The adhesive polymer composition with magnetic properties


(57) Abstract:

The present invention relates to technologies for various adhesive compositions (adhesives, compounds, sealants), with magnetic properties, and may find application in various industries, including the installation of a variety of magnetic systems, electromagnetic actuators and creating coatings that can absorb electromagnetic radiation. The composition comprises a binder is a thermosetting or thermoplastic adhesive based on epoxy resin, phenol resin, perforirovannoi resin, silicone resin, nitrile rubber, acrylic resin; particles of magnetic material (the size of 1-1000 nm), stable surface-active agent; carbon black with a particle size of 0.2-0.3 μm. If necessary, the composition may contain a pigment, a plasticizer. The composition has a storage stability, good adhesion to various surfaces (metal, glass, ceramics, concrete, plastic), high magnetic characteristics. Obtained on the basis of magnetic material can provide the absorption coefficient electroma the technology of obtaining various adhesive compositions (glues, sealants, compounds, compositions for coating), which are magnetic and can be widely used in electronic and electronic industry, engineering, aviation, construction, manufacturing and repair of home appliances.

In particular, the adhesive composition with magnetic properties can be used in the repair and installation of power devices, electrical machines, control devices, for example, for bonding the cores of the coils, chokes, transformers, solenoids and acoustic systems, in the manufacture of cores, as well as materials (adhesives, compounds, coatings) that absorb electromagnetic radiation, etc.

Known ferromagnetic adhesive containing epoxy Dianova resin, the curing agent (triethanolamine), dibutyl phthalate and carbonyl iron [Khrulev C. M. Synthetic adhesives and mastics. - M.: Higher school, 1970, S. 350]. However, due to the fact that particles included in the composition of the filler (carbonyl iron) are quite large (about 3-4 microns), this adhesive is insufficient magnetic permeability and does not meet the high standards of materials such appointment. Known ferroline iron or ferrite grinding from 30 to 80 microns (60-70 wt.%) [EN 2090585, 20.09.97] . However, this ferromagnetic paint is only intended to cover the student boards. Known adhesive compound special purpose applied, in particular, thermal and electronic engineering in the manufacture of film chips containing epoxy resin Dianova (20-60 wt.%), rosin (13-45 wt.%) and the rest is powder-like conductive filler (copper, tungsten, aluminum, beryllium oxide, aluminum oxide) with a particle size of 0.2 to 35 μm [SU 763427, 09 J 9/00, 15.09.1980]. However, this adhesive compound though and has good thermal conductivity and electrical conductivity, does not possess all the necessary complex magnetic properties that determine the possibility of its use as magnetic materials of wide application. There is a method of bonding ferromagnetic plates (in the manufacture of cores) using different adhesives (phenolic-polyvinyl acetate, epoxy), wherein the coating of adhesive on the bonding surfaces carry out subsequent processing in a constant magnetic field 1100-1350 e [SU 594157, 09 J 5/08, 25.02.1978]. However, this method is technologically complex and has a limited purpose. Known adhesive that absorbs microwave radiation, containing the scattering particles from example thermosetting or thermoplastic adhesive (polyamide, ethylene-vinyl acetate). As scattering particles, the adhesive contains a material selected from the group comprising chromium, aluminum, copper, titanium, nitride of titanium, iron, Nickel, carbon, magnetic metal fibers [EP 0424132. 09 J 9/00, 24.04.1991]. The adhesive absorbs radiation 0,252 kcal at a frequency of ~2-20 GHz.

The closest to the technical nature of the claimed invention is an adhesive composition containing an adhesive binder (polyamide, polyacrylates, polymethacrylates, polyurethanes, polyesters, polyethylene, copolymer of ethylene and vinyl acetate) and magnetic nanoparticles with a size of 1-1000 nm. The adhesive composition may be in the form of organic or aqueous dispersion, and may additionally contain various additives target, such as stabilizers and antioxidants, pigments, emulsifiers. The nanoparticles may be composed of paramagnetic and ferromagnetic materials: Fe, Co, Ni, Cr, Mo, W, V, Nb, TA, CE, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; ferrite type Fe3ABOUT3(Me= Mn, Co, Ni, Cu, Zn, Mg or Cd), and be contained in the adhesive composition in an amount of 0.1-40 wt. % [WO 00/34404, 09 J 9/00, 15.06.2000]. The application does not contain any specific information (for example, in the form of examples) of the receipt of this song and its the spectrum of the purpose and operation. This patent is virtually theoretical development related to adhesive compositions (adhesive) containing magnetic nanoparticles.

