JP3894851B2 - Method for producing functional silicone resin composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a method for producing a silicone resin composition that exhibits excellent functionality (deodorant and antimicrobial properties) and has been devised so that the functionality lasts for a long period of time.
[0002]
[Prior art]
  Silicone resin is the safest resin for the human body. Among silicone resins, silicone rubber is used for packing, gaskets, O-rings, plug boots, lunch box and rice cooker packing, underwater glasses and goggles, nipples, industrial, consumer and medical applications. It is used. In addition to molded products, silicone resins are also used as adhesives or adhesives for sealing materials, sealants, human bodies, and the like.
[0003]
  Recently, attempts have been made to make plastics molded products and ceramic products antibacterial using inorganic antibacterial agents, synthetic antibacterial agents, and natural antibacterial agents, but silicone rubber products and silicone rubber adhesives are generally used as they are. It is usually used without any special antibacterial treatment.
[0004]
  In order to give the silicone resin antibacterial properties, the applicant of the present invention disclosed in JP-A 2000-86717 as an elastic or adhesive resin or resin composition selected from silicone resins or various adhesives. A patent application has been filed for an antibacterial resin composition comprising an effective amount of an antibacterial component.
[0005]
  Japanese Patent Application Laid-Open No. 2001-311048 relating to the coating composition includes a film-forming component, a functional component derived from animals and plants, and a component derived from a raw material having an aggregating action. Functional (deodorant, antimicrobial, etc.) coating compositions containing a composite composed of a ceramic component are shown, and there is a word about silicone resins as film-forming components. Here, the functional properties include deodorizing properties, antimicrobials, and the like.
[0006]
[Problems to be solved by the invention]
  Among silicone resins, for example, silicone rubber is used for various purposes as described above, taking advantage of its flexibility, elasticity, resilience, durability, etc., but when used in contact with water. In many cases, the mold grows darker due to molds adhering to and propagating over a long period of use. Moreover, even if it does not appear dirty, it may be a question in terms of hygiene.
[0007]
  In the above-mentioned invention of JP-A-2000-86717, it has succeeded in obtaining excellent antibacterial properties while being safe by blending a plant-derived antibacterial component such as catechin with a silicone resin. Further improvement is required in terms of sustainability when washed with water or used in contact with water.
[0008]
  In the above-mentioned invention of JP-A-2001-311048, even if it is used in contact with water, functionalities such as deodorant and antimicrobial properties are maintained for a long time, but depending on the manufacturing method described in the publication, There were limitations in terms of effectiveness and productivity. The limit of the action effect seems to be due to the fact that it is difficult to make the particle diameter smaller than a certain limit. In terms of productivity, the production of the functional component in the form of a mixture with the ceramic component is preferably agglomerated and then heat treated at a high temperature until dehydration using a crucible or the like, by mechanical means. Since it is usually made into a composite through multiple processes such as pulverization and classification at the end, the burden is large in terms of equipment, labor (man-hours), time, etc., resulting in high product costs. Although it cannot be avoided, the necessary steps cannot be omitted as long as ceramics are handled, and there is a limit to the rationalization of the manufacturing process.
[0009]
  Under such a background, the present invention provides a product having a small particle size with high productivity as a fine powder hybrid product composed of a functional component having a deodorizing property or an antimicrobial property and a ceramic component as an internal additive. By providing a method for producing a functional silicone resin composition that has been devised so that the functionality of the resin can be maintained over a long period of time while making good use of the goodness of the silicone resin. It is intended.
[0010]
[Means for Solving the Problems]
  The method for producing the functional silicone resin composition of the present invention comprises:
  Hybrid of functional component (Y) and ceramic component (Z) obtained by spray drying method from aqueous slurry containing functional component (Y) having deodorant or antimicrobial properties and ceramic component (Z) The silicone resin (X) contains an effective amount of the finely powdered hybridized product (YZ)thing,
  Said functional ingredient (Y) Is a plant-derived component selected from the group consisting of catechins, saponins, tea extract, tea leaf powder, tannin (acid), caffeine, hinokitiol and perilla leaf extract,
  The ceramic component (Z) Consisting of colloidal silica, and
  Fine powder hybridized product by spray drying method (YZ) But functional ingredients (Y) And ceramic components (Z) An aqueous slurry containing a droplet diameter of 10 μm using a nozzle utilizing compressed gas. m The following mist is supplied into the tank of the spray dryer and hot air is blown into the tank, and the inlet temperature of the hot air at that time is set to 180 to 290 ° C and the exhaust temperature is 80 to 220 ° C and the inlet temperature It is obtained by setting at a temperature lower than 30 ° C.It is characterized by.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention will be described in detail below. In the present invention, “deodorant” means deodorization, malodor elimination, harmful gas component removal, etc., and “antimicrobial” means antibacterial, bactericidal, bacteriostatic, antifungal. It is used in the meaning including the property, deodorant property, antiviral property, etc.
