CN114213784A - Plastic containing oyster shell calcined powder, plastic product and plastic manufacturing method - Google Patents
Plastic containing oyster shell calcined powder, plastic product and plastic manufacturing method Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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Abstract
Some embodiments of the present disclosure provide a plastic comprising oyster shell calcined powder, polyvinyl chloride, and an acrylate copolymer, which can improve the antibacterial property of the plastic and avoid the problem of air spots caused by the oyster shell calcined powder. Some embodiments of the present disclosure also provide a method of manufacturing a plastic, comprising: providing oyster shells; calcining oyster shells to obtain oyster shell calcined powder; and smelting the oyster shell calcined powder, polyvinyl chloride and the acrylate copolymer to obtain the plastic. If the oyster shell calcined powder is used as the antibacterial agent for plastics, the processability and the release property of the plastics are not affected, the heat distortion temperature and the rigidity of the plastics can be improved, and the heat stability is better.
Description
Technical Field
Some embodiments of the present disclosure relate to a plastic containing calcined oyster shell powder and a method for producing the same, and more particularly, to a plastic and a method for producing the same, which can improve antibacterial properties and improve the problem of air stain caused by calcined oyster shell powder.
Background
Oysters are one of food in Taiwan and even countries, but waste oysters left after the oysters are eaten are not easy to decompose and process, and long-term accumulation can destroy the ecological environment and generate malodor.
Oyster shells are rich in calcium carbonate and can be used as alkaline cleaning agents, adsorbents, organic fertilizers, or made into products (such as paper). If the oyster shell is calcined and then the calcined oyster shell is ground, the calcined oyster shell powder can be obtained, wherein part or all of the calcium carbonate in the oyster shell is converted into calcium oxide in the oyster shell calcined powder. And the oyster shell calcined powder is reported to have antibacterial property.
How to apply the oyster shell calcined powder to plastics to enable the plastics to have an antibacterial effect is a problem to be solved.
Disclosure of Invention
Some embodiments of the present disclosure provide a plastic comprising oyster shell calcined powder, polyvinyl chloride, and an acrylate copolymer.
In some embodiments, the molecular weight of the acrylate-based copolymer ranges from 100 to 700 million.
In some embodiments, the amount of the calcined oyster shell powder is 3 to 10 parts by weight and the amount of the acrylic copolymer is 0.8 to 10 parts by weight based on 100 parts by weight of polyvinyl chloride.
In some embodiments, the acrylate based copolymer comprises methyl methacrylate and butyl acrylate.
In some embodiments, the weight percentage of the acrylates is 100%, the weight percentage of the methyl methacrylate is 50% to 99%, and the weight percentage of the butyl acrylate is 1% to 50%.
In some embodiments, the acrylate-based composition further comprises butyl methacrylate.
In some embodiments, if the weight percentage of the acrylates is 100%, the weight percentage of methyl methacrylate is 50% to 70%, the weight percentage of butyl acrylate is 10% to 30%, and the weight percentage of butyl methacrylate is 10% to 30%.
Some embodiments in this summary provide a method of manufacturing a plastic comprising: providing oyster shells; calcining oyster shells to obtain oyster shell calcined powder; and smelting the oyster shell calcined powder, polyvinyl chloride and the acrylate copolymer to obtain the plastic.
In some embodiments, in the step of melting the oyster shell calcined powder, the polyvinyl chloride and the acrylate copolymer, the polyvinyl chloride is present in an amount of 3 to 10 parts by weight and the acrylate copolymer is present in an amount of 0.8 to 10 parts by weight, based on 100 parts by weight.
Some embodiments in this summary provide a plastic article comprising the foregoing plastic.
In some embodiments, the plastic article is a pipe, a packaging material, a stationery material, a decorative material, a building material, or a combination thereof.
It is to be understood that both the foregoing general description and the following detailed description are examples, and are intended to provide further explanation of the invention as claimed.
Drawings
The foregoing and other objects, features, and advantages of the invention will be apparent from the following more particular description of the embodiments of the invention, as illustrated in the accompanying drawings in which:
FIGS. 1A and 1B present the degree of gas spotting of plastics to which liquid antimicrobial agents are added in some embodiments of the present disclosure; and
fig. 2 presents the degree of mottling of plastics to which acrylate-based copolymers were added in some embodiments of the present disclosure.