The technical objective of the claimed invention to provide an adhesive composition with increased viability and stability, high magnetic permeability and saturation magnetic flux density, with the ability to absorb high frequency electromagnetic radiation.

The goal of the project is achieved in that the adhesive polymer composition with magnetic properties as the polymer binder includes a thermoplastic or thermosetting adhesive comprising a base selected from the group consisting of epoxy resin, phenol-formaldehyde resin, silicone resin, perchlorovinyl resin, nitrile rubber, acrylic resin; particles of magnetic material with a size of 1-1000 nm, stabilized by surface-active substance and carbon black with a particle size of 0.2-0.3 μm in the following ratio, wt. including:

the above - termoaktivirovannye or thermoplastic adhesive 100;

the above - stabilized nanoparticles mages who hypoxia targeted supplements, such as pigments and plasticizers (dibutyl phthalate or dioctylphthalate).

As the particles of the magnetic material composition contains particles with a size of 1-1000 nm, consisting, for example, Fe, Co, Ni, Cr, rare-earth and other metals, various ferrites, such as ferrites F3O4(M=MP, Fe, Ni, Cu), Ni-Zn and Mn-Zn ferrites, hexaferrites barium and strontium, other ferrites, alloys, Fe-Ni, Fe-Co, Fe-Pt alloys based on rare-earth metals Nd-Fe-B and Sm-Co; Fe-B-Co-R (R - rare earth element), etc.

These particles can be obtained by various known methods: sputtering and evaporation of metals and their alloys in vacuum, the grinding of larger particles of metals or their alloys by using appropriate devices (colloid mill, ultrasonic generators, and so on), chemical methods: recovery in the solution of metal ions to atoms under conditions favorable to the subsequent formation of small metal clusters or aggregates (chemical reducing agents such as hydrazine, borohydride, hydrogen; radiation and electrochemical reducing agents); the synthesis of micelles in solutions of copolymers; thermal decomposition of metal-containing compounds (CARBONYLS, formate, acetate and so on) in melts the form as low-molecular substances, for example, fatty acids such as oleic acid, stearic acid, in the form of 0.1-0.5% solution in hydrocarbon solvent, and macromolecular compounds such as proteins, carboxymethylcellulose, polyvinylpyrrolidone, block copolymers, for example, consisting of blocks of polyethylene oxide, poly(4-vinylpyridine) - derivatives), polystyrene, polyethylenimine, in any combination, both in solution and in the dry state. These methods of obtaining particles are known and described in the literature [Taparko A. C. and others - Journal of physical chemistry, 1996, so 70, 10, 1894; Pileni Meters and other Nano-sized particles in colloidal systems. - Langmuir, 1997, T. 13, 3266; Butenko L. C., and others die Zeit. Phys. D. Atoms, molecules and clusters, 1990, I. 17, S. 283; Pomogailo A. D., Rosenberg, A. S., upland I. E. the Nanoparticles of polymers to metals. - M. : Chemistry, 2000, s.; Nanomaterials: Synthesis, Properties and Applications (Eds.: A. S. Edelstein and R. C. Cammarata). - Institute of Physics Publishing, Bristol and Philadelphia, 1998)]. For example, nanoparticles of metallic iron produced by reduction of compound of iron with hydrogen (250-400oC) followed by stabilization of 0.1-0.5% solution of oleic or stearic acid in a hydrocarbon solvent (e.g. hexane, xylene, benzene, acetone, methanol), filtering, washing and the second composition contains epoxy adhesives (liquid and powder), mostly hot curing epoxy resins cured with dicyandiamide or phthalic, maleic anhydrides, dissolved in ethyl cellosolve with the possible addition of plasticizers, glues D-15, D-23. VK-32-GM and others) [Khrulev C. M. Synthetic adhesives and mastics. - M, High school, 1970, S. 58] ; one-component hot curing compounds (up-A, UE 503 B, UE-s - WUT 5-250-68); compounds of cold hardening up-U (TU 6-05-241-72) based on epoxy modificatory resin and imidazolinone hardeners AND IS 6M AND 5M, and various varnishes epoxy.

