JP2014012752A - Multifunctional resin inclusion paper composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multifunctional resin inclusion paper composition that includes a powder antibacterial composition in which oxidation potential is low while antibacterial, deodorant, and freshness holding abilities of shell burning calcium are satisfactorily maintained; and further a production method of the same that can be used as a tableware for a food product for example in which a shape of a processed product thereof has multifunctionality.SOLUTION: A resin inclusion paper composition includes an antibacterial composition that mixes silica coating shell burning calcium with powder particles of a silica coating zinc oxide and a silica coating titanium oxide as a subsidiary component by at most of 15% by mass of each of the silica coating zinc oxide and the silica coating titanium oxide based on the total mass of the silica coating shell burning calcium.

Description

The present invention relates to a multifunctional resin-containing paper composition and a resin-containing paper composition containing a powder antibacterial composition having a low oxidation potential while sufficiently maintaining the antibacterial, deodorant, and freshness retaining ability of the calcined calcium shell Regarding integrally molded containers

In recent years, with the diversification of our eating habits and lifestyles, various foods have been distributed to the market and produced and shipped in large quantities by food-related manufacturers, etc. Are mass produced, mass consumed and mass discarded. Mass disposal has become a major social problem. Most of the containers are resin containers, which are incinerated or landfilled, causing global warming and soil contamination.

The awareness of people's environment is increasing, and the container and packaging processing methods and the awareness of contractors and consumers are also increasing due to the Containers and Packaging Recycling Law, and so much attention has been focused on containers of paper materials that can be disposed of as combustible materials. ing. However, water resistance, heat resistance, and durability are not sufficient, and therefore, a container of a resin-containing paper composition that can be disposed of as a combustible material has attracted attention, and its research and development has been made. In addition, in consideration of the safety of the container, there is a demand for a container packaging material that can inhibit the growth of bacteria and maintain the freshness of the food material.

With the research and development of the resin-containing paper composition, there is provided a resin-containing paper composition for molding which has a low combustion heat and good fluidity.

In the following prior art documents, these improve the physical properties and performance of the resin-containing paper composition to improve the quality during molding as well as environmental protection. However, the resin-containing paper composition having antibacterial, deodorizing, and food freshness maintaining effects, which are another plus effect for the resin-containing paper composition, is not well known. .

Japanese Patent Laid-Open No. 10-138241 Japanese Patent Application Laid-Open No. 11-222796 JP 2001-181511 A JP 2001-191327 A JP 2009-242299 A JP 2099-35309 A JP 2011-131508 A

The problem to be solved by the present invention is made for the purpose of providing a resin-containing paper composition excellent in the high antibacterial effect, deodorizing effect and sustainability of maintaining food freshness.

As means for solving the above-mentioned problems, the multifunctional resin-containing paper composition according to the present invention includes shell-fired calcium (calcium oxide) obtained by firing biologically-derived calcium at a high temperature with respect to the resin-containing paper composition, and the above-mentioned Calcium hydroxide hydrolyzed to calcium oxide is used. More preferably, the resin-containing paper composition is specially processed as a carrier for supporting the performance of shell calcined calcium as a secondary component in order to improve the water resistance and antibacterial performance. Zinc oxide and titanium oxide with added anti-bacterial properties, water resistance and antibacterial performance, antibacterial and deodorant properties are improved, and each particle is the finest particle and can be easily kneaded into resin-containing paper composition materials. An antibacterial composition excellent in performance and water resistance is contained.

The above-mentioned antibacterial composition is a composite powder obtained by coating fine powder of shell calcined calcium with fine powder silica (amorphous), recondensing particles while exhibiting sufficient antibacterial performance. A composite powder containing zinc oxide and titanium oxide (anatase type and rutile type) coated with fine powder silica (amorphous) as secondary components to prevent body formation and supplement water-resistant antibacterial performance It is an antibacterial composition blended with calcined calcium.

