CN108947326B - Thermal insulation degradable ceramic lunch box and preparation method thereof - Google Patents
Thermal insulation degradable ceramic lunch box and preparation method thereof Download PDFInfo
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- CN108947326B CN108947326B CN201811109501.8A CN201811109501A CN108947326B CN 108947326 B CN108947326 B CN 108947326B CN 201811109501 A CN201811109501 A CN 201811109501A CN 108947326 B CN108947326 B CN 108947326B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
- A45C11/00—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00
- A45C11/20—Lunch or picnic boxes or the like
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/28—Polysaccharides or derivatives thereof
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Abstract
The invention discloses a preparation method of a heat-insulating degradable ceramic meal box, which comprises raw materials of ceramic clay, bamboo fiber, chitosan, glycerol, sodium alginate, an adhesive, an oil-proofing agent and a water-resisting agent, wherein the meal box is divided into a two-layer structure, the inner layer is a ceramic layer, and the outer layer is a degradable fiber layer; the outer layer is a degradable fiber layer, and after a period of time, the outer layer is degraded, so that the pollution to the environment is greatly reduced; the inner layer is a ceramic layer which is still soil after weathering and decomposition after being discarded; the insulation board has the advantages of difficult breakage, light weight, safety, environmental protection, good insulation effect, simple production process, low cost and good economic and social benefits.
Description
Technical Field
The invention relates to the field of lunch boxes, in particular to a heat-insulating degradable ceramic lunch box and a preparation method thereof.
Background
Since the beginning of the 20 th century, plastic products appeared for the first time, the life of people has changed greatly, and the most obvious embodiment of the change is to bring great convenience to the daily life of people. With the rapid development of economic technology, the living standard of people is continuously improved, and the living rhythm is also continuously accelerated, so that the fast food industry which is rapid and convenient is rapidly developed. Nowadays, people gradually realize that plastic products which bring great convenience to people also erode the living space of people, the land becomes barren, marine organisms suffer from toxicity, and the balance of the biological chain is broken. The disposable snack box which is generally used at present can not be heated because the material is not degradable and certain chemical components which are harmful to human bodies are added in the processing and forming process, and the disposable snack box not only can cause great pollution to the environment and certain damage to the human bodies, but also is not environment-friendly and healthy, thereby seriously restricting the development of the fast food industry. Although biodegradable materials are gaining increasing attention, there is a long time still required to completely replace some disposable cutlery boxes.
At present, all disposable lunch boxes on the market do not meet the national standard, and unqualified lunch boxes used for a long time can bring adverse effects to the body.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a heat-insulating degradable ceramic meal box and a preparation method thereof.
The heat-insulating degradable ceramic meal box is divided into a two-layer structure, wherein the inner layer is a ceramic layer, and the outer layer is a degradable fiber layer;
the inner layer comprises the following raw materials in parts by weight:
30-40 parts of ceramic clay,
10-15 parts of chitosan, namely chitosan,
5-7 parts of epoxy resin,
3-5 parts of a binder,
3 to 5 parts of an oil-repellent agent,
the outer layer comprises the following raw materials in parts by weight:
40-60 parts of bamboo fiber,
10-15 parts of chitosan, namely chitosan,
3-5 parts of sodium alginate,
2-4 parts of a binder,
1 to 3 parts of an oil-repellent agent,
selecting 100-200 meshes of bamboo fibers;
selecting chitosan with the molecular weight of 2000-6000;
the binder is one or a mixture of more than one of acrylic resin, methyl cellulose, ethyl cellulose, nitrocellulose ester, polyurethane resin and polyester resin;
the oil-proof agent is a cationic paper fluorocarbon oil-proof agent; the cationic paper fluorocarbon oil-proof agent is a product prepared according to the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university. The acrylic acid ester type cationic polymer is prepared by adding a dispersing emulsifier, an initiator and a stabilizer into acrylate type soft and hard monomers, cationic monomers and fluorine-containing monomers under ultrasonic irradiation.
The preparation process of the heat-preservation degradable ceramic lunch box comprises the following steps:
(a) putting the raw materials of the outer layer (1) into a mixer according to the weight percentage, and uniformly stirring to obtain a mixed solution;
(b) adding the mixed solution obtained in the step (a) into a hot-press forming device, and carrying out hot-press forming on the mixed solution into a die to form a needed lunch box shape, wherein the hot-press time is 30-40 minutes, and the hot-press temperature is 110-120 ℃, so as to obtain a lunch box prototype which is an outer layer (1) fiber layer;
(c) uniformly stirring the inner layer (2) in a mixer to obtain a mixed solution;
(d) coating a plurality of layers of ceramic slurry on the inner wall of the primary type of the lunch box obtained in the step (b) by using the mixed solution obtained in the step (c), drying each time, then coating, and naturally airing or airing until the water content is below 15% to obtain a double-layer lunch box with a waterproof layer inside;
(e) and (d) rapidly drying the double-layer lunch box by using microwaves, wherein the wavelength is 0.001-1m, the frequency is 300-300000MHz, and the water content of the double-layer lunch box is lower than 5%, so as to obtain a product.
