JP3981737B2 - Manufacturing method of resin-inorganic composite structure and resin-inorganic composite film structure - Google Patents

Description

      The present invention relates to a method for producing a resin-inorganic composite structure and a resin-inorganic composite film structure utilizing the impact solidification phenomenon of powder.

  Conventionally known are composite materials of a resin and an inorganic substance for the purpose of improving mechanical properties such as a glass fiber reinforced plastic. For example, Patent Document 1 proposes a structure in which a ceramic porous body having continuous pores is immersed in a molten resin and the continuous pores are impregnated with the resin.

  On the other hand, as a method for producing a composite structure at a temperature close to room temperature, Patent Document 2 and Patent Document 3 propose an aero deposition method (gas deposition method). In this method, an aerosol containing fine particles is collided with a substrate at high speed, the fine particles are crushed and deformed by the impact of the collision, and the new surfaces generated by the crushing and deformation are joined together to form a structure on the substrate. It is.

  Further, Patent Document 4 is cited as a prior art in which the above-described aero deposition method is applied to the production of a composite structure of resin and ceramics. In Patent Document 4, resin particles are coated on the surface of ceramic fine particles to form composite fine particles, and the composite fine particles are collided with the substrate surface at a high speed to deform or crush the composite fine particles. It is disclosed that composite fine particles are recombined through a new surface.

JP 2000-109375 A JP 2000-212766 A JP 2003-183848 A WO02 / 34965 publication

  In the method disclosed in Patent Document 1, since the molten resin is impregnated in the ceramic porous body, the resin must be heated to the melting temperature, and the apparatus becomes large and the working environment tends to deteriorate. Furthermore, in this method, since the resin and ceramics are not mixed at a fine level, even if the composite as a whole exhibits unique characteristics, the characteristics are uniformly expressed in any part of the composite. However, it cannot be used for parts that require uniform characteristics.

  On the other hand, the methods disclosed in Patent Documents 2 to 4 are based on the premise that the inorganic particles are deformed or crushed by mechanical impact, and defects are introduced into the surface of the fine particles in the process of deformation or crushed. There is a disadvantage of losing the characteristics of the raw material powder that it had before deformation or crushing, leading to functional degradation.

In order to solve the above-mentioned problems, the method for producing a resin-inorganic composite structure according to the present invention is such that a composite powder composed of a resin material and an inorganic material is allowed to collide with the surface of a substrate, whereby the resin material in the composite powder is instantaneously produced. The resin-inorganic composite structure was formed by utilizing such deformation or fusion, so that the inorganic particles were not deformed or crushed during the collision process .

Examples of the inorganic material include alumina, zirconia, barium titanate, lead zirconate titanate, titanium oxide, zinc oxide, yttria aluminum garnet, YBCO, and other metal oxide ceramics, aluminum nitride, silicon nitride, carbon nitride, etc. One or two or more of non-oxide ceramics, Al, Mg, Fe metals and intermetallic compounds, Si, Ge, CeO, and GaAs semiconductors can be used.

  As the resin material, one or more of acrylic, fluorine, and styrene can be used.

  The composite powder is preferably coated composite particles in which inorganic particles are coated with a resin. The coated composite particles can be obtained by a mechanical composite treatment.

  The composite powder used preferably has a bimodal particle size distribution. Specifically, based on the particle diameter of the larger peak, the particle diameter of the smaller peak is less than 0.5 in terms of the ratio, and the peak intensity ratio is set to wt% (the larger particle diameter Powder): (Powder having a small particle diameter) = 7: 3 to 9: 1 is used.

Since the resin-inorganic composite structure of the present invention obtained by the above method is not accompanied by deformation or crushing of the inorganic particles, the particle size distribution and crystal structure of the inorganic particles in the structure are substantially the same as the raw inorganic particles. Have

  As the functional film, the thickness is preferably 1 to 500 μm, the pore content is preferably less than 10%, the size of the inorganic particles is preferably 80 nm to 5 μm, and the thickness of the resin between the inorganic particles is preferably less than 5 μm. .

  According to the present invention, when producing a resin-inorganic composite structure using the collision solidification phenomenon of powder on a base material, since the inorganic particles are not deformed or crushed, the characteristics of the raw material powder can be maintained and A functional structure having a very small residual stress can be obtained.

