JP5707836B2 - Resin tableware - Google Patents

Description

The present invention relates to a resin tableware.

Conventionally, ceramic tableware, glass tableware, resin tableware and the like have been widely used as tableware such as bowls, dishes, and bowls.

In particular, resin tableware is light and hard to break, and can be obtained at a low price with a uniform shape and quality, so it is widely used in large-scale facilities such as schools, hospitals, and company cafeterias. Yes.

As a material of the resin tableware, a material having heat resistance and water resistance is desired, and melamine resin, polypropylene resin and the like are usually used. For example, Patent Document 1 discloses a tableware formed by molding a polypropylene resin, the surface of which is subjected to plasma treatment and then coated with a polyurethane resin paint. However, there has never been a resin tableware using a fluororesin.

By the way, since tableware is repeatedly washed and used, it is required to have antifouling properties for facilitating washing and the like. As tableware with improved antifouling properties, for example, Patent Document 2 discloses an antifouling method in which a surface layer containing photocatalytic oxide particles, silicone, and a water-repellent fluororesin is formed on the surface of a substrate such as glass. Tableware is disclosed. Further, Patent Document 3 discloses a coated article including a glass substrate and an antifouling non-adhesive coating attached to the surface of the substrate. However, glass tableware and earthenware tableware have problems such as being easily broken or chipped by an impact, and being heavy.

JP 2006-116220 A Japanese Patent Laid-Open No. 10-137098 Special table 2010-510158 gazette

Resin tableware can be volatilized when heated or when hot food is placed on it, such as relatively low molecular weight components (oligomers), unreacted monomers, plasticizers, and pyrolysis substances. It has been found by the present inventors that the components that are likely to be released may be released, giving off odors, and causing these volatile components to adhere to food.

The present invention provides a tableware that can suppress the release of volatile components from the tableware and can take a meal more comfortably.

The present invention is a resin tableware characterized in that the weight loss rate by heating is 10 ppm / day or less.

The resin tableware of the present invention is preferably made of a fluororesin.

The resin tableware of the present invention preferably contains a pigment.

The resin tableware of the present invention preferably has a specific gravity of 1.1 to 3.0.

The resin tableware of the present invention is also preferably composed of the above-mentioned fluororesin and resin (excluding the fluororesin).

It is preferable that the said fluororesin exceeds 50 mass% with respect to the total mass of a fluororesin and resin (however, except a fluororesin).

The resin (excluding the fluororesin) is preferably at least one selected from the group consisting of melamine resin, polypropylene resin, and polycarbonate resin.

The fluororesin includes polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, polychlorotrifluoroethylene, Chlorotrifluoroethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer, and It is preferably at least one selected from the group consisting of polyvinyl fluoride.

Since the tableware of the present invention has the above-described configuration, it is possible to suppress the release of volatile components, and thus it is possible to suppress the generation of odors and the components volatilized from the tableware from adhering to food. Therefore, a meal can be taken more comfortably.

(A) is a cross-sectional schematic diagram which shows the shape of the dish shape | molded in Examples 1-6, (b) is a plane schematic diagram.

The resin tableware of the present invention has a heating weight loss rate of 10 ppm / day or less. In the resin tableware of the present invention, components having a relatively low molecular weight (oligomers), volatile components such as unreacted monomers, plasticizers, and pyrolysis substances are released from the resin tableware, and the resin tableware can be used during meals. Odor is generated, and components that have volatilized in the food are attached and the taste can be prevented from changing. The heating weight loss rate is preferably 8 ppm / day or less, and more preferably 6 ppm / day or less.
The weight loss by heating (Z) is obtained by preparing a sample obtained by cutting out 3-5 g of the entire resin tableware or a part of the resin tableware, and heating it at 80 ° C. for 1 day (unheated weight (W ₀ )) ( The weight (W ₁ ) after heating for 24 hours and the weight (W ₁₀ ) after heating for 10 days at 80 ° C. (after heating for 240 hours) were measured, and the following formula (1):