[0012]
<Silicone resin (X)>
  As the silicone-based resin (X), a silicone-based resin (including a modified silicone-based resin) or an elastic or adhesive resin or resin composition containing the same as a main component is used.
[0013]
  Silicone rubber is suitably used as the elastic silicone resin. As silicone rubber, for example,
  ・ Heat-curing type silicone rubber: Millable type, liquid rubber (one-part type, two-part type),
  ・ Room-temperature curable liquid silicone rubber: Condensation type (one-component type, two-component type), addition type (one-component type, two-component type), ultraviolet curable type (one-component type),
Etc.
[0014]
  Silicone raw rubber, which is the main component of silicone rubber, is a very high viscosity polymer having a degree of polymerization of about 5000 to 100,000 and an average molecular weight of about 400,000 to 800,000. Examples of the silicone raw rubber include dimethyl silicone raw rubber, methyl vinyl silicone raw rubber, methyl phenyl vinyl silicone raw rubber, and fluorosilicone raw rubber.
[0015]
  An adhesive silicone-based resin, that is, a silicone-based adhesive, is typically composed of a silicone raw rubber that is a high-polymerization degree polymer as an elastomer component and a silicone resin that is a low-polymerization degree polymer as a tackifier component. . When a peroxide such as benzoyl peroxide is added for crosslinking, the cohesive force is further increased.
[0016]
<Functional component (Y)>
  Functional ingredients (Y) In the present invention, catechins (epigallocatechin, epigallocatechin gallate, epicatechin, epicatechin gallate, and mixtures thereof), saponins, tea extract (the most tea, the second tea, the third tea Extracts of teas such as powdered tea, deep-boiled and kabuse, extracts of black tea and oolong tea), tea leaf powder, tannin (acid) (commercially purified tannic acid, high tannic acid containing a large amount of tannic acid such as pentaploid and gallic acid) A plant-derived component selected from the group consisting of a natural plant extract or semi-purified product thereof, caffeine, hinokitiol and perilla leaf extract. theseIn addition to deodorizing and antimicrobial properties, the ingredients often have properties such as harmful small organism repellent properties, relaxation properties, aromatherapy properties, antiallergic properties, antioxidant properties, anti-inflammatory properties, and moisturizing properties. Such properties also have an advantageous effect on commercialization.
[0017]
<Ceramics component (Z)>
  Ceramic component (Z) In the present invention, colloidal silica is used. Other ceramics can be used in combination with colloidal silica.In this case, if a mixture of colloidal silica and other ceramics is used, for example, depending on the type of ceramics on the other side, the target product may be finer and finer than the size regulated by the size of the droplets when drying the droplets. In some cases, it can be used to control the particle size of fine powder.
[0018]
<Fine powder hybrid (YZ)>
  The composite (YZ) can be obtained by spray drying an aqueous slurry containing the functional component (Y) and the ceramic component (Z) described above.And in this invention, the fine powder-like hybrid thing by the spray drying method (YZ) Is manufactured as follows. That is, the above aqueous slurry was mixed with a droplet diameter of 10 μm using a nozzle using compressed gas. m The following mi The hot air is supplied into the tank of the spray dryer as a strike and hot air is blown into the tank, and the inlet temperature of the hot air at that time is set to 180 to 290 ° C. and the exhaust temperature is 80 to 220 ° C. and higher than the inlet temperature This is done by setting the temperature to 30 ° C. or lower.Thereby, a fine powder hybrid product (YZ) in which the functional component (Y) and the ceramic (Z) are hybridized is produced at once.
[0019]
  As the spray drying device, various types such as “blow-up type”, “horizontal type”, “cyclonic type”, etc. can be used as well as “upper down type” in which droplets fall from upper to lower.