Compared with the prior art, the invention has the prominent substantive characteristics and remarkable progress that:
1. ceramic clay
The clay is clay for making pottery and has good plasticity. The ceramic raw material is extracted from a large amount of clay which is the original resource of the earth. The clay has toughness, can be plasticized when meeting water at normal temperature, can be carved in a micro-dry way and can be ground in a full-dry way, can be made into pottery to contain water when being burnt to 700 ℃, and can be vitrified when being burnt to 1230 ℃, almost does not absorb water, and is high-temperature resistant and corrosion resistant.
2. Bamboo fiber
Bamboo fiber is cellulose fiber extracted from naturally growing bamboo, and has natural antibacterial, bacteriostatic, mite removing, deodorant and ultraviolet resisting effects.
The bamboo is a tall and large grass plant which grows rapidly, the stem is wood and is distributed in the tropical zone, subtropical zone and warm zone areas, and the bamboo varieties in China are more than hundreds. The bamboo can quickly recover into secondary bamboo forest by the characteristics of quick growth and strong fertility, the application of the bamboo is continuously expanded, the economic value is high, people can plant the bamboo for afforestation to form an artificial forest, the secondary bamboo forest and the artificial bamboo forest, and the secondary bamboo forest and the artificial bamboo forest spread and expand to the periphery by the strong underground stems. Bamboo has wide application in building materials, papermaking, furniture, daily necessities such as chopsticks, bamboo baskets, baskets and the like, and is a necessity for daily life and industrial materials of people.
Most of the existing catering utensils are made of food-grade plastics, ceramics, glass and the like, and are also made of natural bamboo bodies. With the increasing awareness of environmental protection, renewable natural plant fibers are widely used in the field of materials technology. Bamboo fiber is a cellulose fiber extracted from naturally growing bamboos, and is the fifth largest natural fiber following cotton, hemp, wool, and silk. The bamboo fiber has the characteristics of good air permeability, instant water absorption, strong wear resistance, good dyeing property and the like, and simultaneously has the functions of natural antibiosis, bacteriostasis, mite removal, deodorization and ultraviolet resistance, thereby being a real natural environment-friendly green fiber. Because the yield of the bamboo fiber is high and the raw material bamboo is renewable, the bamboo fiber is greatly beneficial to environmental protection if the bamboo fiber is used for preparing tableware.
3. Chitosan
Chitosan (chitosan) is obtained by deacetylation of chitin (chitin) widely existing in the nature, the chemical name is polyglucosamine (1-4) -2-amino-B-D glucose, and after chitosan is firstly obtained by Rouget of the French nation in 1859 years, the excellent performances of the natural polymer, such as biological functionality and compatibility, blood compatibility, safety, microbial degradability and the like, are widely concerned by various industries, and the application research in various fields, such as medicine, food, chemical industry, cosmetics, water treatment, metal extraction and recovery, biochemistry, biomedical engineering and the like, is greatly advanced.
The method is mainly applied to the industries of food, medicine, agricultural seeds, daily chemical industry, industrial wastewater treatment and the like. The chitosan oligosaccharide has the effects of improving immunity, activating cells, preventing cancer, reducing blood lipid, lowering blood pressure, resisting aging, regulating organism environment, etc., and can be used in the fields of medicine, health promotion and food. In the environmental protection field, chitosan can be used for sewage treatment, protein recovery, water purification and the like. In the field of functional materials, chitosan can be used for membrane materials, carriers, adsorbents, fibers, medical materials and the like. In the field of light textile, chitosan can be used for fabric finishing, health care underwear, papermaking auxiliaries and the like. The agricultural field can be applied to feed addition, seed treatment, soil improvement, fruit preservation and the like. In the field of tobacco, chitosan is a tobacco sheet adhesive with good performance, and has the characteristics of improving the mouthfeel, being nontoxic and free from peculiar smell during combustion and the like.
Are used industrially as binders, thickeners, stabilizers, gelling agents, etc. Also used as a mildewcide for acidic substances, for pickled products, baked products, breads, oil-containing foods, etc., and forms a transparent semi-permeable film on the surface thereof. The chitosan has no reaction with body fluid, affinity to cells, and biodegradability.
