JPH0471935B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an additive for resins in which an organic compound (hereinafter referred to as a useful component) that is useful when added to a resin is encapsulated in an inorganic-walled porous microcapsule base, More specifically, by adding useful ingredients to the resin and encapsulating them in an inorganic-walled porous microcapsule base under reduced pressure,
A resin that can minimize the volatilization of useful substances due to the heat during thermal processing and molding of the resin, allowing more useful substances to remain after molding, thereby increasing its usefulness after molding and maintaining its usefulness. The present invention relates to a method for producing an additive for use. Components useful when added to resins include components intended to exhibit their usefulness during thermoforming of the resin (e.g., heat stabilizers, lubricants, vulcanization accelerators, anti-aging agents, crosslinking agents, etc.). , components intended to exhibit usefulness after thermoforming the resin (for example, slip agents, antistatic agents, antifogging agents, ultraviolet absorbers, fragrances,
There are insect repellents, antibacterial agents, odorants, flame retardants, animal repellents, etc.), and the useful components added to these resins are classified depending on the purpose, type of resin, molding method, etc. [Prior art and its problems] Conventionally, among the components that are useful when added to resins, depending on the type of component that exhibits its usefulness especially after molding the resin, it has been found that some components act during thermoforming of the resin to improve the resin. Because it accelerates thermal deterioration during molding or reduces processing formability, it cannot be used even though its effectiveness is recognized, or even if it is used, its effectiveness is limited because it is only added in a very small amount. I couldn't perform. Also, depending on the type of component that is useful when added to the resin, it may volatilize due to the heat during thermoforming of the resin, so it may be necessary to add more than the amount necessary to exhibit its effectiveness after molding. Therefore, it is not only economically disadvantageous, but also has many drawbacks, such as rapid volatilization over time from the molded product after molding, making permanent effectiveness impossible. In order to improve these drawbacks, conventional techniques include a method of adding useful components to the resin by molecular sieving with zeolites, and a method of adding them by adsorption to an inorganic or organic material with a large surface area. Alternatively, in order to prevent thermal deterioration, methods have been adopted in which large amounts of stabilizers, anti-aging agents, or lubricants are added in combination to prevent deterioration of the resin, but these methods are insufficient and have not yielded satisfactory results. Not obtained. [Means for Solving the Problems] The present inventors have conducted extensive research into ways to improve the above-mentioned drawbacks and to better demonstrate the effectiveness of useful components added to resins. By pre-encapsulating useful components in inorganic-walled porous microcapsules in a substrate under reduced pressure, and then adding them to the resin, adverse effects on the resin can be prevented as much as possible, or when the resin is heated during thermoforming. It has been found that by minimizing the volatilization of the components useful when added to the resin, the efficacy of the components useful when added to the resin becomes extremely high. That is, as a method for encapsulating useful components by adding them to a resin in an inorganic-walled porous microcapsule base, the inorganic-walled porous microcapsule base and the useful components added to the resin are mixed in advance in a liquid state, and then the pressure is reduced. Alternatively, the present invention was completed based on the discovery that the mixture can be more efficiently sealed by mixing under reduced pressure and then gradually returning the pressure to normal pressure. A more specific enclosing method will be explained as follows. That is, Patent No. 1184016 (Special Publication No. 57-55454)