As adhesives on the basis of phenol-formaldehyde resins (rezol and Novolac), the compositions contain, for example, adhesives BF-2, BF-4, on the basis of phenol-formaldehyde resin-modified butyral; phenol-rubber adhesives (VC-3 and VC-4, VC-32-200), which contain phenol-formaldehyde resins and solutions of synthetic Kuchuk (nitrile rubber); phenol-formaldehyde adhesives, modified organosilicon compounds such as alkoxysilane (adhesives BC-10C, SU-350) [Khrulev C. M. Synthetic adhesives and mastics. - M.: Higher school, 1970, S. 65-70] ; silicone adhesives, such as CGT-2 and CGT-3, VC-2 and P-9, based on Cree mixed with epoxy resin [Khrulev Century M Synthetic adhesives and mastics. - M.: Higher school, 1970, S. 87-89]; perchlorovinyl adhesives [Khrulev C. M. Synthetic adhesives and mastics. - M.: Higher school, 1970, S. 97-98].

As the pigment composition may contain titanium dioxide, zinc oxide, etc.

The composition is prepared by the sequential mixing of the starting components, for example, in cleanersalso, mixers and so on, until a homogeneous composition. In the experimentally selected qualitative and quantitative composition of the adhesive composition of the particles is deposited on the surface of particles of carbon black, which acquires magnetic properties, which generally contributes to the stability of the composition and to improve the magnetic properties of the final material increases the magnetic permeability and the ability to absorb electromagnetic radiation) with a small thickness of the layer of the composition of the order of 1-5 microns. The adhesive composition is applied on various substrates (surface): metal, glass, ceramics, plastics, concrete, by known methods (spray, spray, brush, etc), preferably in a pre-heated surface.

The following examples illustrate, but are not limited to being predelegation in ethyl cellosolve, introducing particles of Ni-Zn ferrite stabilized in a 0.3% solution of oleic acid, having an average size of 10 nm, in the amount of 100 wt. 'clock and 10 wt. including carbon black with a particle size of 0.2-0.3 μm. Mix in clearesult until a homogeneous composition (2-5 hours). Get a stable composition with the viability of 120 hours. This composition glued the split cores of the coils and chokes, putting on pre-heated to 120-130oFrom the surface of the adhesive layer with a thickness of 2-3 microns. The relative magnetic permeability of the composition 250.

Example 2. Mix 100 wt. including glue SU-10T (a solution of acetal resin, phenol-formaldehyde resin and alkoxysilane in a mixture of organic solvents; the dry matter content of 15-30%, a viscosity of 120 seconds VZ-1), 200 wt. including particles of iron the size of 200 nm (stabilized with 0.5% solution of stearic acid) and 20 wt. including carbon black with a particle size of 0.2-0.3 μm. The composition is stable, the viability of 6 months. Glue litvanya yokes recruited from round plates, the material of the plate - electrical alloy permalloy grade 45 N, the cores of the electromagnets. Bond strength (tensile strength at separation) 190-195 kg/cm2relative nachalnik R-300K (MRTU 6-05-1290-70), representing a solution of the resin in ethyl alcohol, taken in the amount of 100 wt. 'clock, introducing particles of magnetic material Sm-Co is 200 nm, stabilized by oleic acid (0,2% solution in decane) 200 wt. 'clock and 10 wt. including carbon black. The mixture is stirred until a homogeneous composition. The composition is stable, the viability of 2-3 months. Glue can be used for bonding porcelain, glass, metals, plastics. Magnetic induction saturation of 0.8 T.

Example 4. In glue BF-2 (based on phenol-formaldehyde resin-modified butyral), taken in the amount of 100 wt. 'clock, introducing particles of magnetic material with a size of 30 nm on the basis of mixtures of oxides of Ni, Zn, Co and Fe (stabilized with 0.3% solution of oleic acid in the amount of 300 wt. including carbon black in an amount of 10 wt. am Stirred to obtain a homogeneous composition. Put on different surfaces (glass, porcelain, wood, metal, plastics) with a thin layer; the bonding is carried out at 100-150oC for 1.5-2 hours or at room temperature with exposure (bonded) 3-4 days. Bond strength (shear strength steel plates) 200-350 kg/cm2.