4. The outer layer is a degradable fiber layer, and after a period of time, the outer layer is degraded, so that the pollution to the environment is greatly reduced; the inner layer is a ceramic layer, and the ceramic layer is still soil after weathering and decomposition.
5. Although the takeaway box is provided with the clay raw material, the clay is an inner layer, and the outer layer is provided with the fiber layer, so that the ceramic layer is protected, and the takeaway box is not easy to break and light in the conveying process.
6. The invention adopts the combination of the clay and the bamboo fiber, the shape of the lunch box can be various, and the lunch box is beautiful and durable, and can increase the appetite of people.
7. The heat-insulation brick has the advantages of light weight, safety, environmental protection, difficult breakage, good heat-insulation effect, simple production process and low cost, and brings great economic benefit.
8. The microwave drying speed is high, the effect is good, the high temperature of hot air drying or firing cannot damage the fiber layer, the microwave refers to electromagnetic waves between high frequency and far infrared rays, the thermal efficiency is high, the reaction is sensitive, the heat directly comes from the inside of the dried material, the loss of the heat in surrounding media is very little, the microwave heating cavity does not absorb heat and does not absorb the microwave, all the heat is emitted to act on the green body, and the thermal efficiency is high.
9. The cationic paper fluorocarbon oil-proof agent is a product prepared according to the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university. The acrylic acid ester type cationic polymer is prepared by adding a dispersing emulsifier, an initiator and a stabilizer into acrylate type soft and hard monomers, cationic monomers and fluorine-containing monomers under ultrasonic irradiation. The cationic paper fluorocarbon oil-proof agent has good water-proof effect and no toxicity, and is suitable for paper lunch boxes.
Drawings
FIG. 1 is a schematic structural view of a thermal insulation degradable ceramic meal box;
fig. 2 is a schematic side view of the thermal insulation degradable ceramic meal box.
The reference numbers and names are as follows:
1. an outer layer, 2, an inner layer;
the outer layer is a bamboo fiber layer, and the inner layer is a ceramic layer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Degradable pottery cutlery box keeps warm divide into two-layer structure, and inlayer 2 is the ceramic layer, and outer 1 is the degradable fibrous layer.
The inner layer 2 comprises the following raw materials in parts by weight: 30 parts of clay, 10 parts of chitosan, 5 parts of epoxy resin, 3 parts of adhesive, 3 parts of oil-proof agent, and a product prepared by using the cationic paper fluorocarbon oil-proof agent according to the examples of the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university.
The outer layer 1 comprises the following raw materials in parts by weight: 40 parts of bamboo fiber, 10 parts of chitosan, 3 parts of sodium alginate, 2 parts of adhesive, 1 part of oil-proof agent and a product prepared by the embodiment of a cationic paper fluorocarbon oil-proof agent applied by Guangxi university (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8).
The preparation process of the heat-preservation degradable ceramic meal box comprises the following steps:
(a) putting the raw materials of the outer layer 1 into a mixer according to the weight percentage, and uniformly stirring to obtain a mixed solution;
(b) adding the mixed solution obtained in the step (a) into a hot-press forming device, and carrying out hot-press forming on the mixed solution into a mould to form a needed lunch box shape, wherein the hot-press time is 30 minutes, and the hot-press temperature is 110 ℃, so as to obtain a lunch box prototype which is an outer layer 1 fiber layer;
(c) uniformly stirring the inner layer 2 in a mixer to obtain a mixed solution;
(d) coating a plurality of layers of ceramic slurry on the inner wall of the primary type of the lunch box obtained in the step (b) by using the mixed solution obtained in the step (c), drying each time, then coating, and naturally airing or airing until the water content is below 15% to obtain a double-layer lunch box with a waterproof layer inside;
(e) and (d) quickly drying the double-layer lunch box by using microwaves, wherein the wavelength is 1m, the frequency is 10000MHz, and the water content of the double-layer lunch box is less than 5%, so that a product is obtained.
Example 2
Degradable pottery cutlery box keeps warm divide into two-layer structure, and inlayer 2 is the ceramic layer, and outer 1 is the degradable fibrous layer.
The inner layer 2 comprises the following raw materials in parts by weight: 35 parts of clay, 12 parts of chitosan, 6 parts of epoxy resin, 4 parts of adhesive, 4 parts of oil-proof agent and a product prepared by using the cationic paper fluorocarbon oil-proof agent according to the examples of the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university.