That is, the antibacterial composition is an antibacterial agent having improved antibacterial performance and water-resistant antibacterial performance, in which recombination aggregates of fine powder particles of silica-coated shell shell calcined calcium, silica-coated zinc oxide and silica-coated titanium oxide are not easily formed. It is an antibacterial composition that has improved water resistance antibacterial performance and antibacterial properties of calcium oxide and calcium hydroxide.

Antibacterial composition made by mixing silica-coated shellfish calcined calcium with silica-coated zinc oxide and silica-coated titanium oxide, which are secondary components, makes the particles difficult to recondensate, making the particle size and particle size uniform. Can be planned. The characteristics of the fine particles are that the surface area per mass is the same. The larger the surface area, the lower the bulk specific gravity, fluidity, etc., and the higher the activity, reactivity, and solubility. Therefore, the water and antibacterial performance is dramatically improved as compared with the conventional antibacterial processed product using calcined shell calcium. The sustainability is also the same.

In addition, it is cheaper than other inorganic antibacterial agents and organic antibacterial agents, and the antibacterial composition is extremely fine and does not recondense.・ Fibers, Japanese paper, etc.) are easy to knead and have a feature that the antibacterial composition is hardly dispersed in the manufacturing process of the antibacterial processed product.

In addition, shell calcined calcium, zinc oxide, and titanium oxide are highly safe substances so that there is little concern about adverse effects on the human body and there is almost no adverse environmental impact.

Hereinafter, the antibacterial composition used in the present invention will be described in detail. First, calcium hydroxide already proposed by the present inventor is used as the calcined calcium shell shell. In the present invention, as the calcium hydroxide, fine powder calcium hydroxide obtained by firing a shell or a shell at a high temperature is used. When mineral-derived calcium hydroxide is used, because of its specific gravity and hardness factors, it may cause poor dispersion or change in physical properties of processed products when blended into processed products. In the present invention, biological scallop shells are used. To do. The organism-derived scallop shell is fired at a high temperature of about 830 ° C. to about 1,200 ° C. in a special high-temperature firing decomposition furnace, which causes the scallop shell to change its physical properties to calcium oxide. The most desirable high temperature in the temperature range is around 1,100 ° C., and baking is performed at that temperature for about 1 hour. The fine powder calcium hydroxide obtained by calcining the shell or shell of the present invention at a high temperature is produced by the special hydration method on the calcium oxide obtained by calcining. Specifically, 15% by mass of water is added to the total mass of calcined calcium oxide of scallop shells. As for the blending ratio at that time, 10% by mass is initially added and 5% by mass is added after evaporation. The calcium hydroxide obtained by calcining and adding water is made into a fine powder having an average particle size of 0.1 μm to 13 μm with a jet mill grinder. For this reason, calcium hydroxide, which is a strongly basic (pH≈12.7 to 13.2) fine powder having a bactericidal effect, an antibacterial effect, and a deodorizing effect, is used. The calcium hydroxide has a calcium hydroxide content of 90% or more.

The finely powdered calcium hydroxide (particle size / particle size 0.1 μm to 13 μm) obtained by the above-mentioned production method is likely to recombine with each other and easily form an aggregate. Therefore, in order not to make the recombination condensate, 0.2 mass% to 5 mass% of silica is added and mixed by stirring. Particularly suitable is a coating with a mass ratio of 0.5% to 3% by mass.

Examples of the fine particle silica that can be used in the present invention include SS-30P, SS-50F, E-200A (Tosoh Silica Co., Ltd.) and the like. Further, the silica is limited to an amorphous one.

Silica-coated shell calcined calcium can be obtained routinely using the fine powder silica described above. The silica-coated shell calcined calcium is pulverized again with a special air jet mill, and the average particle size and particle size of the silica-coated shell calcined calcium accumulated in the air dust collector is refined to 0.5 μm to 1.5 μm. The calcined shell shell calcium is the main component of the present invention.

