CN107964119B - Slurry and preparation method thereof, food packaging material and preparation method thereof, and food packaging member - Google Patents
Slurry and preparation method thereof, food packaging material and preparation method thereof, and food packaging member Download PDFInfo
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- CN107964119B CN107964119B CN201711432749.3A CN201711432749A CN107964119B CN 107964119 B CN107964119 B CN 107964119B CN 201711432749 A CN201711432749 A CN 201711432749A CN 107964119 B CN107964119 B CN 107964119B
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- 239000002002 slurry Substances 0.000 title claims abstract description 65
- 239000005003 food packaging material Substances 0.000 title claims abstract description 57
- 235000013305 food Nutrition 0.000 title claims abstract description 54
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 20
- 238000007613 slurry method Methods 0.000 title description 2
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 94
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- 229920000728 polyester Polymers 0.000 claims abstract description 32
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- 239000000203 mixture Substances 0.000 claims abstract description 21
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
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- 241001465754 Metazoa Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
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- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
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- 125000003827 glycol group Chemical group 0.000 description 1
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- 235000020681 well water Nutrition 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Packages (AREA)
- Wrappers (AREA)
Abstract
A slurry for food packaging material comprises water, ethylene glycol and tungsten oxide particles having an average particle diameter of 100nm or less, wherein the tungsten oxide particles comprise W18O49And the total content of the tungsten oxide particles is in the range of 18 wt% to 28 wt% based on 100 wt% of the total amount of the slurry. A food packaging material is formed by carrying out a co-polymerization reaction on a mixture containing the slurry and raw material components for forming polyester, and comprises polyester and tungsten oxide with the average particle size of less than 100nm, wherein the total content of the tungsten oxide particles is 0.1-5 mg based on 100 g of the total amount of the polyester. A food packaging member is formed by heating and forming material components containing the food packaging material, and can accelerate the reheating function of the material, save energy and improve the product quality.
Description
Technical Field
The invention relates to a slurry, a food packaging material and a food packaging member, in particular to a slurry containing tungsten oxide particles with the average particle size range of less than 100nm, a method for preparing the slurry, a food packaging material containing tungsten oxide particles with the average particle size range of less than 100nm, a method for preparing the food packaging material, and a food packaging member containing tungsten oxide particles with the average particle size range of less than 100nm, which can accelerate the fast heating of a crude blank and save energy, and are certified by the Food and Drug Administration (FDA) and are in accordance with the food contact safety.
Background
Chinese mainland publication No. 103732666 discloses a compatible liquid formulation, a container preform and a packaging container.
The liquid preparation comprises a carrier compatible with polyester and tungsten oxide particles dispersed in the carrier, wherein the carrier is glycol, vegetable oil or mineral oil, and the tungsten oxide particles have a formula WO2.72And wherein less than 5 wt% of the tungsten oxide particles have a particle size in excess of 100 μm. In the examples of this patent, the average of the particle sizes of the milled tungsten oxide particles was 1.22 μm, and the median was 0.97 μm (equivalent to 970 nm).
The container preform comprises a polymer composition. The polymer composition includes polyethylene terephthalate (PET) and 12ppm to 50ppm of tungsten oxide particles. The polymer composition is formed by esterification and polycondensation of the liquid preparation and raw material components for forming polyethylene terephthalate, but no examples show whether chemical activity exists or not, and negative effects of the chemical activity and the mutual reaction exist.
The packaging container, such as a beverage bottle, is formed from the container preform by a forming heat treatment. The molding heating treatment is performed by using a quartz infrared heater and a mold. The patent does not suggest that the packaging container is a proof of food safety, so there is a safety concern about the packaging container being used to contain food.
The patent document goes through the possessed formula WO2.72The characteristic of the tungsten oxide particles of (a) absorbing energy of the quartz infrared heater(s) increases the heating rate of the heat treatment of the container preform, thereby enabling the production rate of the packaging container to be increased.
Although the patent may increase the heating rate of the container preform for heat treatment, the container preform of the patent has poor haze and transparency, and the container preform has poor effect of absorbing the energy of the quartz infrared heater.
Disclosure of Invention
Therefore, the first object of the present invention is to provide a slurry which does not cause precipitation and is easy to store, handle and disperse.
Thus, the slurry of the present invention can be used for food packaging materials, and comprises water, ethylene glycol, and tungsten oxide particles having an average particle diameter of 100nm or less, wherein the tungsten oxide particles comprise W18O49And the total content of the tungsten oxide particles is in a range of 18 wt% to 28 wt% based on 100 wt% of the total amount of the slurry, and the tungsten oxide particles can be added in a polymerization manufacturing process to reduce cost, and the components do not react with the manufacturing process to have negative effects.
The second important purpose of the invention is to provide a better technical method for preparing the slurry, which has the advantages of fast production, low cost and excellent quality.
Thus, the method for preparing the slurry of the invention comprises the following steps: a mixing step of mixing ethylene glycol, water and a tungsten oxide substance having an average particle size in the range of greater than 100nm to form a formulated mixture, wherein the tungsten oxide substance comprises W18O49(ii) a And a crushing step of crushing the mixture of the formula to form slurry containing ethylene glycol, water and tungsten oxide particles having an average particle diameter of 100nm or less, wherein the crushing step is performed by sequentially using grinding beads having different sizes in several stages from large to small, and the grinding beads are respectively operated at linear velocities corresponding to the grinding beads from small to large, and successful classification grinding is achieved by a unique technique of the formula.