Example 1
High-purity alumina powder (average particle size 1.89 μm, AA-2 manufactured by Sumitomo Chemical) and non-crosslinked acrylic powder (average particle size 0.08 μm, FS101 manufactured by Nippon Paint) were used as raw materials. Thus, a resin-coated resin-inorganic composite powder was produced. Here, the blending ratio of the resin was 4 mass% with respect to the alumina weight. Incidentally, the blending amount of the resin is an amount necessary to cover 100% of the alumina particle surface with the resin, assuming that the alumina powder and the resin powder are spheres having the average particle diameter.

  For the particle composite, a mechano-fusion system (manufactured by Hosokawa Micron Corporation, AM-20F) capable of applying a strong frictional force and compressive force to the powder layer was used. The weighed alumina powder and resin powder were placed in the container of the above apparatus and treated for 10 minutes at room temperature in the atmosphere.

  FIG. 1 is an electron micrograph of the alumina powder before treatment, and FIG. 2 is an electron micrograph of the powder after treatment. When FIG. 1 and FIG. 2 are compared, the alumina powder is not refined by this treatment. It turns out that the composite powder by which the surface was covered with resin is obtained.

  For the production of the resin inorganic particles as the raw material of the present invention, the compounding by the mechanical method described above was effective. In general, many agglomerated particles are observed in the fine powder. In particular, the resin powder used in this example was a powder containing a large number of agglomerated particles of several μm or more. As shown in FIG. 2, the aggregated resin is crushed without crushing the alumina powder, which is inorganic particles, and the resin particles and the alumina particles are further bonded.

  Moreover, when the coated composite particles after the treatment shown in FIG. 2 and the alumina particles before the treatment are compared in terms of the angle of repose, the angle of repose of the coated composite particles is reduced by about 10 ° and the fluidity is increased.

Using the coated composite particles obtained as described above, an attempt was made to produce a resin-inorganic composite structure using a collision solidification phenomenon.
First, the coated composite particles were aerosolized in He gas and conveyed into a vacuum chamber directly connected to a rotary pump. At this time, the flow rate of He gas was 10 liters / minute, and the pressure in the vacuum chamber was several hundred Pa when the gas was introduced. On the other hand, a glass substrate (non-alkali glass Corning 1737) is set at a location 5 mm away from the nozzle attached to the end of the aerosol carrying tube in the vacuum chamber, and the aerosol is sprayed onto the glass substrate for 30 seconds. I collided.

  An electron micrograph of the obtained structure (resin inorganic composite thick film) is shown in FIG. As can be seen from FIG. 3, it can be seen that the resin-inorganic composite thick film is formed by bonding inorganic particles through the resin. The average particle size of the inorganic particles calculated from the two-dimensional image data photographed with an electron microscope was 1.85 μm. Within the scope of this example, since there is no significant difference between the average particle diameter of the starting alumina raw material and the average particle diameter of the alumina particles in the resin-inorganic composite thick film, the deformation of the inorganic particles in the collision process, It can be said that crushing did not occur.

  In addition, when the composite powder aerosol collided with the glass substrate, the generation of plasma light was not observed, and the XRD of the starting alumina raw material and the resin-inorganic composite thick film both showed the same diffraction pattern of alumina. From these results, it can be said that the inorganic particles were not deformed or crushed by the collision.

  The flow rate of He was preferably 10 liters / minute or more. Since a high gas flow rate of a certain level was necessary for film formation, the composite field including the compression process due to the collision of the powder layer (aerosol) as well as the collision of individual particles deformed (fused) the resin layer. It is considered an essential element.

  The aerosol temperature was preferably room temperature to less than the glass transition temperature (Tg). The glass transition temperature (Tg) of the non-crosslinked acrylic resin is about 65 ° C. However, when the aerosol temperature was raised to a temperature higher than this, no immobilization by the resin occurred. Therefore, the method of the present invention can be said to be a film forming method utilizing instantaneous resin deformation or fusion at a contact point due to collision of a low temperature aerosol.