Detailed Description
It is to be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of the invention. The particular arrangements and examples shown are meant to simplify the present disclosure and not to limit the same. Of course, these are merely examples and are not intended to be limiting. For example, the formation of a first feature over a second feature described below may include direct contact between the two or the two with additional features intervening therebetween. In addition, the present disclosure may repeat reference numerals and/or symbols in the various embodiments. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
The terms used in this specification have their ordinary meaning in the art and in the context of their use. The embodiments used in this specification, including examples of any terms discussed herein, are illustrative only and do not limit the scope and meaning of the disclosure or any exemplary terms. As such, this summary is not limited to some embodiments provided in this specification.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of the present embodiments.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As used herein, the terms "comprising," "including," "having," and the like are to be construed as open-ended, i.e., meaning including, but not limited to.
As used herein, the term "oyster shell" also known as oyster shell refers broadly to the outer shell of all bivalvia mollusks of the oyster superfamily of the order Ostreales.
In this context, the unit "phr" (Parts Per hung Resin) indicates the Parts by weight added by an additive Per one Hundred Parts by weight of virgin rubber.
As described above, the present invention provides a plastic containing a calcined oyster shell powder, a plastic product, and a method for producing a plastic, wherein the obtained plastic has antibacterial properties and the problem of air stain caused by the addition of the calcined oyster shell powder is improved.
In some embodiments of the present disclosure, a plastic is provided, comprising oyster shell calcined powder, polyvinyl chloride, and an acrylate copolymer.
In some embodiments, the oyster shell calcined powder is obtained by calcining oyster shell at a temperature ranging from 900 ℃ to 1200 ℃ (such as 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or any value in any range of the foregoing). In some embodiments, the weight percentage of calcium carbonate in oyster shell is at least 94% (e.g., 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, 100% or any range of values described above) and the weight percentage of calcium oxide in calcined oyster shell is at least 93% (e.g., 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, 100% or any range of values described above). In some embodiments, the oyster shell calcined powder is obtained by respectively performing cleaning treatment, crushing treatment, calcining treatment at a temperature range of 900-1200 ℃, and grinding treatment on oyster shells. It is worth noting that the oyster shell calcined powder is rich in calcium oxide, can release oxygen-containing free radicals, and has excellent bacteriostatic ability.
In some embodiments, the calcined oyster shell powder has a particle size of 7 microns to 500 microns, such as 7 microns, 8 microns, 9 microns, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, 150 microns, 200 microns, 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, 500 microns, or any range of values therein.
In some embodiments, the calcined oyster shell powder is present in an amount of 3 to 10 parts by weight (e.g., 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or any range of values described above) and the acrylate copolymer is present in an amount of 0.8 to 10 parts by weight (e.g., 0.8 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or any range of values described above) based on 100 parts by weight of polyvinyl chloride.
In some embodiments, the acrylate based copolymer comprises methyl methacrylate and butyl acrylate. In some embodiments, the acrylate copolymer may include an alkyl (meth) acrylate and/or a monomer having a styrene group, and the alkyl group of the alkyl (meth) acrylate has a carbon number of 1 to 16 (e.g., a carbon number of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16). In some embodiments, the molecular weight of the acrylate-based copolymer ranges from 100 to 700 million (e.g., 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, or any range of values described above). In some embodiments, the weight percentage of methyl methacrylate is 50% to 99% (e.g., 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, or any range of values) and the weight percentage of butyl acrylate is 1% to 50% (e.g., 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any range of values) if the weight percentage of acrylates is 100%.
In one embodiment, the acrylate copolymer may be obtained by copolymerizing methyl methacrylate and butyl acrylate, wherein the molecular weight may range from 100 to 200 ten thousand (e.g., 100, 150, 200, or any range of values described above). In one embodiment, the weight percentage of the acrylic copolymer obtained by copolymerizing methyl methacrylate and butyl acrylate is 70% to 90% (70%, 75%, 80%, 85%, 90%, 95%, 99%, or any value in the foregoing range) and the weight percentage of butyl acrylate is 10% to 30% (e.g., 10%, 15%, 20%, 25%, 30%, or any value in the foregoing range), based on 100%. In one embodiment, the amount of the acrylic copolymer obtained by copolymerizing methyl methacrylate and butyl acrylate is 0.8 to 10 parts by weight (for example, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight or a value in any range) based on 100 parts by weight of polyvinyl chloride in the plastic.
In some embodiments, the acrylate-based copolymer further comprises butyl methacrylate.