The third important purpose of the present invention is to provide a food packaging material that is colorless or pale in visible light, but has the function of selectively absorbing near infrared rays, has good effects, can accelerate the reheating of the raw blank, improve the production efficiency, and save energy.
The food packaging material of the present invention comprises a polyester and tungsten oxide particles having an average particle diameter of 100nm or less, wherein the tungsten oxide particles comprise W18O49And the total content of the tungsten oxide particles is in a range of 0.1 mg to 5 mg, based on 100 g of the total amount of the polyester. The tungsten oxide particles of the present invention are in D50The optical size particle size absorption effect occurs around 80nm, so that it effectively absorbs the corresponding Near Infrared (NIR) energy, and then the thermal energy absorption effect is larger than that of using 1.0 μm W with larger particle size18O49Has an effect of absorbing heat energy 2 to 5 times, for example, at an equal mass, see (c) in FIG. 3, W having a particle size of 80nm at a wavelength of 1350nm18O49Has a transmittance of 8.3%, whereas in (a) of FIG. 3, W having a particle diameter of 0.5 μm to 2 μm18O49The transmittance of (A) was 56.6%, and it was found from Beer's law that W having a particle size of 80nm18O49Has an absorption of 1.081 (i.e., log0.083) and a particle size of 0.5 to 2 μm W18O49The absorbance of (B) was 0.247 (i.e., log0.566), and it was found that W having a particle size of 80nm was18O49For the wavelength at 1An absorbance at 350nm of 0.5 to 2 μm in particle size to W18O49Is 4.37 times (i.e., 1.081/0.247), which means that W having a particle size of 80nm is used18O49The effect of absorbing heat energy of (a) is that the particle size is 0.5 to 2 μm for W18O494.37 times the effect of absorbing thermal energy.
A fourth object of the present invention is to provide a method for preparing a food packaging material.
Accordingly, the method for preparing a food packaging material of the present invention comprises the steps of: providing raw material components for forming polyester and the slurry; the raw material components for forming the polyester are subjected to esterification reaction and polymerization reaction, the slurry is added in the esterification reaction or the polymerization reaction process, and then the food packaging material containing the polyester and the tungsten oxide particles with the average particle size range of less than 100nm is formed.
The fifth important object of the present invention is to provide a food packaging member with high transparency and low haze, which can uniformly heat the inner and outer surfaces of a blank at the time of heating, and can improve the quality of a processed member without causing brittle fracture.
Therefore, the food packaging member of the present invention is formed by heating and molding the material components containing the food packaging material. Referring to FIG. 2, FIG. 2 is a graph illustrating the penetration rate of different blanks. The NIR energy peaks at 1050nm, and the NIR energy peaks from top to bottom represent the energy distribution curves of the wavelength of light from a quartz lamp, the transmittance curve (hereinafter referred to as "B") of the blank of comparative example 1, the transmittance curve of the blank of example 2, and the transmittance curve of the blank containing 80ppm W in Table 1, respectively18O49The penetration curve of the crude embryo. The symbol B indicates a bottle preform formed only of pure polyethylene terephthalate and having very good absorption of the near infrared ray at 1660nm, but the near infrared ray at 1660nm absorbs 27.5% of the light passing through a depth of 0.5mm of the bottle preform at 4mm according to optical analysisLight, 0.5mm at the depth of 4mm relatively absorbs only 5.85% of light, the difference between the two is 4.7 times, namely when the surface temperature rises to 100 ℃, the innermost part rises only 21.3 ℃, so that the bottle blank with the thickness of 4mm has the problem that the surface (about 0.5mm) temperature is too high, and the inner part is far from enough heat. And referring also to FIG. 3, it can be seen from FIG. 3 that the particle size is 0.5 μm to 2 μm vs. W at the same mass18O49The absorption of 1660nm near infrared is very good, so that the surface temperature is too high and the internal part is not hot enough, and the curve is a flat section in the near infrared region, which shows that the optical size particle size effect is not existed. Referring to the figure 5 of the present invention, the particle size is very concentrated, and the cup-shaped curve of figure 4 is obtained, it can be seen that the food packaging material of the present invention has an optical size particle size absorption effect due to the use of tungsten oxide particles with an average particle size of less than 100nm, the curve is warped so as to reduce the absorption of 1660nm near infrared rays, and has a better absorption effect on 700nm to 1600nm near infrared rays, especially enhance the absorption at 1150nm, so that the inside and outside of the bottle preform can be uniformly heated, thereby avoiding the problem that the inside of the bottle preform is not sufficiently heated due to the excessively high surface temperature, causing the inside defect during the supercooling blowing of the bottle, and the surface overheating promotes the polyethylene terephthalate crystal atomization, both of which cause the food packaging member to crack during the pressure filling. The optical size particle size absorption effect is the rainbow after rain, when the particle size is small to a certain degree, the optical size particle size absorption effect can correspond to an optical frequency, when incident light enters the particle, the incident light can be continuously and totally reflected, so that the particle size has frequency selective absorption, and the absorption effect is 2 to 5 times, as shown in fig. 4.