により求めた値である。なお、本発明の樹脂製食器が２種以上の樹脂からなるものである場合、樹脂製食器の全部に対して上記測定を行うことが好ましい。８０℃での加熱は、例えば、熱風循環炉を用いて行うことができる。熱風循環炉としては、アドバンテック東洋株式会社製の送風定温乾燥器（型番：ＤＲＭ４２０ＤＡ）を用いることができる。
加熱重量減率は、加熱により遊離する物質の量を、１日あたりの遊離量に換算した値である。なお、加熱を開始してから１日間（２４時間）の重量の変化を除いて加熱重量減率を求めるのは、樹脂製食器に含まれる水分の影響を排除するためである。

It is the value calculated | required by. In addition, when the resin tableware of this invention consists of 2 or more types of resin, it is preferable to perform the said measurement with respect to all the resin tableware. Heating at 80 ° C. can be performed, for example, using a hot air circulating furnace. As the hot-air circulating furnace, an air constant temperature dryer (model number: DRM420DA) manufactured by Advantech Toyo Co., Ltd. can be used.
The weight loss rate by heating is a value obtained by converting the amount of a substance liberated by heating into a liberated amount per day. The reason for obtaining the weight loss rate by excluding the change in weight for one day (24 hours) after the start of heating is to eliminate the influence of moisture contained in the resin tableware.

The resin tableware of the present invention is a container or utensil with which food comes into direct contact, for example, a tea bowl, a plate, a bowl, a chopstick, a knife, a fork, or a spoon.

The resin tableware of the present invention is preferably made of a fluororesin. By being made of a fluororesin, it is possible to further suppress the liberation of easily volatile components from the resin tableware.
Moreover, since it is lightweight compared with glass tableware or ceramic tableware, it is excellent in handling property. Furthermore, since it is strong against impact and hard to break, it is excellent in safety.
And compared with the resin tableware which does not contain a fluororesin, specific gravity becomes large and it is easy to sink in water. Therefore, cleaning becomes easy.
Moreover, by using a fluororesin, it is excellent in antifouling property and easy to clean. Furthermore, it has excellent chemical resistance against detergents.

The finding that by using a fluororesin, it is possible to suppress the release of easily volatile components from resin tableware is a new finding found by the present inventors.

The fluororesin is preferably 50% by mass or more based on the total mass of the resin tableware. Moreover, it is more preferable to exceed 50 mass%, it is still more preferable to exceed 60 mass%, it is still more preferable to exceed 70 mass%, and it is especially preferable to exceed 80 mass%. When there is too little quantity of a fluororesin, there exists a possibility that liberation of the component volatilized from resin tableware cannot fully be suppressed.

The fluororesin includes tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride [VF], hexafluoropropylene [HFP], hexafluoroisobutene [HFIB], A monomer represented by CH ₂ = CX ¹ (CF ₂ ) _n X ² (wherein X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10), Perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms), and CF ₂ = CF— OCH ₂ -Rf ² (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) alkyl perfluorovinyl ether derivatives, trifluoroethylene represented by Trifluoro propylene, tetrafluoropropylene, pentafluoropropylene, trifluoperazine Rob Ten, and preferably has at least one fluorine-containing monomer in based polymerization unit selected from the group consisting of tetrafluoroethylene isobutene. The fluororesin may have a polymer unit based on at least one monomer selected from the group consisting of ethylene [Et], propylene [Pr], and alkyl vinyl ether as a fluorine-free monomer. Good.
More preferably, the fluororesin is a polymer containing polymerized units based on at least one monomer selected from the group consisting of TFE, HFP, PAVE, CTFE, VdF and VF. The fluororesin is also preferably a copolymer having a polymerization unit based on Et as a fluorine-free monomer.

In the present specification, the “polymerized unit” means a part on the molecular structure of the fluororesin and a part based on the corresponding monomer.