[0020]
  In addition,The atomized droplet diameter is usually sprayed when it exceeds 10 μm, and 10 μm or less is usually distinguished from mist.In the present invention, a droplet 10 μm m The following mist is supplied into the tank of the spray dryer.
[0021]
  Generally in spray drying methodDroplet formation is performed using a rotating disk (change in the number of rotations), a pressure nozzle (liquid pressure), a two-fluid nozzle (gas pressure), a four-fluid nozzle (gas pressure), and the like.However, in the present invention, it is performed by a gas pressure method using a nozzle using compressed gas.
[0022]
  Among these, the four-fluid nozzle, which is one type of nozzle using compressed air, can spray a large amount of droplets as mist, and thus it is particularly preferable to use such a four-fluid nozzle. Regarding the four-fluid nozzle described below, for example, there is an explanation article by the author of Fujisaki Electric Co., Ltd. on pages 60-65 of “Chemical Equipment, June 2000”, and detailed explanations are also given in the company's catalog and technical data. There is.
[0023]
  In the four-fluid nozzle, two gas paths and two liquid paths are provided on the knife-like nozzle edge, each having a total of four paths, and a slope that is a gas and liquid flow surface at the edge tip is provided. Each fluid is composed of a collision focal point where the fluids gather at one point. The nozzle edge is desirably provided with a straight portion having an appropriate length (for example, an edge length of 1 to 200 mm) depending on the spray amount. The high-speed gas fluid exiting from the gas slit extends thinly while mixing the liquid exiting from the liquid slit at the fluid flow surface. The stretched liquid is further reduced in size by a shock wave generated at the collision focus at the edge tip and carried away as a droplet of several μm.
[0024]
  The four-fluid nozzle is capable of obtaining fine droplet sizes with an average particle size of several μm, sharp droplet size distribution, and arbitrarily controlling the droplet size according to the gas-liquid ratio. Capable of spraying a large amount, self-cleaning external mixing system, so there is no risk of clogging of deposits, continuous spraying for a long time, and spraying while mixing different types of liquids at the tip of the nozzle. It is extremely advantageous in that the spray pattern can be changed by the difference in the number of nozzles and nozzles having different spray amounts can be manufactured while maintaining the performance. The edge nozzle may be a straight type or a circle type.
[0025]
  Although the ratio (as solid content) of the functional component (Y) and the ceramic component (Z) can be variously set, when the latter is 100 parts by weight, the former is 0.1 to 200 parts by weight, particularly 1 to 180 parts. It is preferable to use 2 parts by weight, especially 2 to 160 parts by weight. When the proportion of the functional component (Y) is too small, the functionality is insufficient, and when the proportion of the functional component (Y) is too large, the ceramic component (Z) is relatively short, so that the composite is not possible. Insufficient suppression of elution of the functional component (Y) in the fine powder hybrid (YZ) becomes insufficient.
[0026]
  The solvent of the aqueous slurry is usually water, but may contain an appropriate amount of organic solvent (alcohol or the like).
[0027]
  The solid content concentration of the aqueous slurry is not particularly limited, but it is usually 1 to 70% by weight, particularly 3 to 60% by weight, and especially 5 to 50% by weight in terms of atomization and thermal energy. It is.
[0028]
  In the present invention,For the set temperature, set the hot air inlet temperature.180-290 ° C(Especially190-280 ° C)To do.For the exhaust temperature,80-220 ° C(Especially90 to 200 ° C.) and lower than the inlet temperature by 30 ° C. or more (especially 50 ° C. or more).To do.When the hot air temperature is too low, the drying speed becomes slow and the composite (hybridization) becomes insufficient, so that the sustainability when using the object in contact with water is insufficient. On the other hand, if the hot air temperature is too high,Functional ingredients (Y)May be altered or volatilized. The above temperature range is a temperature condition for efficiently obtaining the target product.
[0029]
  Average particle size of the target (fine powder hybrid (YZ)) derived from the tankIs 10μ m Less thanIt is preferable to control. Control to 5 μm or less, further 3 μm or less, or 2 μm or less is easy. Control of the average particle size can be achieved by controlling the size of the droplets, the particle size of the ceramic component (Z) in the aqueous slurry, and the like. The lower limit is not particularly limited, and may be on the order of submicron (0.1 μm).