Note the -3 (a mixture of the modified silicone resin - polymethylphenyl siloxane - copolymer of butyl methacrylate and methacrylic acid in an organic solvent) as the magnetic particles used stabilized with 0.5% solution in hexane oleic acid nanoparticles hexaferrite barium or Nd-Fe-B with a size of 20 nm and carbon black. Viability composition of 6 months or more. The composition may be used for bonding metals, plastics, fibers and other insulating materials. Cured 3 days at room temperature. Magnetic induction saturation of 0.8 T.

Example 6. Do the same as in examples 1-5, only as an adhesive used perchlorovinyl adhesives (solution perchlorovinyl resin in solvent (acetone, dichloroethane, toluene, ethyl acetate and others), add a plasticizer (dibutyl phthalate) in the amount of 20-30% by weight of the dry resin (for example, glue PV-6); as nanoparticles of magnetic material used, the particles of magnetic material Fe-B-Co-R (R - rare earth metal), stabilized with 0.2% solution of oleic acid in hexane, with a particle size of 300 nm, as well as carbon black. Viability composition 1-2 months. This glue can glue svetopetric will otuput as well as in examples 1 - 6, only as adhesive use rubber adhesives (based on nitrile rubber - glue VDU-3, adhesive Geng-150/ - on the basis of the mixture on BNR rubber SKN-40 and resin VDU), as magnetic particles - particles from a mixture of oxides of Ni, Co, Fe (stabilized with 0.1% solution of oleic acid in decane) with a size of 100 nm. The viability of the composition is not limited. Glue can be used for mounting of various coating materials and thermoacoustic insulation, for fixing ceramic tiles, for bonding rubber to metals, glass, concrete, bonding polystyrene, laminated plastics.

Example 8. Do the same as in examples 1-6, only as magnetic particles using particle Fe-Co ferrite sizes of 10 nm, stable block copolymers of polystyrene and poly(4-vinylpyridine) - derivatives), and the adhesive is any one of the aforementioned adhesive bases. The highest viability butadiene rubber bases (over 6 months), and the lowest in phenol-formaldehyde and perchlorovinyl (about 1 month). The adhesive has an initial relative magnetic permeability of 250 and can be used for special applications, castnets.) based dimethacrylate ethers of polyalkylene glycols with monofunctional acrylates (acrylic acid, methacrylamide) in combination with acrylic thickener, the initiator is benzoyl peroxide, an activator of chloride of copper, the inhibitor is a phenol, introducing particles of Mn-Zn ferrite stabilized polyvinyl alcohol in the amount of 200 wt. 'clock and carbon in an amount of 10 wt. hours the Mixture is mixed, the resulting composition is stable when stored at ambient temperatures for at least one year. The composition cures when spontaneous polymerization without access of air. The composition has good adhesion to metal surfaces and has a working temperature range from -200 to +300oC. the Initial relative permeability of the composition 500.

Obtained on the basis of the proposed adhesive compositions magnetic materials (adhesives, resins, sealants) have a high initial relative magnetic permeability (850) and saturation magnetic flux density (up to 1 T) and can provide the absorption coefficient of the electromagnetic field of at least 30 dB in the frequency range from 100 kHz to 2 GHz for a layer thickness of 6 mm

1. The adhesive polymer composition with magnetic properties, comprising a polymeric binder, the particles of the magnetic material and, if necessary, targeted supplements, characterized in that the polymer from the group consisting of epoxy resin, phenol-formaldehyde resin, silicone resin, perchlorovinyl resin, on BNR rubber, acrylic resin, particles of a magnetic material composition contains particles of a magnetic material of a size of 1-1000 nm, stabilized by surface-active substance, and optionally carbon black with a particle size of 0.2-0.3 μm in the following ratio, wt.h.:

The above thermosetting

or thermoplastic adhesive 100

The above stable

particles of magnetic material 10-1000

Carbon black with size

particles of 0.2-0.3 μm 1-200

2. The adhesive polymer composition under item 1, characterized in that it contains as a possible target additives pigment and/or the plasticizer dibutyl phthalate or dioctylphthalate.


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