The invention has the following effects: through the design of the particle size and the formula component content of the tungsten oxide particles, the slurry does not generate a precipitation phenomenon, so that the slurry is favorable for storage, grinding and dispersion, and is uniformly distributed and dispersed during operation and use, the food packaging material formed by the slurry has a good absorption effect on near infrared rays in a 700nm to 1600nm region, particularly on the near infrared rays of 1150nm, and moreover, a food packaging member formed by the food packaging material has the effects of high transparency and low haze due to small particle size and small addition amount of the tungsten oxide particles. And because the food packaging material has good absorption effect on near infrared rays in the 700nm to 1600nm region, the bottle blank is heated uniformly inside and outside, and polyethylene terephthalate crystal atomization cannot be promoted, so that the food packaging material is applied to a wide-mouth bottle or a soft beverage pressure bottle (CSD bottle), the problem that the wide-mouth bottle is difficult to heat and raise the temperature due to thick bottle wall can be avoided, and the problem that the pressure bottle is broken due to brittle fracture when being easily filled can be solved.
The present invention will be described in detail below.
< slurry >
The tungsten oxide particles in the slurry are required to Contact Food, that is, to meet the Food Contact Substance (FCS) application in Food safety regulations, and are certified by the Food and Drug Administration (FDA), and Food Contact Substance Notification (FCN) is obtained by the FDA to ensure safety in use. The application process of the food contact substance needs to make various dissolution tests, which are necessary for water, acid, alkali, temperature, chemical, physical stability, impurity degree of materials, the intake of dissolved substances to human body, the toxicological analysis and research of the substance to organisms, related genetic diseases, induced carcinogenicity, infectious diseases, various related nano discussions of materials, even including animal and human experiments, etc., and various detailed descriptions and summaries are made for Safety general description (SN for short) and Comprehensive toxicological summary (CTP for short), even the influence of materials on environment, etc. The FDA asserts that the applicant, unable to modify the materials used in the application, and the manufacturing processes used therein, otherwise approves failure, and anyone citations must be reapplied. With the authentication of food contact, it can be said that it is applicable to food contact.
Because the tungsten oxide particles in the slurry are dispersed in the ethylene glycol water, and OH groups on the ethylene glycol can be compatible with the tungsten oxide particle interface and hold the tungsten oxide particles without causing the tungsten oxide particles to agglomerate with each other, the slurry is not easy to precipitate in the storage process, the ethylene glycol is used as one of PET raw materials, and the water is used as wellThe reactants in the esterification are not harmful to the manufacturing process. Preferably, the tungsten oxide particles have a median particle diameter (D)50) And was 0.08 μm. The applicant emphasizes that it is extremely difficult to achieve the nano-grade particle size of tungsten oxide particles, and the D with the effect of optical size and particle size can be prepared by the classification and pulverization treatment and the adjustment of the viscosity and linear velocity of the formulation during the treatment process50The effect of the tungsten oxide particles of 80nm is shown in fig. 3 and 4, and the particle size distribution is shown in fig. 5.
The preparation method of the slurry comprises the following steps: a mixing step and a crushing and dispersing step. The mixing step is mixing ethylene glycol and a tungsten oxide species having an average particle size in the range of greater than 100nm to form a mixture, wherein the tungsten oxide species comprises W18O49. The crushing step is to crush the mixture, and can obtain a finished product with the most energy-saving, the highest efficiency and the best effect. The pulverization is carried out by grinding the mixture separately with a plurality of grinders using a plurality of grinding beads having different particle diameters, or by using a homogenizer. Such as, but not limited to, a high pressure homogenizer. Since the mill or homogenizer is not a main feature of the present invention, and the mill may be a conventionally well-known mill, and the homogenizer may be a conventionally well-known high-pressure homogenizer, the details thereof will not be described herein for the sake of brevity. Such as, but not limited to, zirconium beads. In order to effectively grind the tungsten oxide material to an average particle size of 100nm or less, maintain the structural properties of the tungsten oxide material, and meet the cost-effective grinding time, it is preferable that the size of the grinding beads is in the range of more than 0mm to 1.2 mm. In order to effectively grind the tungsten oxide material to a particle size range of 100nm or less, it is preferable that the operating linear velocity of the grinder is in the range of 8m/s to 14 m/s. Preferably, the pulverization treatment is carried out under the conditions of polishing beads having a size of 1.2mm and an operating linear velocity of 8m/sec, polishing beads having a size of 0.3mm and an operating linear velocity of 11m/sec, and polishing beads having a size of 0.1mm and an operating linear velocity of 14m/sec, in this order.
In order to make the viscosity meet the requirement in the pulverizing treatment process and more effectively pulverize tungsten oxide particles with average particle size range below 100nm, in the pulverizing step, water is added to adjust the viscosity. The addition amount of the water is adjusted according to the requirements of the manufacturing process.
