JPWO2016017671A1 - Scallop baked powder-containing resin molded product and method for producing the same - Google Patents

Abstract

The present invention provides an antibacterial resin molded product that exhibits high antibacterial properties and can sufficiently exhibit the characteristics inherent to the resin molded product. The remaining shell of the scallop shell which has been used for food is washed and dried, and then baked in a furnace at a temperature of about 1,100 ° C. for about 3 hours. The scallop shells were pulverized with an ultrafine pulverizer so that the average particle size was about 1 μm, thereby obtaining a scallop fired powder. Thereafter, the fired powder of scallops obtained was added to a polypropylene monomer, and the monomer was polymerized under predetermined conditions to obtain a polypropylene resin containing fired powder of scallops. And the polypropylene sheet of the predetermined thickness was produced by melt-extruding the obtained polypropylene resin containing the baked scallop powder at a predetermined temperature with a single screw extruder equipped with a T-die. [Selection figure] None

Description

  The present invention relates to a synthetic resin molded product used for packaging of various articles, and more specifically to a resin molded product having an antibacterial function.

  As a resin molded product having an antibacterial function, as disclosed in Patent Document 1, an antibacterial film in which an inclusion compound obtained by inclusion of an isothiocyanate compound or a terpene compound with cyclodextrin is added to a raw material resin, or Patent Document 2 As described above, an antibacterial film is known in which an inorganic antibacterial agent and an antibacterial substance derived from a natural product (that is, a kind selected from herb aloe, green tea catechin, chitosan, wasabi, chili, and hinokitiol) are added to the raw material resin. It has been.

JP-A-6-191562 JP 2005-8783 A

  However, the antibacterial films as described in Patent Documents 1 and 2 exhibit sufficient antibacterial properties unless inclusion compounds, inorganic antibacterial agents, and antibacterial substances derived from natural products are added in a large amount to the raw material resin. I can't let you. Therefore, there exists a malfunction that the characteristic (high intensity | strength, high transparency, etc.) which a film originally has is impaired by an additive.

  An object of the present invention is to solve the problems of the conventional resin molded products having antibacterial functions, exhibit high antibacterial properties, and exhibit antibacterial resin moldings that can sufficiently exhibit the inherent properties of resin molded products. Is to provide goods.

  The invention described in claim 1 is a resin-molded product containing fired scallop powder, characterized in that a fired powder obtained by firing and shelling a scallop shell is added to the raw material resin. The resin molded product referred to in the present invention is a variety of foods such as films, trays, containers, bags, packages, and baluns (partition sheets placed in trays containing lunch boxes, sashimi, etc.). These are resin molded products and various resin molded products that are desired to be antibacterial from a hygienic point of view.

  The invention according to claim 2 is characterized in that, in the invention according to claim 1, the addition amount of the baked scallop powder to the raw material resin is 0.2 mass% or more and less than 5 mass%. .

  The invention according to claim 3 is the addition of a fired powder of scallop shells into a resin raw material monomer, and then polymerizing the resin raw material monomer containing the fired powder to form a synthetic resin pellet. This is a method for producing a resin-molded product containing scallop baked powder, which is obtained by melt-extrusion and molding.

  The resin-molded article containing the scallop shell powder of the present invention can exhibit extremely high antibacterial properties even when the amount of the scallop shell shell powder added is small. Therefore, the characteristics inherent to the resin molded product can be sufficiently exhibited.

  In the resin molded product of the present invention, a fired powder obtained by firing a scallop shell and then pulverizing it is added to the raw material resin. The scallop as referred to in the present invention is a kind of mollusk classified into the genus Mizuhopecten belonging to the bivalve, airfoil, mussel family, and the type is not particularly limited.

  The shell of the scallop shell can be subjected to baking as it is after the shell meat portion has been peeled off for food, but can also be washed and fired after peeling off the shell portion. . As such a cleaning method, it is possible to employ a method of cleaning while applying a coarse pulverization process in a shower in which water is spouted, a method of cleaning in a water tank to which chlorine or the like is added, and the like. The washed scallop shell can be used for baking as it is, but it can also be washed after being sufficiently dried by exposure to sunlight and then used for baking.