The fluororesin includes polytetrafluoroethylene [PTFE], TFE / HFP copolymer [FEP], TFE / PAVE copolymer [PFA], Et / TFE copolymer, polychlorotrifluoroethylene [PCTFE], CTFE / At least one selected from the group consisting of TFE copolymer, Et / CTFE copolymer, polyvinylidene fluoride [PVdF], TFE / VdF copolymer, VdF / HFP copolymer, and polyvinyl fluoride [PVF]. Preferably it is a seed. In the present specification, as described above, when “TFE / HFP copolymer” is described, a polymerization unit based on TFE (TFE unit) and a polymerization unit based on HFP (HFP unit) are included. It means that it is a copolymer containing. The same applies to other copolymers.

PTFE may be a TFE homopolymer or a modified PTFE. In the present specification, the above-mentioned “modified PTFE” means a product obtained by copolymerizing a small amount of a comonomer (modifier) with TFE so as not to impart melt processability to the obtained copolymer.

The modifier in the modified PTFE is not particularly limited as long as it can be copolymerized with TFE. For example, HFP and other perfluoroolefins; CTFE and other chlorofluoroolefins; trifluoroethylene and VdF and other hydrogen-containing materials Perfluorovinyl ether; perfluoroalkylethylene such as perfluorobutylethylene; ethylene and the like. Moreover, 1 type may be sufficient as the modifier used, and multiple types may be sufficient as it.

It does not specifically limit as perfluoro vinyl ether used as a modifier, For example, following general formula (I):
_{CF 2 = CF-ORf (I} )
(Wherein Rf represents a perfluoro organic group), and the like. In the present specification, the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoro organic group may have ether oxygen.

As the perfluorovinyl ether used as the modifier, for example, perfluoro (alkyl vinyl ether) [PAVE] in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (I) is preferable. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

In the modified PTFE, the proportion (mass%) of the modifier in the total amount of the modifier and TFE is usually preferably 1% by mass or less, and more preferably 0.001 to 1% by mass.

In the FEP, the HFP unit is more than 2% by mass, preferably 20% by mass or less, and more preferably 6 to 15% by mass.

As PAVE in said PFA, what has a C1-C6 alkyl group is preferable, and PMVE, PEVE, or PPVE is more preferable. The PFA has a PAVE unit of more than 2% by mass, preferably 8% by mass or less, and more preferably 2.5 to 5% by mass.

The FEP or PFA may be further polymerized with other monomers as long as it has the above-described composition. Examples of the other monomer include PAVE in the case of the FEP, and HFP in the case of the PFA. The said other monomer can use 1 type (s) or 2 or more types.

The other monomer to be polymerized with the FEP or PFA varies depending on the type, but it is usually preferably 1% by mass or less of the mass of the fluororesin. A more preferred upper limit is 0.5% by mass, and a still more preferred upper limit is 0.3% by mass.

The TFE / VdF copolymer preferably has a TFE unit: VdF unit molar ratio of 45 to 85/55 to 15, more preferably 50 to 80/50 to 20. The TFE / VdF copolymer is a copolymer including a polymer unit based on VdF and a polymer unit based on TFE, and may have a polymer unit based on another fluorine-containing monomer. For example, a TFE / VdF / HFP copolymer is also a preferred form.

The Et / TFE copolymer preferably has an Et unit: TFE unit molar ratio of 20-80: 80-20. If the Et unit content is too small, the productivity may be poor, and if the Et unit content is too large, the corrosion resistance may deteriorate. More preferably, the molar ratio of Et unit: TFE unit is 35-55: 65-45. The Et / TFE copolymer is a copolymer including a polymerized unit based on TFE and a polymerized unit based on Et, and may have a polymerized unit based on another fluorine-containing monomer.