[0030]
  Regarding the fineness of the particle diameter and the sharpness of the particle size distribution, it is more appropriate to look at the median diameter and mode diameter rather than the average particle diameter.Fine powder hybrid (YZ) ofParticularly suitable properties are a median diameter of 3 μm or less (preferably 0.3 to 3 μm, especially 0.5 to 2 μm) and a mode diameter of 3 μm or less (preferably 0.3 to 3 μm, particularly 0.5 to 2 μm).
[0031]
<Manufacture of functional silicone resin composition>
  The silicone resin (X) described above contains an effective amount of the finely powdered hybrid (YZ) thus obtained. Inclusion is made with respect to the silicone-based resin (X) before curing (in the case of a pressure-sensitive adhesive, it is performed at the time of preparation or at an arbitrary stage before preparation). Thereby, the intended functional silicone resin composition is obtained.
[0032]
  The ratio between the silicone resin (X) and the finely powdered hybrid (YZ) varies depending on the intended use and also varies greatly depending on the type and purity of the functional component (Y). The effective amount is sufficient to demonstrate functionality. As a guideline, when the total amount of the silicone resin (X) and the fine powder hybrid (YZ) is 100 parts by weight, the proportion of the fine powder hybrid (YZ) is, for example, about 0.1 to 60 parts by weight. In many cases, about 0.5 to 50 parts by weight, more preferably about 1 to 40 parts by weight is added.
[0033]
<Application>
  The resin composition obtained by the method of the present invention can be used in various fields including industrial use, consumer use, and medical use. For example, packing (pressure cooker, jar / pot, electronic jar, lunch box, refrigerator, microwave window frame, etc.); milker, nursing nipple; underwater glasses, snorkel, mouthpiece, goggles band, swimming cap; Rubber stoppers; Coating agents on the tip of injection needles; Connection parts for water and hot water supply equipment; Rubber contacts for calculators, mobile phones, and keyboards; Toys; Wires; Office equipment parts; Tubes for medical and beverage use; , Sealant; pressure-sensitive adhesive, adhesive, and the like.
[0034]
<Action>
  In the resin composition obtained by the method of the present invention,Under certain conditionsObtained by spray drying methodspecificFunctional ingredient (Y) andspecificSince a hybrid of ceramics (Z) is used, the productivity is much higher than that of fine powder hybrids (YZ) of functional components (Y) and ceramics (Z) obtained by a normal process. In addition, since the particle size of the finely hybridized product (YZ) is small and uniform (because the particle size distribution is sharp), the functionality (deodorant and antimicrobial properties) is further improved. And even if this functionality is used for the use which contacts water (including hot water), it will last for a long time. When the functional component (Y) is, for example, hyaluronic acid, when the target is coated on the tip of the injection needle, an effect of improving slipping and not feeling pain is exhibited.
[0035]
【Example】
  The following examples further illustrate the invention.
[0036]
                  (Manufacture of fine powder hybrid (YZ))
  The finely powdered hybrid (YZ) supplies an aqueous slurry containing the functional component (Y) and the ceramic component (Z) in the form of fine droplets into the tank of the spray drying apparatus described below and hot air in the tank. A finely powdered hybrid (YZ) was produced by a spray-drying method in which B was introduced.
[0037]
  FIG. 1 is an explanatory view showing a spray drying apparatus.
  FIG. 2 is an enlarged explanatory view of a four-fluid nozzle in the apparatus of FIG.
[0038]
  1 and 2, (1) is a liquid supply system, (2) is a gas supply system, (3) is a nozzle (four-fluid nozzle), (4) is a device body (tank), (5) is a blower, (6) is a heater, (7) is a cyclone, (8) is a bag filter, and (9) is an exhaust fan.
[0039]
  The liquid supply system (1) and the gas supply system (2) each have two paths, and spray is made at the tip of the nozzle (3) as shown in FIG. The collection (collection) of the product may be performed using both the cyclone (7) and the bag filter (8), or may be performed using either one of them.
[0040]
Production Examples 1-3
  An aqueous slurry was prepared by adding 10 parts by weight of tea catechin having a purity of 30% by weight to 100 parts by weight of an aqueous colloidal silica colloidal liquid having a solid content of 40% by weight and mixing with a homogenizer for 3 minutes.