  In addition, firing (mineralization) of the scallop shell is preferably performed at a temperature of 600 ° C. to 1,600 ° C. using various furnaces, and is performed at a temperature of 800 ° C. to 1,400 ° C. Is more preferable, it is more preferably performed at a temperature of 1,000 ° C. to 1,300 ° C., particularly preferably at a temperature of about 1,100 ° C. ± 50 ° C. Sintering at a temperature lower than 600 ° C. is not preferable because the particle shape is not sufficiently spheroidized in the subsequent pulverization process. On the other hand, calcination at a temperature higher than 1,600 ° C. is uneconomical due to increased energy loss. In addition, the high antibacterial properties that can be exhibited by the baked scallop powder are not preferred. Also, suddenly firing scallop shells at a high temperature is not preferable because the quality of the fired powder tends to be uneven, and heating at a final firing temperature is 200 to 300 ° C. lower than the final firing temperature. Pre-baking is preferably performed within a period of ¼ or more and ½ or less of the time.

  On the other hand, the firing time of the scallop shell depends on the firing temperature, but when firing at a temperature of 600 ° C. to 800 ° C., it is preferably performed for 6 to 8 hours, 800 ° C. to 1, When firing at a temperature of 000 ° C., it is preferably performed for 4 to 6 hours, and when firing at a temperature of 1,000 ° C. to 1200 ° C., it takes 2 to 4 hours. Preferably, it is performed, and when firing at a high temperature of 1,200 ° C. or higher, it is preferably performed for 1 to 2 hours. If the firing time is shorter than the above-mentioned reference time, it is not preferable because the particle shape will not be sufficiently spheroidized in the subsequent pulverization treatment, as opposed to the case where the firing temperature is low. It is not preferable because it is uneconomical due to an increase in energy loss and the high antibacterial properties that can be exhibited by the baked scallop powder.

  Furthermore, after firing the scallop shell, it is necessary to perform a pulverization treatment. By firing the shell of the scallop shell in such a manner and making it brittle, the powder particles of the shell can be shaped like a sphere, and the surface of the final resin molded product Can be made smooth. Such pulverization after firing is preferably performed by a fine pulverizer. The fine pulverizer is capable of pulverizing particles having a particle size of several mm or more so that the particle size is several tens of μm or less. Among them, pulverization can be performed so that the particle size is about 1 μm. An ultrafine mill is also included. Examples of such a fine pulverizer include a pot mill, a vibration mill, a stirring mill, an ang mill, and a jet mill. When forming a thin film as a resin molded product, it is preferable to use an ultrafine pulverizer such as a dry jet mill. In addition, the baked powder of scallop shells preferably has an average particle size of 9 μm or less because the antibacterial properties of the resin molded article are good, more preferably 6 μm or less, and the average particle size is 0. It is particularly preferable that the thickness is in the range of 5 to 5 μm (50 to 500 nm). The average particle size of the fired powder is preferably as small as possible, but it is considered that the lower limit is about 0.1 μm (10 nanometers) at the current technical level.

  In addition, if the scallop shells after firing are pulverized sufficiently after the shells of the scallop shells are sufficiently cooled (after cooling to room temperature (about 23 ° C.)), the crushed scallop shells The re-aggregation does not occur and the average particle size can be adjusted to be small, so that the antibacterial properties of the resin molded product become favorable, which is preferable.

  The raw material resin used in the production of the resin molded product of the present invention is not particularly limited, and various synthetic resins can be used. Polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, ABS resin, AS resin, Acrylic resin, polyurethane, polyamide, polyaceter, polycarbonate, polyester, or a mixture or modified product thereof can be suitably used. In some cases, it is also possible to use FRP (glass fiber reinforced resin). Moreover, it is also possible to make a resin molded product obtained by foaming the above-described resin using a foaming agent. In addition, among these synthetic resins, it is preferable to use those which are flexible when formed into a molded product and have a relatively high gas permeability, and use polyethylene or polypropylene which does not require various additives. Is more preferable.

  In addition, the method of adding the scallop baked powder in the raw material resin is not particularly limited, and the method of adding the scallop baked powder to the raw material resin monomer and then synthesizing the monomer to make a resin (so-called, Use a polymerization method), a method of preparing a so-called master batch having a high concentration and diluting and using the master batch, a method of adding a baked scallop powder into a molten resin, and the like. Can do. In addition, it is preferable to use the addition method at the time of polymerization because the dispersibility of the baked scallop powder in the resin becomes good.