The outer layer 1 comprises the following raw materials in parts by weight: 45 parts of bamboo fiber, 12 parts of chitosan, 4 parts of sodium alginate, 3 parts of adhesive, 2 parts of oil-proof agent, and a product prepared by using the cationic paper fluorocarbon oil-proof agent according to the examples of the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university
The preparation process of the heat-preservation degradable ceramic meal box comprises the following steps:
(a) putting the raw materials of the outer layer 1 into a mixer according to the weight percentage, and uniformly stirring to obtain a mixed solution;
(b) adding the mixed solution obtained in the step (a) into a hot-press forming device, and carrying out hot-press forming on the mixed solution into a mould to form a needed lunch box shape, wherein the hot-press time is 40 minutes, and the hot-press temperature is 120 ℃, so as to obtain a lunch box prototype which is an outer layer 1 fiber layer;
(c) uniformly stirring the inner layer 2 in a mixer to obtain a mixed solution;
(d) coating a plurality of layers of ceramic slurry on the inner wall of the primary type of the lunch box obtained in the step (b) by using the mixed solution obtained in the step (c), drying each time, then coating, and naturally airing or airing until the water content is below 15% to obtain a double-layer lunch box with a waterproof layer inside;
(e) and (d) quickly drying the double-layer lunch box by using microwaves, wherein the wavelength is 1m, the frequency is 50000MHz, and the water content of the double-layer lunch box is less than 5%, so that a product is obtained.
Example 3
Degradable pottery cutlery box keeps warm divide into two-layer structure, and inlayer 2 is the ceramic layer, and outer 1 is the degradable fibrous layer.
The inner layer 2 comprises the following raw materials in parts by weight: 40 parts of clay, 11 parts of chitosan, 7 parts of epoxy resin, 3 parts of adhesive, 4 parts of oil-proof agent and a product prepared by using the cationic paper fluorocarbon oil-proof agent according to the examples of the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university.
The outer layer 1 comprises the following raw materials in parts by weight: 60 parts of bamboo fiber, 15 parts of chitosan, 4 parts of sodium alginate, 4 parts of adhesive, 2 parts of oil-proof agent and a product prepared by the embodiment of a cationic paper fluorocarbon oil-proof agent according to the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university.
The preparation process of the heat-preservation degradable ceramic meal box comprises the following steps:
(a) putting the raw materials of the outer layer 1 into a mixer according to the weight percentage, and uniformly stirring to obtain a mixed solution;
(b) adding the mixed solution obtained in the step (a) into a hot-press forming device, and carrying out hot-press forming on the mixed solution into a mould to form a needed lunch box shape, wherein the hot-press time is 40 minutes, and the hot-press temperature is 120 ℃, so as to obtain a lunch box prototype which is an outer layer 1 fiber layer;
(c) uniformly stirring the inner layer 2 in a mixer to obtain a mixed solution;
(d) coating a plurality of layers of ceramic slurry on the inner wall of the primary type of the lunch box obtained in the step (b) by using the mixed solution obtained in the step (c), drying each time, then coating, and naturally airing or airing until the water content is below 15% to obtain a double-layer lunch box with a waterproof layer inside;
(e) and (d) quickly drying the double-layer lunch box by using microwaves, wherein the wavelength is 1m, the frequency is 100000MHz, and the water content of the double-layer lunch box is less than 5%, so that a product is obtained.
Example 4
Degradable pottery cutlery box keeps warm divide into two-layer structure, and inlayer 2 is the ceramic layer, and outer 1 is the degradable fibrous layer.
The inner layer 2 comprises the following raw materials in parts by weight: 40 parts of clay, 15 parts of chitosan, 7 parts of epoxy resin, 5 parts of adhesive, 5 parts of oil-proof agent and a product prepared by using the cationic paper fluorocarbon oil-proof agent according to the examples of the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university.
The outer layer 1 comprises the following raw materials in parts by weight: 60 parts of bamboo fiber, 15 parts of chitosan, 5 parts of sodium alginate, 4 parts of adhesive, 3 parts of oil-proof agent and a product prepared by the embodiment of a cationic paper fluorocarbon oil-proof agent according to the patent (cationic paper fluorocarbon oil-proof agent and preparation method thereof, application number: 200710024326.8) applied by Guangxi university.