The Et / TFE copolymer is at least one selected from the group consisting of other fluorine-containing monomers and monomers containing no fluorine in addition to Et units and TFE units as a monomer component. It is also one of the preferable forms that it has a monomer unit based on a seed monomer. The other fluorine-containing monomer is not particularly limited as long as it can be added to both ethylene and TFE, but a fluorine-containing vinyl monomer having 3 to 10 carbon atoms is easy to use. For example, hexafluoroisobutylene, _{CH 2 = CFC 3 F 6 H} , HFP and the like. Among them, the following general formula:
CH ₂ = CH-Rf ⁵
A fluorine-containing vinyl monomer represented by the formula (wherein Rf ⁵ represents a perfluoroalkyl group having 4 to 8 carbon atoms) is also one preferred form. Moreover, as a monomer which does not contain fluorine at all, the following general formula:
CH ₂ = ^{CH-R 4}
(In the formula, R ⁴ is not particularly limited in carbon number, and may contain an aromatic ring, and may contain a carbonyl group, an ester group, an ether group, an amide group, a cyano group, a hydroxyl group, or an epoxy group. R ⁴ may not be fluorine.
In addition, the Et / TFE copolymer is an Et / TFE / HFP copolymer, which is one of the preferred embodiments. Further, other fluorine-containing monomers (excluding HFP) or fluorine are used at all. You may have a monomer unit based on the monomer which does not contain. The monomer other than ethylene and TFE is preferably 10 mol% or less, and more preferably 5 mol% or less of the total monomer component of the copolymer composed of ethylene and TFE. Et unit: TFE unit: The molar ratio of monomer units based on other fluorine-containing monomers or monomers not containing fluorine at all is 20-60: 80-20: 0.5-10. Preferably there is.

The above-mentioned PCTFE is a polymer whose polymer units are substantially composed only of CTFE units.

In the CTFE / TFE copolymer, the molar ratio of CTFE units to TFE units is preferably CTFE: TFE = 2 to 98:98 to 2, more preferably 5 to 90:95 to 10, More preferably, it is 20-90: 80-10.

The CTFE / TFE copolymer is preferably a copolymer comprising CTFE, TFE, and a monomer copolymerizable with CTFE and TFE. Monomers copolymerizable with CTFE and TFE include ethylene, VdF, HFP, CH ₂ = CX ¹ (CF ₂ ) _n X ² (wherein X ¹ is H or F, X ² is H, F or Cl, n is an integer of from 1 to 10.) the monomer represented by, PAVE, _{and, CF 2 = CF-OCH 2} -Rf 3 ( wherein, Rf ³ is a perfluoroalkyl of 1 to 5 carbon atoms An alkyl perfluorovinyl ether derivative represented by the following formula :), among which at least one selected from the group consisting of ethylene, VdF, HFP and PAVE is preferable, and it is PAVE. More preferred. Examples of PAVE include those described above. The molar ratio of the total polymerized units of CTFE units and TFE units and monomer units copolymerizable with CTFE and TFE is preferably 90 to 99.9: 10 to 0.1.

In the Et / CTFE copolymer, the molar ratio of Et units to CTFE units is preferably Et: CTFE = 30 to 70:70 to 30 and more preferably 40 to 60:60 to 40.

The PVdF is a polymer whose polymerization units are substantially composed only of VdF units.

The VdF / HFP copolymer preferably has a molar ratio of VdF units to HFP units of 45 to 85/55 to 15, more preferably 50 to 80/50 to 20, still more preferably 60 to 80 / 40-20. The VdF / HFP copolymer is a copolymer including a polymer unit based on VdF and a polymer unit based on HFP, and may have a polymer unit based on another fluorine-containing monomer. For example, VdF / HFP / TFE copolymer is also a preferred form.

As the VdF / HFP / TFE copolymer, a VdF / HFP / TFE molar ratio of 40 to 80/10 to 35/10 to 25 is preferable.

The PVF is a polymer whose polymer units are substantially composed of only VF units.

The fluororesin is at least one polymer selected from the group consisting of PVdF, Et / TFE copolymer and Et / CTFE copolymer from the viewpoint of good moldability and mechanical strength. preferable. More preferably, it is PVdF.

The fluororesin is preferably at least one polymer selected from the group consisting of PTFE, PFA and FEP from the viewpoint of excellent antifouling properties.

The fluororesin is also preferably a melt processable fluororesin. Examples of the melt processable fluororesin include FEP, PFA, Et / TFE copolymer, PCTFE, CTFE / TFE copolymer, Et / CTFE copolymer, PVdF, TFE / VdF copolymer, and VdF / HFP copolymer. It is preferably at least one selected from the group consisting of a polymer and PVF. By using such a melt processable fluororesin, molding can be easily performed.