An inorganic wall porous microcapsule substrate with an outer diameter of 0.1 to 500 microns, preferably 0.5 to 200 microns, manufactured by a method generally called an interfacial reaction method disclosed in
600 millimicrons, wall thickness approximately 0.1 to 30 microns)
and one or more organic compounds (useful components) that are useful when added to the resin are mixed in advance using a stirring mixer or a rotary mixer, and then the pressure is reduced in a pressure reducer to form an inorganic wall porous material. After removing the air in the hollow part of the microcapsule base, the particle wall fineness of the inorganic wall porous microcapsules is reduced by gradually returning the pressure to normal pressure, or by gradually returning the pressure to normal pressure while mixing under reduced pressure. The useful components adhering to the pores and the surface are suctioned by the pressure difference with the hollow part within the microcapsule, making it possible to efficiently encapsulate the useful components. In order to further increase the encapsulation efficiency, it is preferable to reduce the pressure to a level just before the useful components boil and vaporize, and therefore it is preferable to measure the vapor pressure of the organic compound. Further, as will be described later, useful components include those that are liquid at room temperature and those that are solid, and the latter may be melted in advance at a temperature above the melting point or dissolved using an appropriate solvent and mixed in liquid form. , this resin additive is added to the resin and fully exhibits its usefulness after molding without adverse effects such as thermal deterioration on the resin. Because it has the property of slow-release, the useful ingredients added to the resin do not ooze out to the surface all at once, but gradually ooze out, so the useful ingredients are permanently released over a long period of time. Its performance can be sustained. In the present invention, it is most preferable to encapsulate components that are useful when added to the resin and provide usefulness after the resin is molded. It is also possible to use an inhibitor, a crosslinking agent, a vulcanization accelerator, etc., encapsulated in an inorganic porous microcapsule substrate whose walls are thin enough to be destroyed during molding. In addition, the type of resin used or its purpose, or even the inorganic-walled porous microcapsule base itself, is useful for improving the performance of the resin. For example, the additive for the resin of the present invention, which encapsulates a slip agent, can be used for polyolefin, polyester, nylon, etc. Since it is also effective as an anti-blocking agent for films, there is no need to separately add anti-blocking agents such as talc, silica, and zeolite. Therefore, the inorganic-walled porous microcapsule substrate used in the present invention can be added alone to the resin as an anti-blocking agent. [Example of inorganic wall porous microcapsule substrate] The inorganic wall porous microcapsule substrate used in the present invention is disclosed in Japanese Patent No. 1184016 (Japanese Patent Publication No. 57-55454)
A hollow porous inorganic compound manufactured according to the interfacial reaction method disclosed in 2006. Typical examples of the compound include silica, alumina, magnesium oxide, zinc oxide, cadmium oxide, titanium oxide, iron oxide, nickel oxide, Oxides such as cobalt oxide, chromium oxide, manganese oxide, lead oxide, copper oxide, zirconium oxide, antimony oxide, magnesium hydroxide,
Hydroxides such as calcium hydroxide, aluminum hydroxide, zinc hydroxide, cadmium hydroxide, iron hydroxide, nickel hydroxide, cobalt hydroxide, chromium hydroxide, lead hydroxide, copper hydroxide, aluminum carbonate,
Magnesium carbonate, zinc carbonate, calcium carbonate,
barium carbonate, cadmium carbonate, cobalt carbonate,
Carbonates such as nickel carbonate, chromium carbonate, lead carbonate, copper carbonate, magnesium silicate, calcium silicate, barium silicate, zinc silicate, cadmium silicate, aluminum silicate, lead silicate, cobalt silicate, silicic acid nickel, silicates such as copper silicate, sulfates such as magnesium sulfate, calcium sulfate, barium sulfate, zinc sulfate, cadmium sulfate, lead sulfate, magnesium sulfite, calcium sulfite, barium sulfite, zinc sulfite, cadmium sulfite, lead sulfite Sulfites, magnesium sulfide, calcium sulfide, barium sulfide, zinc sulfide, etc.