[0041]
  Using this aqueous slurry, Fujisaki Electric Co., Ltd. research spray dryer "Micro Mist Dryer MDL-050-TypeM" (equipped with a four-fluid nozzle)
  ・ Edge length 2mm
  ・ Air slit 0.2mm
  ・ Liquid slit 0.2mm
  ・ Air volume: approx. 25L / min
  ・ Amount of spray liquid: about 10ml / min
  ・ Air pressure 0.7MPa
  ・ Hot air volume 1m^ThreeAbout / min
The target product was recovered with a cyclone (CY) and / or a bag filter (BF).
[0042]
  The conditions and results are shown in Table 1. In addition, the hot air inlet temperature was set to around 200 ° C. or around 250 ° C. because it was confirmed in previous experiments that complexation (hybridization) was insufficient and a large amount of raw catechin remained at about 150 ° C. The recovered amount of Production Example 3 is 94.6 + 877 = 971.6 g after 2 hours, and 94.6 + 877 + 722 = 1693.6 g after 3 hours. The particle size distribution was measured using “SALD-200V ER” manufactured by Shimadzu Corporation.
[0043]
[Table 1]
  
                      Production Example 1  Production Example 2  Production Example 3
  
  time (min) Five Five 60 120 180
  Inlet temperature (℃) 200 250 250 250 250
  Exhaust temperature (℃) 85 107 99 102 111
  Tower pressure (min) 0.4 0.5 0.8 0.7 0.6
  Supply air volume (m^Three/ min) 1.1 0.85 0.85 0.85 0.87
  1 air
    Pressure (MPa) 0.69 0.69 0.69 0.69 0.68
    Flow rate (NL / min) 80 80 80 80 80
  2 air
    Pressure (MPa) 0.69 0.69 0.69 0.69 0.69
    Flow rate (NL / min) 80 80 80 80 80
  1 liquid
    Flow rate (ml / min) 20 20 20 20 10
  2 liquids
    Flow rate (ml / min) 20 20 20 20 10
  Recovery (g) 46.8 32.6 94.6 877 722
  Median diameter (μm) 5.614 6.075 5.808 6.412 5.949
  Mode diameter (μm) 6.512 6.514 6.512 7.527 6.512
  Average particle size (μm) 5.598 6.298 5.873 6.624 6.217
  Standard deviation 0.293 0.324 0.302 0.329 0.321
  25% diameter (μm) 3.680 3.914 3.782 4.071 3.874
  50% diameter (μm) 5.614 6.075 5.806 6.412 5.949
  75 % Diameter ( μ m) 8.018 9.114 8.519 9.734 8.899
[0044]
Production Examples 4-6
  Spray drying was performed according to Production Example 1, except that the aqueous slurry having the following composition was used. The conditions and results are shown in Table 2.
  Production Example 4 Tea catechin with a purity of 30% by weight 17.5% by weight, colloidal silica aqueous colloidal liquid 10% by weight with a solid content of 40% by weight, 12.5% by weight of pulverized talc having an average particle size of 0.5 μm and 60% by weight of water.
  (Production Example 5) 17.5% by weight of tea catechin having a purity of 30% by weight, 5% by weight of an aqueous colloidal colloidal silica solution having a solid content of 40% by weight, 12.5% by weight of ground talc having an average particle size of 0.5 μm and 65% by weight of water.
  (Production Example 6) 17.5 wt% of tea catechin having a purity of 30 wt%, 12.5 wt% of pulverized silica having an average particle size of 1.5 µm, 5 wt% of an aqueous colloidal silica colloid having a solid content of 40 wt% and 65 wt% of water.
[0045]
[Table 2]
  
  Production Example 4 Production Example 5 Production Example 6
  Inlet temperature (℃) 225 225 224
  Exhaust temperature (℃) 106 102 100
  Median diameter (μm) 4.146 5.765 1.596
  Mode diameter (μm) 4.216 5.633 1.529
  Average particle size (μm) 4.133 6.141 1.608
  Standard deviation 0.275 0.363 0.221
  25% diameter (μm) 2.778 3.570 1.093
  50% diameter (μm) 4.146 5.765 1.596
  75 % Diameter ( μ m) 5.978 9.212 2.350
[0046]
  In addition, 100% by weight of an aqueous colloidal liquid of colloidal silica having a solid content of 40% by weight (Functional ingredients (Y)None), with median diameter 7.490μm, mode diameter 7.527μm, average particle diameter 8.589μm, standard deviation 0.243, 25% diameter 5.976μm, 50% diameter 7.490μm under conditions of inlet temperature 250 ° C and exhaust temperature 105 ° C The 75% diameter was 9.851 μm.