Zinc oxide used as a supporting agent for the silica-coated shell calcined calcium is used as a secondary component in the silica-coated shell calcined calcium. The fine zinc oxide can be obtained by conventional methods such as the French method and the American method. Examples of commercially available fine zinc oxide particles that can be used in the present invention include FINEX-25, FINEX-50, and FINEX-75 (Sakai Chemical Industry Co., Ltd.).

However, in consideration of cost, zinc oxide particles K8405 (Kanto Chemical Co., Inc.) and the like can be used in addition to the fine zinc oxide. Although a re-grinding process must be performed, there is a merit that it is considerably cheaper when considering the production cost effectiveness.

In order to obtain a silica-coated zinc oxide using fine particle zinc oxide, the fine particle zinc oxide is preferably 0.2% by mass to 5% by mass, and particularly preferably 0.5% by mass to 3% by mass. The coating is carried out at a ratio, pulverized again with a special air jet mill, and the product accumulated in the air dust collector is used.

When the proportion of the fine particle silica to the fine particle zinc oxide is blended to 10% by mass or more, the antibacterial properties and catalytic effects, which are the characteristics of zinc oxide, are reduced. What is blended in 0.5 mass% to 5 mass% is used.

Another composition used as a supporting agent for the silica-coated shell calcined calcium as a secondary component in the silica-coated shell calcined calcium uses fine particle titanium oxide (anatase type, rutile type).

Commercially available products of fine particle titanium oxide used as a supporting agent for silica coated shell calcined calcium as a secondary component in silica coated shell calcined calcium include, for example, titanium (IV) anatase type 40167-01 and titanium (IV) rutile type 40982. -00 (Kanto Chemical Co., Inc.).

In this embodiment, fine particle titanium oxide (anatase type) is used, but fine particle titanium oxide (rutile type) can also be used depending on the external use.

A silica-coated titanium oxide is obtained by using the fine particle titanium oxide (anatase type) or fine particle titanium oxide (rutile type). The fine particle titanium oxide is coated with fine particle silica preferably at 0.2% by mass to 5% by mass, particularly preferably 0.5% by mass to 3% by mass. Then, pulverize and use the material accumulated in the air dust collector.

If the proportion of the fine particle silica to the fine particle titanium oxide is compounded to 10% by mass or more, the antibacterial properties and catalytic effects, which are the characteristics of the titanium oxide, are reduced. What was blended in 0.2 mass% to 5 mass% is used.

In the present invention, the blending ratio of the antibacterial composition containing powder particles of silica-coated shell calcined calcium, silica-coated zinc oxide, and silica-coated titanium oxide is determined based on the total mass of the antibacterial composition powder. Zinc oxide and silica-coated titanium oxide are mixed to a maximum of 15% by mass. When the blending ratio of the silica-coated shell shell calcined calcium is over 5% by mass, the ratio of the bactericidal effect, the antibacterial effect, the deodorizing effect, etc. will not change much.

Therefore, 5% by mass of powder particles of silica-coated zinc oxide and silica-coated titanium oxide are mixed with respect to the total mass of the silica-coated shells calcined calcium, and the mixing ratio is 5 parts by mass divided into 3 times. To do. Thereafter, stirring is performed for 5 to 10 minutes in a high-speed stirrer to obtain fine powder accumulated using an air dust collector.

In this manner, an antibacterial composition in which silica-coated shellfish calcined calcium is mixed with silica-coated zinc oxide and silica-coated titanium oxide can be obtained. The specific particle size and particle size of the antibacterial composition can be appropriately selected according to the form of the antibacterial processed product, and the mixing ratio of silica-coated zinc oxide and silica-coated titanium oxide, which are secondary components, is also particularly high. It is not limited.

This antibacterial composition can be manufactured according to the said manufacturing method. In such a production method, by performing the blending operation of the blend ratio of silica-coated zinc oxide and silica-coated titanium oxide with respect to the silica-coated shell-fired calcium, it is possible to exhibit excellent antibacterial properties derived from the shell-fired calcium and A practical antibacterial composition in which no condensate is observed is obtained, and can be used for various external uses (pharmaceuticals, quasi drugs, cosmetics, skin cleansing agents, etc.) and antibacterial processed products.