< food packaging Material >
The raw material component for forming polyester is, for example, but not limited to, a raw material component for forming polyethylene terephthalate (PET). Such as, but not limited to, polyethylene terephthalate. The preparation method of the food packaging material comprises the following steps: raw material components for forming the polyester are subjected to esterification reaction and polycondensation reaction, and the slurry is added before the polycondensation reaction. The polyester is a conventionally known polyester, and the raw material components for forming the polyester are selected according to the selected polyester, for example, when the selected polyester is polyethylene terephthalate, the raw material components for forming the polyester include terephthalic acid and ethylene glycol. The temperature or time of the esterification and polycondensation reaction is adjusted depending on the polyester to be formed. The operating temperature range of the esterification reaction is 210 ℃ to 270 ℃. The polycondensation reaction is carried out at an operating temperature in the range of 260 ℃ to 290 ℃. The operating pressure range of the polycondensation reaction is 250mmHg or less. In order to promote the polycondensation reaction, the food packaging material is prepared by a method further comprising the step of adding a catalyst. Such as, but not limited to, antimony trioxide (Sb)2O3) Phosphoric acid stabilizer, antimony acetate, germanium oxide or titanium catalyst, etc. Such as, but not limited to, titanium tetrabutylate. But none of the catalyst additions adversely affect the slurry reaction.
The tungsten oxide particles of the food packaging material have an average particle size of 100nm or less, so that the tungsten oxide particles and the food packaging material have an optical size particle size effect in which light of a certain frequency is totally reflected again when entering the particles, thereby increasing an extinction heat absorption effect, controlling the particle size so as to correspond to the frequency of light waves of near infrared rays to be produced, and thus absorbing the near infrared rays more effectively. Experiments prove that the absorption effect of the tungsten oxide particles on near infrared rays is superior to that of all near infrared ray heat absorption materials on the market at present, the tungsten oxide particles are designed by an optical theory, the heat absorption and the temperature rise of the inner part and the outer part of a rough blank can be uniform, bottle breaking can not be caused, and food contact safety specifications can be met. In the food packaging material of the present invention, since the structure of the tungsten oxide particles has the micro-pores, during the condensation polymerization reaction, the polyester will enter the micro-pores of the tungsten oxide particles, so that the tungsten oxide particles are bound by the polyester, thereby causing the characteristic that the tungsten oxide particles are less prone to be migrated (Migration), and having better food safety. In addition, the tungsten oxide particles of the present invention have an average particle size of less than 100nm, and compared with the tungsten oxide particles with a large particle size in the prior art, the tungsten oxide particles can correspond to the light wave frequency of the near infrared ray used for production due to the optical size effect, as shown in fig. 3 and 4, the absorption effect of the near infrared ray is more than 3 times, and the PET itself can be avoided from absorbing the NIR part of 1660nm, so as to avoid the problem that the surface of the blank is overheated and the inside of the blank is not hot, and as can be seen from the curves of fig. 2 and 4, the heat absorption section of the tungsten oxide particles improves the problem that the blank is cold-stretched and blown into a bottle, i.e., the blank is not hot enough and blown into a bottle below the glass transition point (Tg point).
< food packaging Member >
The food packaging member has the characteristics of high transparency, low haze, difficult brittle fracture and the like, and the tungsten oxide particles are difficult to migrate and dissolve out of the food packaging member. The manufacturing process of the food packaging member of the invention conforms to the specification and the certification of the U.S. food and drug administration, and the food contact substance notice is formally obtained and the notice number is FCN1669, thereby being safely used for packaging food. The food packaging component of the invention uses a test method FDA177.1630 dissolution test set by the U.S. food and drug administration, uses an Inductively Coupled Plasma (ICP) instrument with high precision to measure the migration amount of tungsten, and the test result shows that when the tungsten oxide particle content in the food packaging component of the invention is 50ppm (calculated by the total amount of the polyester being 40 g), only about 0.05ppb is dissolved into water in a 1000 g bottle, the dissolution amount is far lower than the dissolution amount of 0.5ppb specified in the U.S. FDA21CFR10.115, even the tungsten content in drinking tap water is 3.32ppb and the tungsten content in well water is 10ppb, so the food packaging component of the invention is safe for food contact, and does not influence human body building.
Such as, but not limited to, a container in contact with food or a sheet in contact with food. Such as, but not limited to, beverage bottles. Such as, but not limited to, a wrapper.
The preparation method of the food packaging member comprises the following steps: the material components containing the food packaging material are subjected to heating treatment and molding treatment. The heat treatment is performed by an infrared heater. The heat source temperature and the main radiation wavelength of the infrared heater are selected according to the manufacturing process and materials. The infrared heater has a heat source temperature such as, but not limited to, a color temperature of 2050 ℃. The main radiation wavelength of the infrared heater is for example, but not limited to 1250 nm. Such as, but not limited to, infrared quartz tubes. The molding process is performed by using a mold. The mould is selected according to the desired shape of the food packaging unit. The food packaging material has the effect of optical size and particle size, so that the near infrared rays can be more effectively absorbed in a required section, and the preparation method of the food packaging member has the advantages of energy conservation and high production speed.
To make the features and details of the present invention more apparent to those skilled in the art, and to achieve the above-mentioned objects and other objects, the present invention provides:
a slurry for food packaging material, comprising ethylene glycol, water and tungsten oxide particles having an average particle diameter in the range of 100nm or less, wherein the tungsten oxide particles include W18O49, and the total content of the tungsten oxide particles is in the range of 18 wt% to 28 wt% based on 100 wt% of the total amount of the slurry.
Wherein the median value (D) of the tungsten oxide particles50) The particle size may be 0.08 μm.