[0047]
Comparative production example 1
  10 parts by weight of tea catechin having a purity of 30% by weight is mixed with 100 parts by weight of an aqueous solution of aluminum phosphate having a concentration of 20% by weight, and the pH is adjusted to 3 to 4 to obtain an aqueous colloidal silica colloidal solution having a solid content of 40% by weight. 50 parts were added and mixed to bring the pH to neutral. Since the slurry gradually aggregated, it was transferred to a crucible while it could be handled, heated in an electric furnace, dried at 100 to 300 ° C., and heat-treated. As a result, hard amorphous aggregates were obtained, which were finely pulverized with an automatic mortar and classified with a sieve to obtain particles having a particle size of 100 to 325 mesh (147 to 43 μm). Subsequently, this aggregate was heat-treated in an electric furnace.
[0048]
                    (Manufacture of functional silicone resin composition)
Example 1, Comparative Example 1, Control Example 1
  100 parts of a silicone rubber raw material as an example of the silicone resin (X) is obtained by using 5 parts by weight of the finely powdered hybrid (YZ) obtained in Production Example 1 or 5 parts by weight of the pulverized aggregate of Comparative Production Example 1. The mixture was added to and mixed, and allowed to cure at room temperature to obtain a sheet-like cured product. As a control example 1, a cured product was also obtained when no functional component (Y) was added.
[0049]
(Antibacterial activity)
  Using these cured products as samples, antibacterial activity against Staphylococcus aureus ATCC 6538P was examined by a bacterial count reduction rate test. That is, a bouillon suspension of a test bacterium was poured into a sterilized sample, and the number of viable bacteria after culturing at 37 ° C. for 18 hours in an airtight container was measured to obtain an increase / decrease value relative to the number of inoculated bacteria. The results are shown below and in Table 3. The unprocessed cloth was a standard cotton cloth.
[0050]
・ Inoculation count (A) is 8.4 × 10^Four , Log A is 4.9
・ Non-processed number of bacteria⁷ , Log B is 7.3
Log B-log A = 2.4> 1.5 (test is valid)
Increase / decrease value = log C-log A
-Increase / decrease value difference = (log B-log A)-(log C-log A)
[0051]
[Table 3]
  
  Additives Amount added Bacteria count log C Increase / decrease value Difference
  Control Example 1 − − 7.3 2.4 0.0
  Example 1 Production Example 1 (YZ) 5 wt Part 3.3 -1.6 4.0
  Comparative Example 1 Comparative Production Example 1 5 wt part 5.2 0.3     2.1
  Aggregates of
    (Sample weight is 0.2g)
[0052]
(Deodorant)
  In addition, using these sheet-like cured products, the components causing odor are brought into contact with each other under the following conditions to adsorb the components to the sheet, and then washed with water, and then the degree of odor remaining on the sheet is determined. Evaluation was made by a sensory test. The results are shown in Table 4.
  ・ Odor component Fish odor: The sheet was immersed for 2 hours in water containing a fish arabe, immersed in running water for about 30 minutes, then the sheet was taken out and air-dried, and the degree of odor was examined.
  ・ Odor component Garlic odor: Leave the sheet in a state where the garlic crushed in a grater diluted with water is left overnight, soak it in running water for about 30 minutes, take out the sheet, air dry, and examine the degree of odor It was.
  ・ Odor component 3. Machine oil odor: Leave the sheet immersed in machine oil for 1 hour, wash it with detergent-containing water three times, soak it in running water for about 30 minutes, take out the sheet, air dry, and the degree of odor I investigated.
  Sensory evaluation: The case of Control Example 1 was used as a reference (evaluation of X), X was the same as Control Example 1, Δ was a slight improvement over Control Example 1, and it was significantly improved over Control Example 1. The case where it is marked with □, and the case where it is markedly improved as compared with the control example 1 was evaluated as ◯.