Further, the dark part in FIG. 3 was a part filled with pores or resin. In this example, the alumina powder did not have a particle size distribution such that small particles were packed between the particles.
As a small particle, an alumina powder (AKP-50, manufactured by Sumitomo Chemical Co., Ltd.) having an average particle diameter of 0.3 μm has a bimodal particle size distribution of about 3: 7 (small particles are small) in a mixing ratio with the alumina particles. When used, a nearly dense film was obtained. In addition, the composite particles having a particle size distribution of 7: 3 to 9: 1 were used in the range of the present example, in terms of% by weight (powder with a large particle size) :( powder with a small particle size) = 7: 3 to 9: 1. In some cases, a dense film was obtained within the scope of electron microscope observation.

  In addition, the film formation rate in this example was about 30 μm / second. As described above, one of the factors for obtaining such a high film formation rate is to increase the fluidity of the powder by compositing as described above. If the flow resistance of the powder is high, the clogging frequency in the transfer pipe or nozzle may increase, and it can be said that high powder flow is a necessary powder design item for scaling up to mass production process. .

(Example 2)
When a thick resin-inorganic composite film was produced under the same conditions using a crosslinked acrylic resin and a polystyrene resin instead of the non-crosslinked acrylic resin of Example 1, the same results were obtained.

  The method for producing a resin-inorganic composite structure according to the present invention and the resin-inorganic composite structure obtained by the production method include biochip materials such as DNA chips, protein chips, and cell chips, artificial bones, artificial tooth roots, and medical catheters. Biomaterials such as, wear-resistant surface coating of sliding members, antifouling surface coating, water-repellent coating, hydrophilic coating, anti-oxidation film, anti-rust material, anti-corrosion material, antibacterial anti-fouling material, low dielectric material, selective absorption filter, Fluorescent solar concentrator fluorescent films, dye lasers, microsphere lasers, nonlinear optical materials such as ultrafast optical switches, photonics device elements, photochromic materials, dye-sensitized solar cells, heat-resistant protective coatings for building materials, circuits It can be used for dielectric films for substrates, functionally gradient materials, porous materials, and the like.

Electron micrograph of alumina powder before compounding Electron micrograph of powder after compounding It is an electron micrograph of a structure (thick film), (b) has expanded (a) 2 times.

Claims (6)

A method of manufacturing a composite structure of a resin material and an inorganic material by colliding a composite powder composed of a resin material and an inorganic material with the surface of the substrate , wherein the composite powder has a bimodal particle size distribution. Yes, on the basis of the particle diameter of the larger peak, the particle diameter of the smaller peak is less than 0.5 in terms of the ratio, and the peak intensity ratio is in weight% (powder with larger particle diameter) : (Powder with a small particle diameter) = 7: 3 to 9: 1, and the formation of the composite structure is a collision process by utilizing instantaneous deformation or fusion of the resin material in the composite powder. A method for producing a resin-inorganic composite structure characterized in that the inorganic particles are not deformed or crushed .   The method for producing a resin-inorganic composite structure according to claim 1, wherein coated composite particles obtained by coating inorganic particles with a resin are used as the composite powder. A composite structure of a resin material and an inorganic material formed by colliding a composite powder composed of a resin material and an inorganic material against the surface of the substrate, wherein the composite powder has a bimodal particle size distribution, Based on the particle diameter of the larger peak, the particle diameter of the smaller peak is less than 0.5 in terms of the ratio, and the peak intensity ratio is wt%, (powder with larger particle diameter): ( Small particle size powder) = 7: 3 to 9: 1, and the inorganic particles constituting the composite structure are not deformed or crushed upon collision, and the particle size distribution of the inorganic particles in the resin-inorganic composite film A resin-inorganic composite structure characterized in that the crystal structure is the same as that of the raw material inorganic particles. 4. The resin-inorganic composite structure according to claim 3 , wherein the resin-inorganic composite film has a thickness of 1 to 500 μm and a pore content of less than 10%. The resin-inorganic composite structure according to claim 3 , wherein the inorganic particles have a size of 80 nm to 5 μm. 4. The resin-inorganic composite structure according to claim 3 , wherein the resin thickness between the inorganic particles is less than 5 [mu] m.