A method of making a slurry comprising the steps of: a mixing step of oxidizing ethylene glycol, water and a mixture of water and an organic solvent having an average particle size in the range of more than 100nmMixing tungsten species to form a formulation mixture, wherein the tungsten oxide species comprises W18O49(ii) a And a crushing step, namely crushing the mixture of the formula, wherein the crushing treatment is carried out by sequentially utilizing a plurality of grinding beads with the sizes from large to small and grading from small to large corresponding to the operating linear speeds of the grinding beads respectively so as to achieve economic nano particle size.
A food packaging material comprises polyester and tungsten oxide particles with average particle diameter of 100nm or less, wherein the tungsten oxide particles comprise W18O49And the total content of the tungsten oxide particles is in a range of 0.1 mg to 5 mg, based on 100 g of the total amount of the polyester.
Wherein the tungsten oxide particles have a median diameter of 0.08 μm and have an excellent optical size particle diameter absorption effect corresponding to NIR.
Wherein the tungsten oxide particles have a median particle size of 0.08 μm and have an optical size particle size effect on infrared heat production. The optical size effect, NIR emitted from a quartz lamp, has a corresponding maximum absorption wavelength spectrum for a specific size particle size of the material, which is called optical size particle size effect, and the particle size has a peak light wave absorption value of more than 2 times or even 5 times relative to the prior art (corresponding to the chinese continental publication No. 103732666).
The tungsten oxide particles have a median particle size of 0.08 mu m, a heat absorption peak value of about 1200nm, and avoid a 1660nm NIR area absorbed by PET, and the large-particle-size absorption peak value is moved to the 1660nm NIR area, so that the problems that the surface of a rough blank is overheated and the interior of the rough blank is not heated are caused, and the tungsten oxide particles are newly applied by utilizing an optical technology.
Wherein the food packaging material conforms to the approved specification of FDA FCN 1669.
FDA number FCN1669 certifies compliance with the food bulletin, and the pointers to the original applicant, others, refer to the respective applications that must be filed.
A method of preparing a food packaging material comprising the steps of: providing raw material components for forming polyester and the slurry as described above; the raw material components for forming the polyester are subjected to esterification reaction and polymerization reaction, the slurry is added in the esterification reaction or the polymerization reaction process, and then the food packaging material containing the polyester and the nano tungsten oxide particles with the average particle size range of less than 100nm is formed.
Wherein the slurry is added in the polymerization reaction process, and the tungsten oxide W in the slurry is made18O49Ethylene glycol and water are involved in the polymerization reaction. Besides the feasibility of experiment and better quality, the FCN1669 bulletin is approved by FDA and can be used for food packaging.
The food packaging member is formed by heating and molding the material components containing the food packaging material, wherein the heating is performed by using an infrared heater.
Drawings
Other features and effects of the present invention will be apparent from the embodiments with reference to the accompanying drawings, in which:
FIG. 1 is a spectral diagram of the color temperature of various quartz lamps;
FIG. 2 is a spectrum of the transmission of different rough blanks;
FIG. 3 is a spectral diagram illustrating W of different sizes18O49The penetration rate of (c);
FIG. 4 is a spectrum showing the transmittance of example 1 of the slurry of the present invention, showing the dishing phenomenon at 1150nm, which is an indication of the optical size particle diameter; and
FIG. 5 is a distribution diagram of particle size measured by actual laser, illustrating the actual distribution of particle size of tungsten oxide particles in the slurry of the present invention.
Detailed Description
The invention will be further described in the following examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
EXAMPLE 1 food packaging Member
Preparation of slurry: 3000 g of W having an average particle size of 25 μm18O4910500 g of water and 1500 gThe ethylene glycol of (2) was put in a first grinding mill (trade name: ASADA Haita; model: LMJ20), subjected to a first grinding treatment with zirconium beads having a size of 1.2mm and an operating line speed of 8m/sec, and ground to 0.6. mu.m. Then, it was transferred to a second grinding mill (brand: MiTSIU, Mitsui, model: SC220), subjected to a second grinding treatment with zirconium beads having a size of 0.3mm and an operating linear velocity of 11m/sec, and ground to 0.20. mu.m. Then transferred to a third grinding mill (brand: Hi-Team Corp.; model: NANO-M2), subjected to a third grinding treatment with zirconium beads having a size of 0.1mm at an operating line speed of 14M/sec, and ground to a desired size. The slurry comprises water, ethylene glycol and a median particle size (D)50) Is 80nm W18O49. The water content is 70 wt%, the ethylene glycol content is 10 wt%, and the W is calculated by taking the total amount of the slurry as 100 wt%18O49The content of (B) is 20 wt%. No dispersant is needed to be added in the preparation process of the slurry, so that the slurry is more in line with food safety.