The fluororesin is preferably at least one polymer selected from the group consisting of PVdF, Et / TFE copolymer, and PFA.

The content of each monomer unit of the copolymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The fluororesin preferably has a melting point of, for example, 150 to 330 ° C. The melting point of the fluororesin is obtained as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) apparatus (manufactured by Seiko). .

The fluororesin preferably has a melt flow rate (MFR) of 5 to 100 g / 10 minutes. If the MFR is too large, the mechanical strength may not be sufficient.

The fluororesin can have a melt flow rate within the above range by adjusting the copolymer composition and molecular weight. In the present specification, the melt flow rate is a value measured at a temperature of 372 ° C. and a load of 5 kg according to ASTM D3307-01 when the fluororesin is PFA or FEP. When the fluororesin is neither PFA nor FEP, it is a value measured at a temperature of 297 ° C. and a load of 5 kg in accordance with ASTM D3159.

The resin tableware of the present invention may contain a resin other than the fluororesin as long as the weight loss rate by heating is 10 ppm / day or less.

The resin tableware of the present invention is also one of preferred forms that is made of a fluororesin and a resin (however, excluding the fluororesin). The resin (excluding the fluororesin) can also be referred to as a fluorine-free resin, for example.

When the resin tableware of the present invention is made of a fluororesin and a resin (excluding the fluororesin), the fluororesin is 50 masses relative to the total mass of the fluororesin and the resin (excluding the fluororesin). % Or more is preferable. When there is too little fluororesin, there exists a possibility that liberation of the volatile component which generate | occur | produces from resin tableware cannot fully be suppressed. The fluororesin is preferably more than 50% by mass, more preferably more than 60% by mass, and more than 70% by mass with respect to the total mass of the fluororesin and the resin (excluding the fluororesin). Furthermore, it is preferable and it is especially preferable to exceed 80 mass%.

Examples of the resin (excluding fluororesin) include, for example, polypropylene, polycarbonate, methacrylic resin, acrylonitrile / butadiene / styrene (ABS) resin, polymethylpentene, polystyrene, polyethylene terephthalate, melamine resin, phenol resin, and non-resin. At least one resin selected from the group consisting of saturated polyester resins is preferred. Among these, at least one resin selected from the group consisting of melamine resin, polypropylene resin, and polycarbonate resin is more preferable.

Of the above resins (excluding fluororesins), those having a melting point (for example, polypropylene) preferably have a melting point of, for example, 100 to 250 ° C.
The melting point of the above resins (excluding fluororesins) was determined as the temperature corresponding to the maximum value in the heat of fusion curve when the temperature was raised at a rate of 10 ° C./min using a DSC apparatus (Seiko). It is.

Of the above resins (excluding fluororesins), those having a melting point such as polycarbonate are preferably those having a Tg of 80 ° C. or higher. Tg is determined by dynamic viscoelasticity measurement according to ASTM E1640-94.

It is preferable that the resin (excluding the fluororesin) has a melt flow rate (MFR) of 1 to 80 g / 10 minutes. The MFR is more preferably 50 g / 10 minutes or less. If the MFR is too large, the mechanical strength may not be sufficient.

In the present specification, the melt flow rate of the above resin (excluding the fluororesin) is a value measured at a temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238, for example, in the case of polypropylene. In the case of polycarbonate, it is a value measured at a temperature of 300 ° C. and a load of 1.2 kg in accordance with ASTM D1238.