In addition, the antibacterial composition can contain various components used in various external compositions as necessary as long as the desired effects of the present invention are not impaired. Specifically, various medicinal components, moisturizers, surfactants, preservatives, colorants, fragrances, oils and the like can be contained as necessary.

In the present invention, the shell-calcined calcium (calcium oxide fine powder) and the calcium oxide hydrated (calcium hydroxide fine powder) are used for the resin-containing paper composition. In contrast, the fine powder containing zinc oxide in calcium hydroxide, the fine powder containing titanium oxide in calcium hydroxide, and the fine powder containing zinc oxide and titanium oxide in calcium hydroxide. Is contained.

The multifunctional resin-containing paper composition according to the present invention maintains the antibacterial and deodorizing ability of the resin-containing paper composition considering the global environment while maintaining the freshness of the food material while inhibiting the growth of bacteria. It can also have an effect that can be done.

Hereinafter, the multifunctional resin-containing paper composition according to the present invention will be described in detail. The present invention is not limited to the following embodiments and experimental examples.

In the multifunctional resin-containing paper composition of the present invention, the resin-containing paper composition as a base material has a fine paper powder having an average particle size of 20 μm or more and less than 45 μm in a mass ratio of 55 mass% to 75 mass%. Polypropylene, polyethylene, polystyrene, olefinic elastomer, nylon, polybutylene terephthalate, polyethylene terephthalate, acrylonitrile-styrene copolymer synthetic resin, acrylonitrile-butadiene-styrene copolymer synthetic resin, thermoplastic resin, etc. It is a resin-containing paper composition obtained by mixing with the resin.

In addition, the said mass ratio means the ratio with respect to the total mass of a resin containing paper composition. When the fine paper powder content is less than 50% by mass, the expression of functions such as strain absorbability during molding based on the flexible structure of the paper powder is suppressed, and environmental performance is also reduced. On the other hand, when the fine paper powder content exceeds 60% by mass, paper powder that does not exhibit dissolution fluidity at the molding temperature hinders the fluidity of the resin, increases the possibility of molding defects, and increases the molding pressure. Energy consumption increases and environmental performance decreases.

The resin is polyethylene, polypropylene, olefin elastomer, polystyrene, AS resin (acrylonitrile-styrene copolymer synthetic resin), ABS resin (acrylonitrile-butadiene-styrene copolymer synthetic resin), nylon, PBT (polybutylene terephthalate), PET ( Polyethylene terephthalate) and thermoplastic resin, and the mass ratio is 25% by mass or more and less than 45% by mass.

In order to improve the kneadability between the fine paper powder and the resin, it is preferable to add a surface modifier and perform a surface modification treatment. The surface modifier improves kneadability by enhancing the interaction between paper dust and resin.

The surface modifier is preferably contained in the range of 0.1 wt% to 5 wt%. Particularly preferred is a content in the range of 0.5 mass% to 3 mass%. If the addition amount of the mass ratio surface modifier is less than 0.1% by weight, a sufficient kneadability improvement effect cannot be obtained, and if it exceeds 5% by weight, there is a high possibility that adverse effects such as exudation on the surface of the molded product will occur. Become.

Moreover, by containing a resin modifier, interaction with paper powder is improved and kneadability is made favorable. The content of the resin modifier is preferably contained in the range of 0.5% by weight to 10% by weight. More preferably, it is contained in the range of 3% by mass to 7% by mass. If the addition amount of the resin modifier is less than 0.5% by weight, the modification effect is poor, and if it exceeds 10% by weight, the inherent properties of the resin such as rigidity and strength may be impaired.

By molding the resin-containing paper composition into pellets from the above inspection and applying it to the raw material, the kneading of the resin-containing paper composition pellets and the antibacterial composition resin kneaded pellets becomes easy, and the multifunctional resin-containing composition of the present invention is contained. A paper composition can be produced.