[0053]
[Table 4]
  
  Additives Amount added Odor 1 Odor 2 Odor 3
  Control Example 1 − − × × ×
  Example 1 Production Example 1 (YZ) 5 wt Part ○ ○ to □ ○
  Comparative Example 1 Comparative Production Example 1 5 wt parts □ □ to △ □
  Aggregates of
[0054]
Example2-6
  In Production Example 1, in place of 10 parts by weight of tea catechin having a purity of 30% by weight, the ones shown in Tables 5 and 6 below were used. An aqueous slurry was prepared by adding 10 parts by weight of the sex component (Y) and mixing with a homogenizer for 3 minutes. Using this aqueous slurry, a finely powdered hybrid (YZ) was produced under the same conditions as in Production Example 1.
[0055]
  Next, in the same manner as in Example 1, 5 parts by weight of the finely powdered hybrid (YZ) thus obtained was added to and mixed with 100 parts of a silicone rubber raw material as an example of the silicone resin (X). The sheet was allowed to cure at room temperature to obtain a sheet-like cured product. As Control Example 2, a cured product was also obtained when no functional component (Y) was added.
[0056]
(Anti-mold performance)
  The following agar medium was thinly attached to the surface of these cured products, and the superiority or inferiority of the antifungal performance was examined. The results are shown in the following Table 5 (shown together with the cases of Example 1 and Comparative Example 1).
[0057]
  As the fungal culture solution, a commercially available modified GAM agar medium was used, which was naturally dissolved after being heated and dissolved in a flask. As for fungi, 0.5 ml each of a previously prepared black fungus solution (100 mg / 500 ml pure water) was planted in 100 ml of the medium solution. The growth of mold fungi was observed for 14 days at 35 ° C. and 95% RH using a constant temperature and humidity chamber.
[0058]
[Table 5]
  
  Additive occurrence frequency Observation Result
  Control Example 2 +++ Large mold on the surface
  blank +++++ Mold occurs
  Comparative Example 1 Comparative Manufacturing Example 1 ++ Slight mold on the surface
  Example 1 Production Example 1 + Slight mold on the surface
  Example 2 Tea Saponin-No Mold Generation
  Example 3 Hinokitiol-No generation of mold
  Example4  Perilla leaf extract + slight mold on the surface
  Example5  Tannic acid + Slight mold on the surface
  Example 6 Catechin + CuO - No mold generation
  (Note) Examples2-6IsFunctionalityOnly component (Y) is listed.
[0059]
(Deodorant)
  In the same manner as in Example 1, the deodorizing properties for the odor components 1, 2, and 3 were examined. The results are shown in Table 6.
[0060]
[Table 6]
  
  Additive Odor 1 Odor 2 Odor 3
  Control Example 1-× × ×
  Example 1 Production Example 1 (YZ) ○ ○ to □ ○
  Comparative Example 1 Comparative Production Example 1 □ □ to △ □
  Aggregates of
  Example 2 Tea Saponin ○ ～ □ □ ○ ～ □
  Example 3 Hinokitiol ○ ~ □ □ ○ ~ □
  Example4  Perilla leaf extract ○ 〜 □ □ ○ 〜 □
  Example5  Tannic acid ○ 〜 □ □ ○ 〜 □
  Example 6 Catechin + CuO ○ ○ to □ ○
  (Note) Examples2-6IsFunctionalityOnly component (Y) is listed.
[0061]
Production Examples 7-9
  In Production Example 1, except that the spray-drying conditions were changed, 10 parts by weight of the functional component (Y) was added to 100 parts by weight of an aqueous colloidal colloidal silica solution having a solid content of 40% by weight and mixed for 3 minutes with a homogenizer. Thus, an aqueous slurry was prepared. Using this aqueous slurry, a finely powdered hybrid (YZ) was produced under the same conditions as in Production Example 1. Conditions and results are shown in Table 7.
[0062]
[Table 7]
  
  Production Example 7 Production Example 8 Production Example 9
  Inlet temperature (℃) 225 225 224
  Exhaust temperature (℃) 106 102 100
  Median diameter (μm) 1.188 1.286 1.263
  Mode diameter (μm) 0.990 1.145 1.145
  Average particle size (μm) 1.234 1.319 1.323
  Standard deviation 0.195 0.200 0.215
  25% diameter (μm) 0.871 0.926 0.898
  50% diameter (μm) 1.188 1.286 1.263
  75 % Diameter ( μ m) 1.688 1.831 1.871
[0063]
Example7-9
  Next, in accordance with Example 1, 5 parts by weight of the fine powder hybrid product (YZ) obtained in Production Examples 7 to 9 was added to 100 parts of a heat vulcanized silicone rubber raw material as an example of the silicone resin (X). And mixed, heated and vulcanized and cured to obtain a sheet-like cured product.