It is one of the preferable forms that the resin tableware of the present invention has a fluororesin layer made of fluororesin. It is preferable that the said fluororesin layer is provided in the surface side which food contacts. As a form of such resin tableware, for example, a form in which a resin layer made of the above resin (excluding the fluororesin) and a fluororesin layer are laminated can be mentioned. That is, the resin tableware of the present invention may include a fluororesin layer and a resin layer, and the fluororesin layer may be provided on the surface side in contact with food. By forming the fluororesin layer on the surface that comes into contact with food, it is possible to prevent the components that easily volatilize from being released from the resin layer and adhere to the food. Such a resin tableware is preferably a container such as a tea bowl, a dish or a bowl.
Further, for example, a resin part made of resin (excluding fluororesin) and a form in which the surface of the resin part is covered with a fluororesin layer may be mentioned. Such a resin tableware is preferably an instrument such as a knife, fork or spoon.
In this way, the combined use of the above-mentioned resins (excluding fluororesins) and fluororesins suppresses the release of volatile components generated from resin tableware, and the cost is lower than when only fluororesins are used. Can be achieved.
The resin tableware of the present invention is a container in which a resin layer made of the above resin (excluding fluororesin) and a fluororesin layer are laminated, or a resin portion made of resin (excluding fluororesin) It is also preferable that the surface of the resin part is an instrument covered with a fluororesin layer.

The thickness of the fluororesin layer is preferably 500 μm or more. For example, in the case of a resin tableware in which a fluororesin layer is formed on the resin layer, if the thickness of the fluororesin layer is too thin, the liberation of volatile components may not be sufficiently suppressed. The upper limit of the thickness of the fluororesin layer is not particularly limited because it varies depending on the thickness, size, etc. of the resin tableware obtained, but the thickness of the fluororesin layer is preferably, for example, 5 mm or less.

The fluororesin layer is preferably formed by injection molding or compression molding.

As a manufacturing method of the resin tableware of this invention, it is preferable to include the process of shape | molding by injection molding or compression molding, and obtaining the resin tableware, for example. More preferably, it includes a step of obtaining a resin tableware by molding a fluororesin by injection molding.

The step of obtaining a resin tableware by molding a fluororesin by the injection molding is preferably a step of obtaining a resin tableware by, for example, injecting and molding a molten or softened fluororesin into a mold. More specifically, the step is preferably a step of injecting molten fluororesin into a mold and cooling to solidify to obtain resin tableware. The temperature of the molten fluororesin may be a temperature at which the fluororesin melts, but for example, a temperature that is 30 to 100 ° C. higher than the melting point of the fluororesin is preferable.

The step of molding the fluororesin by the compression molding to obtain the resin tableware is, for example, the step of charging the fluororesin into a mold and molding the fluororesin using a compression molding press to obtain the resin tableware. preferable. For example, the mold temperature is preferably 30 to 80 ° C. higher than the melting point of the fluororesin. The molding time is preferably 150 seconds to 30 minutes, for example.

The resin tableware of the present invention may also be manufactured by insert molding. When the resin tableware of the present invention is formed from a fluororesin and a resin (excluding the fluororesin), the resin tableware is produced by placing a pre-molded fluororesin in a mold. The method may include a step of injecting a molten resin (excluding the fluororesin) into the mold and insert molding the pre-molded fluororesin. The pre-molded fluororesin may be molded by injection molding or may be molded by compression molding.

The resin tableware of the present invention may also be manufactured by two-color molding. When the resin tableware of the present invention is formed from a fluororesin and a resin (excluding the fluororesin), the resin tableware can be produced by, for example, injecting molten fluororesin into a mold. And a step of injecting and molding a molten resin on the molded fluororesin. By two-color molding, a molded product that is a partially different member can be molded with higher productivity than insert molding.