Preparation of food packaging material: raw material components containing 38 kg of terephthalic acid (TPA), 900 g of isophthalic acid (IPA) and 18.16 kg of ethylene glycol and the slurry are put into a preparation tank at a certain molar ratio, then the mixture is put into a pressurizing kettle and subjected to an esterification reaction at a temperature of 250 ℃ for 6.5 hours, when the degree of esterification is about 95%, the mixture is put into a vacuum kettle, and a first polycondensation reaction is carried out at a temperature of about 270 ℃ and a vacuum pressure of about 100mmHg, and at the same time, 230ppm of antimony trioxide (based on the total amount of polyethylene terephthalate) and 35ppm of a phosphoric acid stabilizer (based on the total amount of polyethylene terephthalate) are added. Then, a second polycondensation reaction is carried out at a temperature of 270 ℃ to 290 ℃ and a pressure of less than 1mmHg to form a mixed component having a viscosity of 0.55dL/g to 0.60 dL/g. Introducing the mixed components into a pump (pump), extruding in strips, rapidly cooling with cooling water, cutting into granules with a cutter to obtain 50kg wet ester granules, and subjecting the wet ester granules to solid state polymerization at 200 deg.C to obtain food packaging material with viscosity of 0.72dL/g to 0.88dL/g suitable for food contactThe total weight of the feed was 1.00002 kg, the polyethylene terephthalate (PET) content was 1 kg, and the average particle diameter was 80nm of W18O49The content of (A) is 0.02 g. W18O49The experiment proves that the nano-material is inert and has no negative effects of the chemical activity of the nano-material and the like. Then the solid state polymerization manufacturing process is used for enhancing the viscosity and reducing the harmful and sanitary low molecular weight oligomer, thus the PET polyester granules which meet the food contact and have high heat absorption can be obtained.
Preparation of food packaging member: the food packaging material was dehumidified and dried, and then introduced into an injection molding machine (Husky) including a mold. The food packaging material is plasticized into a melt in the injection molding machine and injected into the mold to form a molded body, and then the molded body is cooled to form a rough blank with a wall thickness of about 4 mm.
Then, the preform was heated for about 0.5 minute by using an infrared quartz lamp (main radiation wavelength: about 1250 nm; heat source temperature: about 2050 ℃; manufacturer's brand: Sidel) during bottle blowing so that the inner and outer portions of about 4mm of the preform reached the glass softening and converting point, and finally, high-pressure blow molding was performed to form a container for containing food. The wall thickness of the container is about 0.35 mm.
Example 2
The procedures for preparation of a slurry, a food packaging material, and a food packaging member were similar to those of example 1, except that the food packaging material of example 2 contained 1 kg of polyethylene terephthalate and 0.04 g of W having an average particle diameter of 80nm18O49。
Comparative example 1 food packaging Member
The process for the preparation of the food packaging material, and the preparation of the food packaging member were similar to those of example 1 except that the slurry of the present invention was not added.
Comparative example 2 food packaging Member
Preparation of slurry: will be provided with3 kg of W having an average particle diameter of 25 μm18O4910.5 kg of water and 1.5 kg of ethylene glycol were placed in a first mill (trade mark: ASADA Haita; model: LMJ20), and a first milling treatment was carried out with zirconium beads having a size of 1.2mm and at an operating linear velocity of 8m/sec, and milled to 0.6. mu.m, but the prior art 10373266 milled to 0.97. mu.m only. Then, the resultant was transferred to a second grinding mill (brand: MITSU Mitsu; model: SC220), subjected to a second grinding process using zirconium beads having a size of 0.3mm at an operating linear velocity of 11m/sec, and ground to a desired size. The slurry comprises water, ethylene glycol and a median particle size (D)50) W of 0.20 μm18O49. The water content is 70 wt%, the ethylene glycol content is 10 wt%, and the W is calculated by taking the total amount of the slurry as 100 wt%18O49The content of (B) is 20 wt%.
Comparative example 2 the procedure for preparing a food packaging material and a food packaging member was the same as that of example 1. Referring to FIG. 3 and based on beer's law, the food packaging material of comparative example 2 used W of 0.20 μm18O49So that the heat absorbing effect thereof was only the food packaging material of example 1 (containing D)50Is 80nm W18O49) 0.5 times of the total weight of the powder.
Comparative example 3 food packaging Member
Preparation of slurry: 3 kg of W having an average particle diameter of 25 μm18O4910.5 kg of water and 1.5 kg of ethylene glycol were placed in a mill (trade name: MiTSIU for Mitsui; model: SC220), and subjected to milling treatment with zirconium beads having a size of 1.2mm at an operating linear velocity of 8m/sec, and milled to a desired size. The slurry comprises water, ethylene glycol and a median particle size (D)50) W of 0.6 μm18O49. The water content is 70 wt%, the ethylene glycol content is 10 wt%, and the W is calculated by taking the total amount of the slurry as 100 wt%18O49The content of (B) is 20 wt%.
Comparative example 3 Process for producing food packaging Material and food packaging MemberThe process. Referring to FIG. 3a and based on beer's law, the food packaging material of comparative example 3 used W of 0.97 μm18O49So that the heat absorbing effect thereof was only the food packaging material of example 1 (containing D)50Is 80nm W18O49) 0.2 to 0.3 times.
Evaluation item
Particle size (unit: nm) measurement: a MALVERN-2000 laser particle size analyzer was used. 1 μm-1000 nm.
The transmittance (unit:%) was measured: for W of different sizes using SHIMADZU-2600UV-Visible-NIR18O49The slurry of example 1 was measured in FIG. 4, in example 2 with the material of the present invention, and in comparison with the blank of comparative example 1 without the material of the present invention (wall thickness of 4 mm). When measuring the bottle blank, the bottle blank is irradiated from one side and the measurement is received from the other side of the bottle blank, and the thickness is 8 mm.