[0064]
(Deodorant)
  Using these sheet-like cured products, the deodorizing properties for the odor components 1, 2, and 3 were examined in the same manner as in Example 1. The results are shown in Table 8.
[0065]
  For the sensory evaluation, the case of the previous Control Example 1 was used as the reference (evaluation of ×), the case equivalent to the Control Example 1 was ×, the case where a slight improvement was seen over the Control Example 1, and the case of the Control Example 1 The case where it was considerably improved was evaluated as □, the case where it was remarkably improved as compared to Control Example 1, and the case where the effect that was clearly superior to that of Example 1 was obtained was evaluated as ◎.
[0066]
[Table 8]
  
  Additive Odor 1 Odor 2 Odor 3
  Control Example 1-× × ×
  Example 1 Production Example 1 (YZ) ○ ○ to □ ○
  Comparative Example 1 Comparative Production Example 1 □ □ to △ □
  Aggregates of
  Example7  Production Example 7 (YZ) ◎ ◎ to ○ ◎
  Example8  (YZ) of Production Example 8 ◎ ◎ to ○ ◎
  Example 9 Production Example 9 (YZ) ◎ ◎ ~ ○ ◎
[0067]
【The invention's effect】
  In the present invention,specificFunctional ingredient (Y) andspecificFrom aqueous slurry containing ceramic component (Z)Under certain conditionsThe silicone resin (X) is allowed to contain an effective amount of the fine powder hybrid product (YZ) obtained by hybridizing the functional component (Y) and the ceramic (Z) obtained by the spray drying method.
[0068]
  Therefore, according to the present invention, as the internal additive, it is possible to obtain a fine powdery hybrid product composed of a functional component and a ceramic component with a small and uniform particle size with good productivity. While maintaining the above, the resin has excellent functionality, and even if it is used in contact with water, the functionality lasts for a long time.
[0069]
  And since the fine powder hybrid product (YZ) in which the functional component (Y) and the ceramic component (Z) are hybridized can be manufactured at once, the conventional method of mixing, heat treatment, pulverization and classification is used. Compared with productivity, man-hours, equipment, thermal energy, time required, etc., it is much more advantageous. In particular, it is advantageous to use a four-fluid nozzle as the nozzle.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing a spray drying apparatus used in a method of the present invention.
FIG. 2 is an enlarged explanatory view of a four-fluid nozzle in the apparatus of FIG.
[Explanation of symbols]
  (1)… Liquid supply system,
  (2)… Gas supply system,
  (3)… Nozzle (four fluid nozzle),
  (4)… System unit (tank),
  (5)… Blower,
  (6)… Heater,
  (7)… Cyclone,
  (8)… Bug filter,
  (9)… Ventilator

Claims (2)

Hybrid of functional component (Y) and ceramic component (Z) obtained by spray drying method from aqueous slurry containing functional component (Y) having deodorant or antimicrobial properties and ceramic component (Z) The silicone resin (X) contains an effective amount of the pulverized fine powder hybrid (YZ) ,
The functional component (Y) is a plant-derived component selected from the group consisting of catechins, saponins, tea extract, tea leaf powder, tannin (acid), caffeine, hinokitiol and perilla leaf extract. ,
The ceramic component (Z) is made of colloidal silica; and
The pulverulent hybrid product by spray drying method of (YZ) is an aqueous slurry containing the functional component (Y) and the ceramic component (Z), the following droplet diameter 10 [mu] m using a nozzle using compressed gas Mist is supplied into the tank of the spray dryer and hot air is blown into the tank, and the inlet temperature of the hot air at that time is set to 180 to 290 ° C. and the exhaust temperature is 80 to 220 ° C. from the inlet temperature. preparation of functional silicone resin composition characterized by also be done by setting a low temperature 30 ° C. or higher, it is obtained by.   The process according to claim 1, wherein the ratio of the finely powdered hybridized product (YZ) to 100 parts by weight of the total amount of the silicone resin (X) and the finely powdered hybridized product (YZ) is 0.1 to 60 parts by weight.

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