The resin tableware of the present invention preferably contains a pigment. The resin tableware of the present invention preferably contains a pigment of a desired color according to the pattern drawn on the resin tableware. The pigment is not particularly limited, and may be an inorganic pigment or an organic pigment. Examples of inorganic pigments include ceramic pigments such as glass fine powder, glass balloons, and ceramic beads; metal strip pigments such as aluminum, iron, zirconium, and cobalt; titanium oxide, magnesium oxide, barium oxide, calcium oxide, and oxidation Metal oxide pigments such as zinc, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide, nickel oxide, manganese oxide, chromium oxide, iron oxide, copper oxide, cerium oxide, aluminum oxide; iron oxide-oxidation Complex oxide pigments such as manganese, iron oxide-chromium oxide, copper oxide-magnesium oxide; metal pigments such as Si and Al, Fe, magnesium, manganese, nickel, titanium, chromium, calcium; and iron-chromium, bismuth- Manganese, iron-manganese, manga - alloy pigments such as yttrium; mica, silicon nitride, coated pigment which has been subjected to surface treatment, luster pigments, and barium sulfate. The above pigments can be used alone or in combination of two or more. Examples of organic pigments include azo pigments, azomethine pigments, lake pigments, thioindigo pigments, anthraquinone pigments (anthanthrone pigments, diaminoanthraquinonyl pigments, indanthrone pigments, flavanthrone pigments, anthrapyrimidine pigments. Perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, quiniphthalone pigments, quinacridone pigments, isoindoline pigments, isoindolinone pigments, carbon pigments 1 type or 2 types or more can be illustrated. Examples of the pigment include Cr ₂ O ₃ , Fe ₂ O ₃ , (Ti, Ni, Sb) O ₂ , (Ti, Cr, Sb) O ₂ , CoAl ₂ O ₄ , Co ₂ TiO ₄ , and CuCr ₂ O. ₄ , TiO ₂ , 2NiO · 3BaO · 17TiO ₂ , (Ti, Cr, Nb) O ₂ , Co (Al, Cr) ₂ O ₄ , and (Zn, Fe) Fe ₂ O _4. Preferably it is at least one compound. More preferably, it is selected from the group consisting of CoAl ₂ O ₄ , Co ₂ TiO ₄ , TiO ₂ , 2NiO · 3BaO · 17TiO ₂ , Co (Al, Cr) ₂ O ₄ , and (Zn, Fe) Fe ₂ O _4. At least one compound.
The pigment is preferably 0.01% by mass or more, and more preferably 0.5% by mass or more with respect to the total mass of the resin tableware. Moreover, it is preferable that a pigment is 10 mass% or less with respect to the total mass of resin tableware.

The resin tableware of the present invention preferably has a specific gravity of 1.1 to 3.0. It sinks into water when its specific gravity is 1.1 or more. Therefore, cleaning is easy. On the other hand, if the specific gravity is too large, the weight increases and the handleability may be poor. The resin tableware of the present invention preferably has a specific gravity of 1.3 or more, and more preferably 1.5 or more. The resin tableware of the present invention preferably has a specific gravity of 2.8 or less, and more preferably has a specific gravity of 2.6 or less.

The present invention is also a method for suppressing odor of resin tableware, which includes a step of manufacturing a resin tableware made of a fluororesin and a step of using food on the resin tableware. The step of manufacturing the resin tableware made of fluororesin can be carried out by the above-described method for manufacturing resin tableware, and is preferably a step of forming the resin tableware by injection molding or compression molding.

The present invention is also a method for facilitating washing of resin tableware, which includes a step of manufacturing resin tableware made of a fluororesin and a step of immersing and washing the resin tableware in water. The step of manufacturing the resin tableware made of fluororesin can be carried out by the above-described method for manufacturing resin tableware, and is preferably a step of forming the resin tableware by injection molding or compression molding.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

In Examples and Comparative Examples, tableware was evaluated by measuring the weight loss by heating and performing an odor test after sealed heating by the following methods.

(Measurement of weight loss by heating)
Heating weight loss rate (Z) is a sample obtained by cutting out 3-5g of a piece of tableware and putting it in a hot air circulating furnace (model number: DRM420DA, manufactured by Advantech Toyo Co., Ltd.) at 80 ° C. Measure the weight (W ₀ ) before entering the furnace, the weight (W ₁ ) after 1 day (24 hours) after entering the hot air circulating furnace (W ₁₀ ) after 10 days (240 hours), and Formula (1):

により求めた値である。

It is the value calculated | required by.