Next, the blending ratio of the antibacterial composition resin kneaded pellets with respect to the resin-containing paper composition that is the base material of the multifunctional resin-containing paper composition in the present invention will be described.

Here, the base material of the antibacterial composition resin kneaded pellets is limited to polypropylene, and the implementation is performed. First, 30% by mass of the antibacterial composition is blended with polypropylene as a base material and kneaded with a resin kneader. The mass ratio at this time means the ratio of the base material to the total mass of polypropylene. Moreover, the content of the antibacterial composition can be arbitrarily adjusted.
In this way, antibacterial composition resin kneaded pellets are produced.

As the antibacterial composition, shell calcined calcium (calcium oxide fine powder) and calcium hydroxide fine powder obtained by adding water to the calcium oxide are used. The antibacterial composition resin in the same manner as described above in any of the fine powder containing zinc oxide and the fine powder containing titanium oxide in the calcium hydroxide and the fine powder containing zinc oxide and titanium oxide in the calcium hydroxide Kneaded pellets can be produced.

The antibacterial composition resin kneaded pellets obtained by the above production method are kneaded and blended with the resin-containing paper composition pellets and a resin kneader. At this time, the antibacterial composition is molded and kneaded so as to have a content of 5% by mass or more and less than 15% by mass. The mass ratio at this time means a ratio to the total mass of the antibacterial composition resin kneaded pellets and the resin-containing paper composition pellets.

The present invention will be specifically described with reference to examples, but the technical scope of the present invention is not intended to be limited by these examples. Moreover, content is the mass% with respect to the inclusion object unless there is particular notice.

[Efficacy test]
(1) Antibacterial effect MIC value test [Minimum growth inhibitory concentration measurement method I (antibacterial product technology council)] This is a method for measuring the minimum necessary amount of antibiotics (in vitro) to inhibit bacterial growth. As a result of diluting, culturing with bacteria, and determining the concentration (ppm) of which the growth of the bacteria is controlled (minimum growth inhibitory concentration)], the resin contained in the antibacterial composition The multifunctional resin-containing paper composition having a blending ratio of the containing paper composition of 5% by mass showed significantly more antibacterial performance than the resin-containing paper composition. [Table 1]

(2) Deodorization test (gas removal performance evaluation test)
The method defined by the deodorant processed fiber product certification standards As a result of the application to the fiber evaluation technology council, the multifunctional resin-containing paper composition having an antibacterial composition containing resin-containing paper composition content of 5% by mass The odor eliminating performance appeared more markedly than the resin-containing paper composition. [Table 2]

[Prototype comparison evaluation method]
(3) JIS Z 2801, 5.2 (antibacterial test)
The antibacterial test is performed using a test piece of a multifunctional resin-containing paper composition containing 5% by mass of the resin-containing paper composition containing the antibacterial composition and a resin-containing paper composition (containing no antibacterial composition). The evaluations made are described below. Test bacteria: Staphylococcus aureus NBRC12732, Escherichia coli Escherichia Coli NBRC 3972, the result is a multifunctional resin-containing paper composition containing 5% by mass of the resin-containing paper composition in the antibacterial composition Was significantly more antibacterial than the resin-containing paper composition. [Table 3]

The sample used in [Table 1] is a resin-containing paper composition (antibacterial composition) containing 5% by mass of secondary component silica-coated zinc oxide and silica-coated titanium oxide based on the total weight of the calcined calcium shellfish shell calcined calcium of the present invention. Resin plate pieces (5 cm × 5 cm). As a comparative sample, a resin plate piece (5 cm × 5 cm) of a resin-containing paper composition (containing no antibacterial composition) was used.

The sample used in [Table 2] is a resin-containing paper composition (antibacterial composition) containing 5% by weight of each of the secondary components silica-coated zinc oxide and silica-coated titanium oxide based on the total weight of the calcined calcium shellfish shell calcined calcium of the present invention. The mechanically pulverized powder was used. As a comparative sample, a mechanically pulverized powder of a resin-containing paper composition (containing no antibacterial composition) was used.