The preparation process of the heat-preservation degradable ceramic meal box comprises the following steps:
(a) putting the raw materials of the outer layer 1 into a mixer according to the weight percentage, and uniformly stirring to obtain a mixed solution;
(b) adding the mixed solution obtained in the step (a) into a hot-press forming device, and carrying out hot-press forming on the mixed solution into a die to form a needed lunch box shape, wherein the hot-press time is 30-40 minutes, and the hot-press temperature is 110-120 ℃, so as to obtain a lunch box prototype which is an outer layer 1 fiber layer;
(c) uniformly stirring the inner layer 2 in a mixer to obtain a mixed solution;
(d) coating a plurality of layers of ceramic slurry on the inner wall of the primary type of the lunch box obtained in the step (b) by using the mixed solution obtained in the step (c), drying each time, then coating, and naturally airing or airing until the water content is below 15% to obtain a double-layer lunch box with a waterproof layer inside;
(e) and (d) rapidly drying the double-layer lunch box by using microwaves, wherein the wavelength is 1m, the frequency is 200000MHz, and the water content of the double-layer lunch box is less than 5%, so as to obtain the product.
Claims (3)
1. The preparation method of the heat-preservation degradable ceramic meal box is characterized in that the heat-preservation degradable ceramic meal box is divided into a two-layer structure, wherein the inner layer (2) is a ceramic layer, and the outer layer (1) is a degradable fiber layer;
the inner layer (2) comprises the following raw materials in parts by weight:
30-40 parts of ceramic clay,
10-15 parts of chitosan, namely chitosan,
5-7 parts of epoxy resin,
3-5 parts of a binder,
3-5 parts of an oil-proofing agent;
the outer layer (1) comprises the following raw materials in parts by weight:
40-60 parts of bamboo fiber,
10-15 parts of chitosan, namely chitosan,
3-5 parts of sodium alginate,
2-4 parts of a binder,
1-3 parts of an oil-proofing agent;
the oil-proof agent is a cationic paper fluorocarbon oil-proof agent;
the preparation process of the heat-preservation degradable ceramic meal box comprises the following steps:
(a) putting the raw materials of the outer layer (1) into a mixer according to the weight percentage, and uniformly stirring to obtain a mixed solution;
(b) adding the mixed solution obtained in the step (a) into a hot-press forming device, and carrying out hot-press forming on the mixed solution into a die to form a needed lunch box shape, wherein the hot-press time is 30-40 minutes, and the hot-press temperature is 110-120 ℃, so as to obtain a lunch box prototype which is an outer layer (1) fiber layer;
(c) uniformly stirring the inner layer (2) in a mixer to obtain a mixed solution;
(d) coating a plurality of layers of ceramic slurry on the inner wall of the primary type of the lunch box obtained in the step (b) by using the mixed solution obtained in the step (c), drying each time, then coating, and naturally airing or airing until the water content is below 15% to obtain a double-layer lunch box with a waterproof layer inside;
(e) and (d) rapidly drying the double-layer lunch box by using microwaves, wherein the wavelength is 0.001-1m, the frequency is 300-300000MHz, and the water content of the double-layer lunch box is lower than 5%, so as to obtain a product.
2. The method for preparing a thermal insulation degradable ceramic meal box according to claim 1, wherein the bamboo fiber is selected from 100 to 200 mesh.
3. The method for preparing a thermal insulation degradable ceramic meal box according to claim 1, wherein the chitosan is selected from chitosan with molecular weight of 2000-6000.
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Citations (5)
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|---|---|---|---|---|
| CN1513919A (en) * | 2003-08-22 | 2004-07-21 | 杨长利 | Biodegradable composition and its use in manufacturing dinnerware |
| JP2009275087A (en) * | 2008-05-13 | 2009-11-26 | Japan Polypropylene Corp | Propylene-based composite resin composition, and extrusion molded product using the same |
| CN202653737U (en) * | 2012-07-31 | 2013-01-09 | 东营市康森秸秆制品有限公司 | Degradable dish |
| CN106317923A (en) * | 2016-08-15 | 2017-01-11 | 陈隽 | Manufacturing method of green and environmentally friendly tableware |
| CN108175235A (en) * | 2017-12-26 | 2018-06-19 | 微徽房地产经纪（上海）有限公司 | A kind of Washing-free bowl and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513919A (en) * | 2003-08-22 | 2004-07-21 | 杨长利 | Biodegradable composition and its use in manufacturing dinnerware |
| JP2009275087A (en) * | 2008-05-13 | 2009-11-26 | Japan Polypropylene Corp | Propylene-based composite resin composition, and extrusion molded product using the same |
| CN202653737U (en) * | 2012-07-31 | 2013-01-09 | 东营市康森秸秆制品有限公司 | Degradable dish |
| CN106317923A (en) * | 2016-08-15 | 2017-01-11 | 陈隽 | Manufacturing method of green and environmentally friendly tableware |
| CN108175235A (en) * | 2017-12-26 | 2018-06-19 | 微徽房地产经纪（上海）有限公司 | A kind of Washing-free bowl and preparation method thereof |
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