(Odor test after sealed heating)
The tableware is heated for 24 hours in a hot air circulating furnace (model number: DRM420DA, manufactured by Advantech Toyo Co., Ltd.) at 80 ° C. The mixture is allowed to cool in the outside air, and thereafter, three pieces of tableware cut into 4.5 to 5 g are put into a 300 cc SUS autoclave, sealed, and then heated at 100 ° C. for 24 hours.
Before the autoclave is cooled, the autoclave is opened, the odor is removed, and the presence / absence and strength of the odor is evaluated in three stages. Repeat the same test on 5 people and count how many were evaluated at each stage.

Example 1
A dish having the shape shown in FIG. 1 was formed using PFA (product number: AP210, manufactured by Daikin Industries, Ltd.) as a raw material by an injection molding machine. The injection molding conditions are shown in Table 1.

(Example 2)
A dish having the shape shown in FIG. 1 was formed using ETFE (product number: EP521, manufactured by Daikin Industries, Ltd.) as a raw material by an injection molding machine. The injection molding conditions are shown in Table 1.

(Example 3)
A dish having the shape shown in FIG. 1 was formed using PVdF (product number: VP825, manufactured by Daikin Industries, Ltd.) as a raw material by an injection molding machine. The injection molding conditions are shown in Table 1.

Example 4
Using an injection molding machine, PFA containing colorant (100 parts by weight of AP210 and 5 parts of H3305 (containing titanium oxide, PFA color masterbatch, manufactured by Dainichi Seika Kogyo Co., Ltd.)) is used as a raw material. A dish of the shape shown was molded. The injection molding conditions are shown in Table 1. The finished compact is white and looks like ceramic.

(Example 5)
A dish was formed in the same manner as in Example 4 except that H3381 (containing iron oxide, carbon, PFA color master batch, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used instead of H3305. The finished compact is brown and looks like a wooden tableware.

(Example 6)
PVdF (VP825) is heated at 250 ° C. for 25 minutes and then compression-molded to form a sheet 1 of 0.5 mmt. An acrylic cast plate (Acrylite L, colorless 001, thickness 1 mmt, manufactured by Mitsubishi Rayon Co., Ltd.) is sandwiched between sheets 1 and held at 190 ° C. for 30 minutes while being pressurized at 15 g / cm ² . By this operation, the sheet 2 having a three-layer structure of PVdF-acrylic-PVdF is obtained. Furthermore, after heating the sheet 2 at 200 ° C. and 25 ° C., the sheet 2 was sandwiched between the molds, compressed and deformed, and formed into a dish shape as shown in FIG.

(Comparative Example 1)
A commercially available cup made of polypropylene was subjected to measurement of weight loss by heating and odor test after sealed heating.

(Comparative Example 2)
About the commercially available melamine resin porridge, the measurement of the weight loss rate by heating and the odor test after sealed heating were performed.

(Comparative Example 3)
A commercially available transparent case made of polystyrene was subjected to measurement of weight loss by heating and odor test after sealed heating.

Table 2 shows the results of the measurement of the weight loss by heating and the odor test after sealed heating for the dishes obtained in Examples 1 to 6 and the cups, bowls and transparent cases of Comparative Examples 1 to 3.

The tableware of the present invention can suppress the release of easily volatile components such as components (oligomers) having a relatively low molecular weight, unreacted monomers, plasticizers, and pyrolysis substances from the tableware. It can be taken comfortably and can be used at various dining venues.

1: dish

Claims (5)

Made of fluororesin and resin (excluding fluororesin),
The fluororesin exceeds 50 mass% with respect to the total mass of the fluororesin and the resin (excluding the fluororesin),
A resin tableware having a heating weight loss rate of 10 ppm / day or less. Tableware according to claim 1 further comprising a pigment. The resin tableware according to claim 1 or 2 , wherein the specific gravity is 1.1 to 3.0. The resin tableware according to claim 1, 2 or 3 , wherein the resin (excluding the fluororesin) is at least one selected from the group consisting of melamine resin, polypropylene resin and polycarbonate resin. Fluoropolymers are polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, ethylene / tetrafluoroethylene copolymer, polychlorotrifluoroethylene, chloro Trifluoroethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer, and The resin tableware according to claim 1, 2, 3, or 4, which is at least one selected from the group consisting of vinyl chloride.

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