature of 80° C. or higher can form a thinner and more uniform adhesive layer, and can also provide a more uniform laminate with a higher coverage. On the other hand, polymers without functional groups such as oxazoline groups were unable to adhere to the surface of the carbon material, and a laminate could not be obtained. When the content of functional groups was less than 10%, a fully satisfactory adhesive and laminate could not be obtained. Furthermore, it was confirmed that these highly functional laminates and composites can be obtained only by the manufacturing method of the present invention. In particular, when using polymers with a high content of functional groups, homopolymers of vinyl monomers with oxazoline groups, etc., a thin, uniform, and strong adhesive layer is formed, maximizing the unique functions of carbon materials such as CNTs. The various laminates and composites obtained can be suitably used in various fields.

Example 13 and Comparative Examples 5-6
(1) Preparation of CNT-coated diamond 95 parts by weight of dispersion 9 prepared from diamond particles DM10 and dispersant NMP and 5 parts by weight of adhesive (D1) containing 100% polymer (B2) are placed in a reaction vessel. The mixture was charged and stirred at 100° C. for 3 hours, and then the diamond particles coated with the polymer were removed by filtration and washed by slowly pouring 1 L of ethanol over them. After washing, the coated diamond particles and 95 parts by mass of dispersion liquid 11 were charged into a reaction vessel and stirred at 100°C for 3 hours.Then, the diamond particles coated with BCNT were removed by filtration, and 1 L of ethanol was slowly poured over them. Washed. The coating operation with BCNT was performed five times, and after the final ethanol washing, drying was performed by heating at 80° C. for 1 hour to obtain a CNT-coated diamond. Note that the CNT coverage rate was 41.0%.

(2) Preparation of wire saw A piano wire (Japan Fine Steel) with a diameter of 0.1 mm and a length of 50 cm was immersed in an acidic solution at 50° C. for 3 minutes for etching treatment. The treated piano wire was dipped in a slurry of diamond particles and phenolic resin, and the slurry of diamond particles and phenol resin was applied to the piano wire by pulling it up through a hole with a diameter of 0.15 mm. After applying the coating, hot air was applied to the piano wire using a heat gun for 2 minutes, and then heated in an oven at 200° C. for 8 hours to produce a diamond resin bond wire saw. As the diamond particles, Example 13 used CNT-coated diamond, and Comparative Examples 5 and 6 used untreated diamond DM10 and Ni-coated diamond, respectively. The surface conditions of these diamonds are shown in FIGS. 11-13.

(3) Cutting test of silicon ingot A wire saw was stretched on a pedestal with a width of 30 cm, both ends were fixed so that the tension was 10 N, and the silicon ingot or silicon wafer was fixed so as to be in the center of the wire saw. The pedestal was reciprocated at a stroke width of 150 mm and a speed of 200 mm/sec, and the silicon ingot was pushed into a wire saw at a speed of 15 μm/sec to perform cutting for 15 minutes. After cutting, the depth of cut of the silicon ingot and the surface roughness of the cut surface of the silicon wafer were evaluated by the following methods, and the results are shown in Table 4.

Depth of cut After the cutting test, the cut made in the silicon ingot was photographed using an optical microscope, and the depth of cut (mm) was measured by image analysis. Note that the value of the cutting depth is the average value of three tests.

Surface roughness (Ra)
After the cutting test, the cut surface of the silicon wafer was photographed using a white interferometer, and the surface roughness (Ra) (μm) was measured by image analysis. Note that the value of surface roughness (Ra) is the average value of three tests.

As is clear from the results in Table 4, when using the CNT-coated diamond resin bond wire saw, the silicon ingot was cut deeply and the surface roughness of the silicon wafer was low.