The sample used in [Table 3] is a resin-containing paper composition (antibacterial composition) containing 5% by mass of each of the secondary components silica-coated zinc oxide and silica-coated titanium oxide based on the total weight of the calcined calcium shellfish shell calcined calcium of the present invention. Resin plate resin piece (5 cm × 5 cm). As a comparative sample, a resin plate of a resin-containing paper composition (containing no antibacterial composition) was used.

[Food freshness preservation test] (Change over time)
Multifunctional resin-containing paper composition in which the proportion of silica-coated zinc oxide and silica-coated titanium oxide is 5% by mass with respect to the silica-coated shell calcined calcium, with respect to time-dependent changes in bacterial growth and off-flavor generation using cooked rice A bowl with a processed lid showed a remarkable effect in antibacterial performance and generation of a strange odor than a bowl with a resin-containing paper composition-processed lid. As an inspection method, after confirming that steam does not come out after 2 hours have passed since cooking rice, add 150g each to a bowl with a multifunctional resin-containing paper composition processing lid and a bowl containing a resin-containing paper composition processing lid The lid was put on and stored at room temperature (20 ° C. ± 15 ° C.) and normal humidity (48% to 85%). [Table 4]

［表４］に用いた試料は、樹脂含有紙組成物（抗菌組成物無配合）で加工した蓋付どんぶりを用いた。比較試料は本発明のシリカ被膜貝殻焼成カルシウム総重量に対して副次成分シリカ被膜酸化亜鉛、シリカ被膜酸化チタンを各５質量％配合した樹脂含有紙組成物（抗菌組成物配合）で加工した蓋付どんぶりを用いた。（共に常温常湿保存）

The sample used in [Table 4] was a bowl with a lid processed with a resin-containing paper composition (without antibacterial composition). The comparative sample is a lid processed with a resin-containing paper composition (containing an antibacterial composition) containing 5% by mass of each of the secondary components silica-coated zinc oxide and silica-coated titanium oxide based on the total weight of the silica-coated shell calcined calcium of the present invention. A cooked bowl was used. (Both stored at room temperature and humidity)

Claims (9)

A resin-containing paper composition containing fine powdered calcium hydroxide obtained by firing shells or shellfish at a high temperature. A resin-containing paper composition comprising zinc oxide powder particles in fine powdered calcium hydroxide obtained by firing shells or straw at high temperature. A resin-containing paper composition comprising fine powder calcium hydroxide obtained by firing shells or shellfish at high temperature and powder particles of titanium oxide. A resin-containing paper composition comprising zinc oxide powder particles and titanium oxide powder particles in fine powder calcium hydroxide obtained by firing shells or shellfish at a high temperature. The particle size and particle size of finely powdered calcium hydroxide obtained by firing shells or shellfish at a high temperature is 0.5 μm to 1.5 μm on average. A resin-containing paper composition containing silica-coated zinc oxide and silica-coated titanium oxide powder particles. When the silica-coated shell calcined calcium is added 0.2 mass% to 5 mass% of fine-particle silica and mixed with stirring, it is particularly preferable to coat so as to be coated at a mass ratio of 0.5 mass% to 3 mass%. A resin-containing paper composition containing an antibacterial composition. The silica-coated zinc oxide is characterized in that the fine particle silica is preferably coated in a mass ratio of 0.2% by mass to 5% by mass, particularly preferably 0.5% by mass to 3% by mass with respect to the fine particle zinc oxide. A resin-containing paper composition containing an antibacterial composition which is a secondary component. The silica-coated titanium oxide is characterized in that the fine particle silica is preferably coated at a mass ratio of 0.2% by mass to 5% by mass, particularly preferably 0.5% by mass to 3% by mass with respect to the fine particle titanium oxide. Is a secondary component. The resin-containing paper composition is characterized in that 5 mass% of powder particles of silica-coated zinc oxide and silica-coated titanium oxide are mixed with respect to the total mass of the silica-coated shell calcined calcium.