L, La and Lb: the values of L, La and Lb are based on the color form defined by CIE1976 by the International Lighting Association in 1976, L represents the whiteness of 100 at most 0 and at most 0, La positive represents red, and negative represents green; lb positive for yellow and negative for blue, measured with a Macbeth color eye 2145 spectrometer, operating with an observation angle of 2 ° and a light emitting source of D65. When the test sample is a bottle embryo, the sample thickness is determined to be 4 mm.
Haze value of the green body (Haze, unit:%): a Konica Minolta haze meter was used. The haze value is (Td/Tt) multiplied by 100, wherein Td is the dispersion transmittance; tt is total light transmittance, ASTM-D1003 method.
Measuring the heat absorption effect: the following table 1 shows the measurement results of the surface temperature of the raw blanks of examples 1 to 2 and comparative example 1, which were heated by an infrared quartz lamp and measured by a temperature-sensitive gun. The higher the temperature, the better the endothermic effect of the raw embryo.
TABLE 1
From the experimental data in Table 1, it is understood that the near infrared ray absorption effect of the green pellets formed from the slurry of the present invention is excellent as compared with the near infrared ray absorption effect of the green pellets of comparative example 1, and the absorption temperatures are raised by 22 ℃ in terms of heat increment rate of 25.9% (22X 100%/(110-25 normal temperature)) and 40 ℃ in terms of heat increment rate of 47.0% (40X 100%/(110-25 normal temperature)), respectively. Furthermore, the haze of the green stock formed from the slurry of the present invention was low compared to the haze of the green stock of comparative example 1 of table 1, indicating that the food packaging member of the present invention has high transparency. In addition, as can be seen from the data in fig. 3, compared to the tungsten oxide particles with a large particle size in the prior art, the tungsten oxide particles of the present invention are finer, have a better effect, have an optical size particle size effect, and can further correspond to the light wave frequency of the near infrared rays for production, so that the absorption of the near infrared rays is 3 times to 5 times or more.
For comparison, the inventors of the present invention present the experimental data of the chinese continental publication No. 103732666 described in paragraph [0002] of the prior art in tables 2 and 3. The patent adds tungsten oxide particles of different particle sizes at the inlet of the injection molding machine. The experimental data in tables 2 and 3 were obtained by testing the temperature rise in an oven, which was about half of the effect of the present invention. The problem is that the temperature rise is caused by surface measurement, but the temperature rise is not caused in the surface measurement, and the average actual temperature rise is only about 9.5 ℃, so that the 1/3 effect is only caused. If the effect of the prior art patent case 1/3 is not correct enough based on the spectrum scanning experiment, the analysis of the case by the spectrum scanning and the mutual verification of the actual experiment by the infrared irradiation are most correct.
TABLE 2
TABLE 3
| Additive material | L* | a* | b* | Reheat improvements | L is decreased |
| C93 control (blank) | 81.57 | -0.17 | 1.70 | N/A | N/A |
| 25ppm of unground WO2.72 | 78.81 | -1.51 | 1.81 | 9.36 | 2.75 |
| 25ppm of unground WO2.9 | 80.25 | -0.61 | 2.28 | 5.56 | 1.31 |
| 25ppm of milled WO2.72 | 78.02 | -1.76 | 0.26 | 15.76 | 3.55 |
| 25ppm of milled WO2.9 | 80.66 | -0.63 | 2.09 | 4.48 | 0.91 |
| 6ppm U1 carbon Black | 74.73 | 0.16 | 3.05 | 7.7 | 6.83 |
| 6ppm TiN titanium nitride | 73.51 | -0.70 | -0.28 | 10.16 | 8.06 |
Referring to FIG. 3, FIG. 3 is a diagram illustrating W with equal mass and different dimensions18O49Spectral transmittance of (a). (a) in FIG. 3 represents W of 0.5 μm to 2 μm18O49Transmittance curve of (2), (b) in FIG. 3 represents W of 200nm18O49Transmittance curve of (5), (c) in FIG. 3 represents W of 80nm18O49The penetration curve of (A) in FIG. 3 shows a needle-like shape W of 60nmx10nm18O49And (e) in FIG. 3 shows a needle-like W of 40nmx7nm18O49The transmittance curve of (a). As can be seen from the spectral curves in FIG. 3, different sizes of tungsten oxide have such a large difference in NIR absorption, and tungsten oxide with a smaller particle size has a greater NIR absorption effect than tungsten oxide with a larger particle size, so that the use of tungsten oxide with a smaller particle size is advantageous in thatThe formulation and polishing method used in the present invention can be achieved in a low cost and economical manner.
Material W for scheme18O49CAS Reg.No.12037-57-9, Thin Solid Films,130(1985), 181-.
For the FDA FCN1669 certification, please refer to the file name FDA _ FCN1699 in other fields of the document attached to the patent application.
In summary, the present invention utilizes the design of the particle size and the formula content of the tungsten oxide particles to prevent the slurry from generating precipitation phenomenon, thereby facilitating the storage, dispersion and operation, and the food packaging material formed by the slurry has good absorption effect on near infrared rays.