  Furthermore, the amount of the scallop baked powder added is preferably in the range of 0.05% by mass or more and less than 20% by mass of the entire resin molded product, and more preferably 0.1% by mass or more and less than 10% by mass. Preferably, it is particularly preferably 0.2% by mass or more and less than 5% by mass. By adjusting the addition amount of the scallop baked powder within the range of 0.05% by mass or more and less than 20% by mass, it becomes possible to prevent the scallop baked powder from agglomerating in the raw resin, and the resin composition It is possible to improve the antibacterial property of the. If the amount of scallop baked powder added is less than 0.05% by mass, the antibacterial properties of the resin composition will be insufficient, and on the contrary, the amount of scallop baked powder added is 20% by mass. Above this, it is not preferred that any method is used, which not only makes it difficult to avoid agglomeration of the baked scallop powder, but also causes the original properties of the resin composition to deteriorate.

  In addition, the raw material resin contains a lubricant, an anti-blocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light-proofing agent, an impact resistance improving agent, and other antibacterial agents as long as the properties are not impaired. For example, various additives such as bamboo charcoal and activated carbon) can be included. In addition, when using bamboo charcoal and activated carbon together, it is preferable to use those addition amount less than the addition amount of the baking powder of a scallop, and to use in the range of 0.03 mass% or more and less than 15 mass%.

  Moreover, when a surfactant is added to the raw material resin, the antibacterial function of the baked scallop powder is higher due to the interaction with the moisture absorption function of the surfactant, and the antibacterial properties of the resin molded product are even better. Since it becomes a thing, it is preferable. As such surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorosurfactants and the like can be suitably used. Among them, it is preferable to use a nonionic surfactant having a high hygroscopic function, and examples of the nonionic surfactant include a pyralkylene glycol compound mainly composed of an adduct of polyalkylene oxide, an ester of a polyhydric alcohol, Examples include ethers of alcohol, fatty acid amides of alcohol amine, and the like. Specifically, polyethylene glycol, polypropylene glycol, polymethylaethylene glycol, copolymers of these glycols, monoesters, diesters or triesters of higher fatty acids, amides of higher fatty acids and alcohol amines, etc. are preferably used. it can. And it is preferable to add such a surfactant in the raw material resin within a range of 0.1 mass% or more and less than 10 mass% by mixing one or more kinds.

  Hereinafter, the resin molded product according to the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments of the examples and is appropriately changed without departing from the gist of the present invention. Is possible. Moreover, the physical property and the evaluation method of a characteristic in an Example and a comparative example are as follows.

[Antimicrobial properties]
A starch aqueous solution (concentration: 10% by mass) was dropped on the obtained sheet, and E. coli was dropped into the aqueous solution and left at 30 ° C. for 5.0 hours. It was. Then, sensory evaluation of the change in the number of the E. coli was performed in the following four stages.
◎ ・ ・ There was almost no change in the number of E. coli.
A slight increase (approximately 10 times or less) in the number of E. coli was observed.
Δ: An increase (approximately less than 100 times) in the number of E. coli was observed.
X: A large increase (approximately 100 times or more) in the number of E. coli was observed.

[transparency]
The transparency of the obtained polyethylene film was visually evaluated in the following four stages.
◎ ・ ・ Very transparent.
○ ・ ・ High transparency.
△ ・ ・ Transparency is slightly low.
× ·· Low transparency.

[Tensile properties]
The obtained polypropylene film was cut into a predetermined strip shape, conditioned for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and then using a tensile tester under the same conditions, and using JIS K- The film was conditioned in accordance with 7127 at a tensile speed of 200 mm / min (chuck distance = 100 mm), and the ratio of tensile stress to the corresponding strain within the tensile proportional limit was determined by the tensile modulus (Young's modulus: kgf / Mm ² ). And the tensile characteristic was evaluated in the following four steps from the numerical value of the tensile elastic modulus.
◎ ·· tensile modulus = 150kgf / mm ² or more ○ ·· tensile modulus of elasticity = 50kgf / mm ² or more 150kgf / mm less than ² △ ·· tensile modulus of elasticity = 50kgf / mm less than ²

<Manufacture of resin molded products>
The remaining scallop shells (about 100 kg) that had been used for edible shellfish were immersed in a chlorine-containing water tank (chlorine concentration: about 1,000 ppm) for a predetermined time (about 8 hours). Thereafter, the scallop shells were exposed to sunlight and dried sufficiently. Thereafter, the dried scallop shells were fired in a furnace at a temperature of about 1,100 ° C. for about 3 hours. Furthermore, the fired scallop shell powder was obtained by pulverizing the fired scallop shells with an ultra-fine pulverizer to an average particle size of about 1 μm.