Surface photograph of CNT/CF laminate (Example 1) Surface photograph of CNT/DM75 laminate (Example 3) Surface photograph of CNT/DM50 laminate (Example 5) Surface photograph of CNT/DM10 laminate (Example 6) Surface photograph of CNT/BN laminate (Example 7) Surface photograph of CSCNT/DM50 laminate (Example 8) Surface photograph of CNT/SCBN laminate (Example 9) Surface photograph of CNT/NMC laminate (Example 10) Surface photograph of CNT/LCO laminate (Example 11) CF surface photograph (Comparative Example 1) Surface condition of CNT-coated diamond (Example 13) Surface condition of untreated diamond (Example 13) Surface condition of Ni-coated diamond (Example 13)

The adhesive for carbon materials of the present invention, the carbon laminate, carbon/ceramic laminate, carbon/metal laminate, and carbon/resin composite obtained using the adhesive are manufactured using special dispersion and surface treatment techniques and equipment. The carbon material can be easily manufactured by the manufacturing method of the present invention without requiring any process or deterioration of the original characteristics of the carbon material. The various carbon laminates and carbon/resin composites obtained by the present invention can impart electrical conductivity, thermal conductivity, and mechanical properties to general-purpose resins, and have excellent properties such as heat resistance, impact resistance, and electrical conductivity. It can be suitably used in various industrial fields as a material having characteristics. In addition, various engineering plastics are used for molding, especially interior and exterior parts related to automobiles and transportation equipment such as bumpers, instrument panels, console boxes, roof sheets, panel covering materials, and electrical components, daily necessities products such as home appliances, furniture, and miscellaneous goods, and medical materials. Suitable for packaging materials such as products, food containers, food packaging, general packaging, coating materials for electric wires and cables, industrial materials such as architecture and civil engineering, stationery and office supplies, and compatibilizers or adhesives for various polymer alloys. It is.

Claims (13)

A carbon material (C) and diamond, diamond-like carbon, ceramics, A laminate formed by laminating one or more materials selected from the group consisting of active materials ,
The carbon material (C) is selected from the group consisting of carbon nanotubes, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, cup-stacked carbon nanotubes, carbon nanofibers, graphene, fullerene, nanodiamonds, and nanodiamond-like carbon. A laminate comprising at least one nano-sized carbon material . The carbon material (C) is carbon nanofiber (CNF) and/or carbon nanotube (CNT), and is made of one or more materials selected from the group consisting of diamond, diamond-like carbon, ceramics, and active materials. The laminate according to claim 1, wherein the coverage of CNF and/or CNT bonded to the surface is 10% or more. 3. A resin-bonded grindstone characterized in that the laminate according to claim 2 is a laminate of carbon nanofibers (CNF) and/or carbon nanotubes (CNT) and diamond, and contains the laminate. The laminate according to claim 2 is a laminate of carbon nanofibers (CNF) and/or carbon nanotubes (CNT) and diamond, and a saw wire containing the laminate. A polymer (B) containing as a constituent unit a vinyl monomer (A) having a functional group that reacts with active hydrogen on the surface of one or more materials selected from the group consisting of diamond, diamond-like carbon, ceramics, and active materials. The carbon material (C) is brought into contact with the contained adhesive (D) to form an adhesive layer by chemical bonding between the material and the adhesive, and then the carbon material (C) is brought into contact with the adhesive layer and bonded by chemical bonding. A method for manufacturing a laminate comprising:
The carbon material (C) is selected from the group consisting of carbon nanotubes, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, cup-stacked carbon nanotubes, carbon nanofibers, graphene, fullerene, nanodiamonds, and nanodiamond-like carbon. A method for producing a laminate made of at least one nano-sized carbon material . The laminate according to claim 1, wherein the functional group that reacts with active hydrogen is one or more functional groups selected from an oxazoline group, a glycidyl group, an isocyanate group, and a carbodiimide group. The laminate according to claim 1, wherein the constituent units derived from the vinyl monomer (A) constituting the polymer (B) are 10 mol% or more. The laminate according to claim 1, wherein the polymer (B) has a glass transition temperature (Tg) of 80°C or higher. The laminate according to claim 1, wherein the structural unit derived from the vinyl monomer (A) having an oxazoline group constituting the polymer (B) exceeds 90 mol%. 6. The method for producing a laminate according to claim 5, wherein the functional group that reacts with active hydrogen is one or more functional groups selected from an oxazoline group, a glycidyl group, an isocyanate group, and a carbodiimide group. 6. The method for producing a laminate according to claim 5, wherein the constituent units derived from the vinyl monomer (A) constituting the polymer (B) are 10 mol% or more. The method for producing a laminate according to claim 5, wherein the polymer (B) has a glass transition temperature (Tg) of 80°C or higher. 6. The method for producing a laminate according to claim 5, wherein the structural unit derived from the vinyl monomer (A) having an oxazoline group constituting the polymer (B) exceeds 90 mol%.