Sulfides such as cadmium sulfide and lead sulfide, magnesium phosphate, calcium phosphate, barium phosphate,
Phosphates such as zinc phosphate, cadmium phosphate, aluminum phosphate, lead phosphate, and copper phosphate; phosphites such as magnesium phosphite, calcium phosphite, barium phosphite, and lead phosphite; Borates such as magnesium acid, calcium borate, barium borate, zinc borate, cadmium borate, aluminum borate, lead borate, copper borate, iron borate, cobalt borate, nickel borate, chloric acid Magnesium, calcium chlorate, zinc chlorate, aluminum chlorate, magnesium bromate,
Oxygen halogen salts such as calcium bromate, barium bromate, zinc bromate, magnesium perchlorate,
Perhalogen oxygen salts such as calcium perchlorate, barium perchlorate, zinc perchlorate, magnesium perbromate, calcium perbromate, barium perbromate, zinc perbromate, hydrotalcite compounds, zeolite compounds, etc. can be given. [Example of components useful when added to resin] Components useful when added to resin used in the present invention are substances that are added to the resin and exhibit their usefulness after molding, and substances added to the resin. Substances that exhibit their usefulness during thermoforming are preferably liquid at room temperature, but substances that are solid at room temperature may also be used by dissolving them in substances that are liquid at room temperature, such as organic solvents, plasticizers, and water. I can do it. Typical examples include cationic, anionic, nonionic, and petaine fluorine-based antistatic agents;
Slip agents such as fatty acid amide type organic siloxane, drip-proof and anti-fogging agents such as polyhydric alcohol fatty acid esters, UV absorbers such as hindered amine type, triazole type, benzophenone type, natural or synthetic fragrances, natural or synthetic insect repellents, natural or synthetic antibacterial agents, natural or synthetic odorants,
Flame retardants such as halogenated organic compounds and organic phosphorus compounds, thiazole type, guanidine type, thiuram type,
Vulcanization accelerators such as thiourea type and dithiocarbamate type, anti-aging agents such as amine type, phenol type, thiophenol type, thiopropion ester type, and organic phosphite type, organic copper compounds, organic tin compounds, and phenols. antifungal agents such as organic nitrogen sulfur compounds, natural or synthetic rat repellents, crosslinking agents such as organic peroxides, coupling agents such as silane and titanium compounds, organotin compounds, organometallic compounds, and epoxies. Examples include heat stabilizers such as synthetic oils and fats and epoxy resins. [Description of Target Resin] The resin used in the present invention refers to synthetic resins in general, and representative examples thereof include polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, polypropylene, polymethylpentene, and polybutene.
1. Polybutadiene, polystyrene, acrylonitrile resin, AS resin, ABS resin, MBS resin,
Polyphenylene ether, polyphenylene sulfate, fluororesin, silicone resin, polymethacrylstyrene, methacrylic resin, polyamide, polyimide, polyimide amide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl alcohol, polyvinyl ether, polyacetal, poly Allyl sulfone, polyarylate, isopropylene rubber, polybutadiene rubber, etc. Furthermore, two or more copolymers of the monomers constituting these resins with each other or with other resins, and two or more polymer blends of these with each other or with other resins are listed. be able to. [Example] Next, the present invention will be specifically explained with reference to Examples. Example 1 After dissolving 200 g of diethanolamine alkyl phosphate (electrostripper N, an antistatic agent manufactured by Kao) in 100 g of butyl carbitol, the average particle size was
200 g of a 2.0 micron silica wall porous microcapsule base is uniformly mixed using a tumbler mixer, the mixture is left at room temperature under a reduced pressure of 20 mm of mercury for 30 minutes, and then gradually reduced to normal pressure over a period of approximately 3 hours. 498 g of microcapsule powder encapsulating an anionic antistatic agent was obtained. Example 2 60 g of lauryl trimethyl ammonium chloride (Kao antistatic agent Cortamine 24P) and 40 g of a silica-walled porous microcapsule substrate with an average particle size of 2.0 microns were uniformly mixed in a closed small test ribbon mixer, and this mixture was 30 columns of mercury at room temperature
After leaving for 20 minutes under a reduced pressure of 30 mm of mercury, the pressure was returned to normal pressure in 2 hours, and the mixture was uniformly mixed again in the same way. The mixture was returned to give 97 g of microcapsule powder encapsulating a cationic antistatic agent. Example 3 80 g of a calcium carbonate wall porous microcapsule substrate with an average particle size of 2.0 microns was placed in a closed small ribbon mixer for testing, and the pressure was reduced to 10 mm of mercury column.
While stirring under reduced pressure, 120 g of lauryl betaine (Anhidol 24B, an antistatic agent made by Kao) was gradually added, and the pressure was reduced for 30 minutes while stirring.
The pressure was gradually returned to normal pressure over time to obtain 198 g of microcapsule powder encapsulating a betaine type antistatic agent. Example 1 The antistatic agent encapsulating additive of the present invention obtained in Examples 1 to 3 was added to a polyvinyl chloride resin composition under the conditions shown in Table 1 to prepare a sheet with a thickness of 0.5 mm. Stability and chargeability were tested. For comparison, a similar test was conducted using a separately weighed additive without encapsulation, and the results are also shown in Table 2. Table 1 Compound composition PVC (Zeon 103EP) 100 parts by weight DOP (Sansocizer) 40〃 Liquid stabilizer (BZ-180) 1.5〃 Powder stabilizer (PSE-402) 0.6〃 Antistatic agent Table 2 Processing conditions Test roll temperature 170±2℃ Kneading time 5 minutes Press temperature and time 170±2℃×3 minutes Press pressure 120Kg/cm ²

【table】

[Table] As shown in Table 2, the present invention is superior to the comparative example.