  The fired powder of scallops obtained as described above was added to a polypropylene monomer, and the monomer was polymerized under predetermined conditions to obtain a polypropylene resin containing fired scallop powder. The amount of the scallop fired powder added was adjusted to about 8% by mass with respect to the entire polypropylene resin containing the scallop fired powder.

  The pelletized polypropylene resin composition is obtained by kneading and extruding the polypropylene resin containing the scallop shell powder obtained as described above while being melted by a 29 mmφ twin-screw extruder at a set temperature of 200 ° C. It was. Thereafter, the pellets were used to melt and extrude at a mold temperature of 230 ° C. using a single screw extruder equipped with a T die to produce a polypropylene sheet having a thickness of 1 mm. Further, the sheet was stretched 5 times and 10 times in the MD direction (longitudinal direction) and TD direction (width direction) at a stretching temperature of 155 ° C. by a tenter type biaxial stretching machine, and the thickness = about 100 μm of polypropylene. A film was obtained. Thereafter, the obtained polypropylene sheet and polypropylene film were used to evaluate the above three items of “antibacterial properties”, “transparency” and “tensile properties”. The evaluation results are shown in Table 1 together with the composition of the resin molded product.

[Examples 2 to 4]
Example 1 except that the amount of the scallop baked powder added to polypropylene was changed to 3.0% by mass, 15.0% by mass, and 20.0% by mass when preparing the polypropylene sheet and film, respectively. The polypropylene sheets and films of Examples 2 to 4 were prepared in the same manner as in the above. And the polypropylene sheet and polypropylene film of those Examples 2-4 were evaluated by the same method as Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Examples 5 and 6]
Similar to the preparation of Example 1, except that when the polypropylene sheet and film were prepared, the firing temperature and firing time of the scallop shell were changed to 700 ° C. × 7 hours and 1,300 ° C. × 1 hour, respectively. Thus, the polypropylene sheets and films of Examples 5 and 6 were prepared. The polypropylene sheets and polypropylene films of Examples 5 and 6 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Example 7]
A scallop baked powder tablet was molded by pressing the scallop shell baked powder obtained in the same manner as in Example 1 into a flat columnar shape while applying pressure by a predetermined weight (about 3 g). . On the other hand, a polypropylene homopolymer (chip shape) was obtained by polymerizing the same polypropylene monomer as in Example 1 without adding the baked scallop powder. After that, the scallop baked powder tablet and the polypropylene homopolymer were put into a predetermined hopper so that the added amount of the scallop baked powder was 8% by mass and sufficiently stirred. . After that, the sheet of Example 7 was obtained by kneading and extruding the polypropylene added with the scallop baked powder at a set temperature of 200 ° C. with a twin screw extruder (29 mmφ). Furthermore, the polypropylene film of Example 7 was obtained by stretching the sheet in the same manner as in Example 1. The polypropylene sheet and polypropylene film of Example 7 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Examples 8 and 9]
When preparing the polypropylene sheet and film, the addition amount of the baked scallop powder to the polypropylene was changed to 0.5% by mass and 1.0% by mass, respectively, as in the preparation of Example 1. The polypropylene sheets and films of Examples 8 and 9 were prepared. The polypropylene sheets and polypropylene films of Examples 8 and 9 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Example 10]
The polypropylene of Example 10 was prepared in the same manner as in the preparation of Example 1, except that when the polypropylene sheet and film were prepared, the firing temperature and firing time of the scallop shells were each changed to 700 ° C. × 1 hour. Sheets and films were prepared. The polypropylene sheet and polypropylene film of Example 10 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Example 11]
When preparing the polypropylene sheet and film, the amount of scallop baked powder added to polypropylene was changed to 3.0% by mass, and the scallop shell firing temperature and firing time were each 1,150 ° C. × The polypropylene sheet and film of Example 11 were prepared in the same manner as in Example 2 except that the time was changed to 4 hours. Then, the polypropylene sheet and polypropylene film of Example 11 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Example 12]
When preparing a polypropylene sheet and a film, an example was prepared in the same manner as in Example 2, except that 1.0% by mass of a nonionic surfactant (polyethylene glycol) was added to the raw material polypropylene resin. Twelve polypropylene sheets and films were prepared. The polypropylene sheet and polypropylene film of Example 12 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Example 13]
A polypropylene sheet and a film of Example 13 were prepared in the same manner as in Example 2 except that the average particle size was adjusted to about 0.5 μm when obtaining the scallop powder. The polypropylene sheet and polypropylene film of Example 13 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Example 14]
The fired powder of scallop shells obtained in the same manner as in Example 1 was added to a polystyrene monomer, and the monomer was polymerized under predetermined conditions to obtain a polystyrene resin containing fired powder of scallop shells. The amount of the scallop fired powder added was adjusted to about 3% by mass with respect to the entire polystyrene resin containing the scallop fired powder.