The above description is only an example of the present invention, and the scope of the present invention should not be limited by the above description, and all the simple equivalent changes and modifications made according to the claims and the contents of the patent specification should be included in the scope of the present invention.
Claims (9)
1. A method of making a slurry comprising the steps of:
a mixing step of mixing ethylene glycol, water and a tungsten oxide substance having an average particle size of greater than 100nm to form a formulated mixture, wherein the tungsten oxide substance comprises W18O49；
A crushing step of crushing the mixture of the formulation to form a slurry containing ethylene glycol, water and tungsten oxide particles having an average particle diameter of 100nm or less, wherein the crushing step is performed by sequentially classifying a plurality of kinds of grinding beads having sizes from large to small in order from small to large in accordance with the operating linear velocities of the grinding beads, respectively, wherein the crushing step further comprises a step of placing the tungsten oxide particles, water and ethylene glycol in a first grinder, and performing a first grinding process with zirconium beads having a size of 1.2mm and an operating linear velocity of 8 m/sec;
transferring to a second grinding machine, and performing second grinding treatment with zirconium beads with size of 0.3mm and operation linear velocity of 11 m/sec;
transferring to a third grinding machine, performing a third grinding treatment with zirconium beads having a size of 0.1mm and an operating linear velocity of 14m/sec, and grinding to a desired size to obtain a slurry.
2. A slurry for food packaging material prepared by the method of preparing a slurry according to claim 1, comprising:
ethylene glycol, water and tungsten oxide particles having an average particle diameter of 100nm or less, wherein the tungsten oxide particles comprise W18O49And the total content of the tungsten oxide particles is in the range of 18 wt% to 28 wt% based on 100 wt% of the total amount of the slurry.
3. The slurry of claim 2 wherein the median value (D) of the tungsten oxide particles50) The particle size was 0.08. mu.m.
4. A food packaging material comprises polyester and tungsten oxide particles with average particle diameter of 100nm or less, wherein the tungsten oxide particles comprise W18O49And the total content of the tungsten oxide particles is in a range of 0.1 mg to 5 mg, based on 100 g of the total amount of the polyester.
5. The food packaging material of claim 4, wherein the tungsten oxide particles have a median particle size of 0.08 μm.
6. The food packaging material of claim 4, wherein the food packaging material complies with FDA certified FCN 1669.
7. A method of preparing a food packaging material comprising the steps of: providing raw material components for forming polyester and the slurry of claims 2 to 3; the raw material components for forming the polyester are subjected to esterification reaction and polymerization reaction, and the slurry is added in the esterification reaction or the polymerization reaction process, so that the food packaging material containing the polyester and the nano tungsten oxide particles with the average particle size of less than 100nm is formed.
8. The method for preparing food packaging material of claim 7, wherein the slurry is added during the polymerization reaction, and tungsten oxide W in the slurry is caused to be present18O49Ethylene glycol and water are involved in the polymerization reaction.
9. A food packaging member formed by subjecting a material composition comprising the food packaging material according to any one of claims 4 to 6 to a heating treatment and a molding treatment, wherein the heating treatment is performed by an infrared heater.
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| PCT/CN2018/120380 WO2019128705A1 (en) | 2017-01-05 | 2018-12-11 | Slurry and preparation method therefor, food packaging material and preparation method therefor, and food packaging component |
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| TW106100252A TWI628212B (en) | 2017-01-05 | 2017-01-05 | Slurry and preparation method thereof, food packaging material and preparation method thereof, and food packaging member |
| TW106100252 | 2017-01-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732666A (en) * | 2011-07-21 | 2014-04-16 | 彩色矩阵控股公司 | Polymeric materials |
| CN106238036A (en) * | 2012-06-01 | 2016-12-21 | 株式会社东芝 | Aqueous dispersion, the use coating of aqueous dispersion, photocatalysis membrana and goods |
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| JP2008044609A (en) * | 2006-03-30 | 2008-02-28 | Sumitomo Metal Mining Co Ltd | Sunshine screen for vehicle window and vehicle window |
| BRPI0818911A8 (en) * | 2007-11-05 | 2018-12-11 | Basf Se | composition, process for the preparation of hydrogen and tungsten bronze or a hydrogen and tungsten bronze composition, particle dispersion, and use of hydrogen and tungsten bronze particles or particles containing hydrogen and tungsten bronze |
| WO2009110234A1 (en) * | 2008-03-04 | 2009-09-11 | 株式会社 東芝 | Aqueous dispersion, coating material using the same, membrane using the same, and article using the same |
| US9870842B2 (en) * | 2013-06-12 | 2018-01-16 | Ppg Industries Ohio, Inc. | Rapidly curable electrically conductive clear coatings |
| TWI628212B (en) * | 2017-01-05 | 2018-07-01 | 黃宗之 | Slurry and preparation method thereof, food packaging material and preparation method thereof, and food packaging member |
-
2017
- 2017-01-05 TW TW106100252A patent/TWI628212B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732666A (en) * | 2011-07-21 | 2014-04-16 | 彩色矩阵控股公司 | Polymeric materials |
| CN106238036A (en) * | 2012-06-01 | 2016-12-21 | 株式会社东芝 | Aqueous dispersion, the use coating of aqueous dispersion, photocatalysis membrana and goods |
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| TWI628212B (en) | 2018-07-01 |
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