This shows that it is very effective as it does not interfere with the thermal stability of PVC. Example 4 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane (AFR flame retardant made by Asahi Glass)
-1010) was dissolved in 445 g of butyl cellosolve, and this was mixed with 333 g of a silica-walled porous microcapsule substrate with an average particle size of 3.5 microns in a small super mixer (manufactured by Kawada Seisakusho). After reducing the pressure for an hour, the pressure was gradually returned to normal over a period of 2 hours to obtain 996 g of microcapsules containing 22.2% of flame retardant. Example 2 The flame retardant-encapsulated additive for the resin of the present invention of Example 4 was added to additive-free styrene resin to prepare a 1 mm thick sheet under the conditions shown in Table 3, and the thermal stability and flammability were tested. For comparison, a composition having the same ratio as in Example 4 was simply mixed and subjected to the test. Table the results.
4. In the flammability test, one side of a test piece with a width of 1 cm and a length of 12 cm was ignited with a gas burner, and the burning distance was measured for 20 seconds. Table 3 Compounding composition Additive-free styrene resin 100 parts by weight Zinc stearate 1.0〃 Antioxidant (Irganox 1076) 0.3〃 Antimony trioxide 3.0〃 Additives Table 4 Processing conditions Test roll 170℃ x 5 minutes Press 180℃ x 3 minutes Gear oven 190℃

[Table] As shown in Table 4, the resin additive of the present invention showed little thermal deterioration, and its flame retardancy was almost the same as that of the comparative example. Example 5 40 g of an aluminum hydroxide-walled porous microcapsule substrate was placed in a pressure reducer equipped with a screw-type stirrer that was depressurized to 15 mm of mercury at room temperature, left to stand while stirring for 30 minutes, and then 60 g of D-limonene was gradually added while stirring. After addition, leave it for 20 minutes while continuing to stir.
While stirring was continued, the pressure was gradually returned to normal pressure over 2 hours for encapsulation, followed by washing with 100 ml of ethanol and air drying to obtain 96.4 g of microcapsules containing 56.4% of D-limonene. Comparative Example A For comparison with Example 5, activated CS-10040g and D-
A mixture containing 60 g of limonene was prepared and used for comparison in Test Example 3. Test Example 3 The ingredients shown in Table 5 were added to low-density polyethylene (Showa Denko Shorex 108F MI = 0.8), kneaded for 5 minutes with a test roll at 160°C, and then a film with a thickness of 0.2 mm was formed using a press at 180°C. It was prepared and tested. (1) D-limonene retention Cut the molded film into squares of 5 cm on each side, hang it indoors for 7 days, then put it in a polyethylene bag and fill it with air.After leaving it at room temperature for 24 hours, the air in the polyethylene bag was The amount of D-limonene volatilized was determined using a detection tube, and the case where D-limonene was added alone was set as 1 for comparison. (2) Film haze Measured in accordance with ASTMD-1003-6 (3) Anti-blocking properties After promoting film adhesion for 24 hours at 45°C and 50 g/ ^cm2 , the film was subjected to shortcut tensile testing. The maximum stress (g/cm ² ) required to shear off 10 cm ² of the adhesive surface of the film using a tester at a tensile strength of 500 mm/min is shown. The results are shown in Table-5.

[Table] As shown in Table 5, it was confirmed that when the resin additive of the present invention was used, the retention of D-limonene was outstanding and the anti-blocking effect was also exhibited.

Claims (1)

[Claims] 1 An inorganic wall porous microcapsule substrate with a diameter of 0.1 to 500 microns manufactured by an interfacial reaction method,
Organic compounds useful to be added to the resin can be added to the resin in an inorganic-walled porous microcapsule matrix by mixing in liquid form and then reducing pressure, or by mixing in liquid form under reduced pressure and then gradually returning to normal pressure. 1. A method for producing an additive for resins, which comprises encapsulating an organic compound useful as a resin additive.