  And the pelletized polystyrene resin composition is obtained by kneading and extruding the scallop-baked polystyrene resin obtained as described above while being melted by a 29 mmφ twin screw extruder at a set temperature of 120 ° C. It was. Thereafter, by using the pellets, a polystyrene sheet having a thickness of 1 mm was produced by melt extrusion at a mold temperature of 125 ° C. by a single screw extruder equipped with a T die. Further, the sheet was stretched 5 times and 10 times in the MD and TD directions at a stretching temperature of 110 ° C. by a tenter type biaxial stretching machine to obtain a polystyrene film having a thickness of about 100 μm. Thereafter, the obtained polystyrene sheet and polystyrene film were used to evaluate the above three items of “antibacterial properties”, “transparency” and “tensile properties”. The evaluation results are shown in Table 1 together with the composition of the resin molded product.

[Comparative Example 1]
When polymerizing polypropylene, a polypropylene sheet and a polypropylene film of Comparative Example 1 were prepared in the same manner as in Example 1 except that the baked scallop powder was not added to the polypropylene monomer. Then, the polypropylene sheet and film of Comparative Example 1 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

[Comparative Example 2]
The remaining clam shell (approx. 100 kg) with the shellfish portion edible was immersed in a chlorine-containing water tank (chlorine concentration: about 1,000 ppm) for a predetermined time (about 5 hours). Thereafter, the clams shells were exposed to sunlight and dried thoroughly. Thereafter, the dried clam shells were fired in a furnace at a temperature of about 1,100 ° C. for about 3 hours. Furthermore, the clam shells after firing were pulverized with an ultra-fine pulverizer so that the particle size was about 1 μm, thereby obtaining a fired clam powder. Then, when polymerizing polypropylene, a fired clam powder was added to the polypropylene monomer instead of the fired powder of scallops (note that the added amount of the fired powder of clam is 8% by mass). Except for these changes, a polypropylene sheet and a polypropylene film of Comparative Example 2 were prepared in the same manner as in Example 1. Then, the polypropylene sheet and the polypropylene film of Comparative Example 2 were prepared in Example 1. The evaluation results are shown in Table 1 together with the composition of the polypropylene sheet and film.

  From Table 1, it can be seen that the polypropylene sheet of the example to which the baked scallop powder was added has very good antibacterial properties, and the transparency and tensile properties of the polypropylene sheet are also good. On the other hand, it can be seen that the polypropylene sheet of the comparative example to which the baked scallop powder was not added has poor antibacterial properties.

  Since the resin molded product according to the present invention exhibits excellent effects as described above, it can be suitably used for food packaging applications.

Claims (3)

  A scallop fired powder-containing resin-molded product, characterized in that a fired powder obtained by firing a scallop shell and then pulverizing it is added to the raw material resin.   The scallop fired powder-containing resin-molded product according to claim 1, wherein the amount of the scallop fired powder added to the raw material resin is 0.2% by mass or more and less than 5% by mass.   After adding the baked scallop shell powder into the resin raw material monomer, the resin raw material monomer containing the baked powder is polymerized to form a synthetic resin pellet, and the synthetic resin pellet is melt extruded and molded. A method for producing a molded resin product containing a baked scallop powder.