In one embodiment, the acrylate copolymer may be obtained by copolymerizing methyl methacrylate, butyl acrylate, and butyl methacrylate, wherein the molecular weight may range from 350 to 700 thousands (e.g., 350, 400, 450, 500, 550, 600, 650, 700 thousands, or any range of values described above). In one embodiment, the weight percentage of the acrylate copolymer obtained by copolymerizing methyl methacrylate, butyl acrylate, and butyl methacrylate is 50% to 70% (e.g., 50%, 55%, 60%, 70%, or any value in the foregoing range), the weight percentage of methyl acrylate is 10% to 30% (e.g., 10%, 15%, 20%, 25%, 30%, or any value in the foregoing range), and the weight percentage of butyl methacrylate is 10% to 30% (e.g., 10%, 15%, 20%, 25%, 30%, or any value in the foregoing range), based on 100%. In one embodiment, the acrylic copolymer obtained by copolymerizing methyl methacrylate, butyl acrylate and butyl methacrylate is 0.8 to 10 parts by weight (for example, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight or a numerical value in any of the above ranges) based on 100 parts by weight of polyvinyl chloride.
In some embodiments, the plastic further comprises other adjuvants including, but not limited to, stabilizers (e.g., organotin stabilizers, barium zinc stabilizers, or combinations thereof), internal slip agents (e.g., stearic alcohol, stearic amine, butyl stearate, glyceryl monostearate, or combinations thereof), external slip agents (e.g., paraffin waxes, stearic acids, polyethylene waxes, oxidized polyethylene waxes, or combinations thereof).
In some embodiments of the present disclosure, there is provided a method of manufacturing a plastic, comprising: providing oyster shells; calcining oyster shells to obtain oyster shell calcined powder; and smelting the oyster shell calcined powder, polyvinyl chloride and the acrylate copolymer to obtain the plastic.
In some embodiments, the step of calcining the oyster shell is performed at a temperature in a range between 900 ℃ and 1200 ℃, such as 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or any of the foregoing ranges.
In some embodiments, the method further comprises performing a washing process and a pulverizing process on the oyster shell before the step of calcining the oyster shell. In some embodiments, the method further comprises performing a grinding process on the oyster shell calcined powder after the step of calcining the oyster shell. In some embodiments, the cleaning process, the pulverizing process, the calcining process, and the grinding process are performed separately on the oyster shells.
In some embodiments, in the step of melting the calcined oyster shell powder, the polyvinyl chloride, and the acrylate copolymer, the weight parts of the polyvinyl chloride, if calculated as 100 parts by weight, are 3 to 10 parts by weight (e.g., 3, 4, 5, 6, 7, 8, 9, 10, or any range of values) and the weight parts of the acrylate copolymer are 0.8 to 10 parts by weight (e.g., 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any range of values).
In some embodiments of the present disclosure, a plastic article is provided comprising oyster shell calcined powder, polyvinyl chloride, and a plastic of an acrylate copolymer. In some embodiments, the plastic article is a pipe, a packaging material, a stationery material, a decorative material, a building material, or a combination thereof.
A series of procedures for measuring the antibacterial property and physical property of a plastic to which a calcined oyster shell powder is added and analysis results thereof are provided below to specifically describe some embodiments of the present disclosure.
Preparation of oyster shell calcined powder
First, oyster shells are provided. Then, after the oyster shells are washed, the oyster shells are coarsely crushed into oyster shell particles. Then, the oyster shell particles are calcined at a temperature ranging from 900 ℃ to 1200 ℃. Then, the calcined oyster shell particles are ground to obtain the oyster shell calcined powder with the average particle size of not more than 500 microns. The calcium carbonate in the original oyster shell can be converted into calcium oxide after being calcined, and the oyster shell calcined powder used in some embodiments of the invention contains more than 93 weight percent of calcium oxide.
Antibacterial property test of plastics
In order to analyze the antibacterial effect of the oyster shell calcined powder rich in calcium oxide and polyvinyl chloride which are jointly prepared into plastic, the plastic is prepared. The calcined oyster shell powder prepared by the method, polyvinyl chloride and an auxiliary agent (organic tin, glyceryl monostearate, stearic acid, calcium carbonate, an acrylate copolymer A (an acrylate copolymer obtained by copolymerizing 80 weight percent of methyl methacrylate and 20 weight percent of butyl acrylate and having a molecular weight of 100 to 200 ten thousand) are uniformly mixed according to the formula of the following table 1 to form a material stack (bank), then the material stack is uniformly smelted at 190 to 200 ℃, then the material stack is plasticized by a double-roll rolling turbine and cooled to prepare a plastic test piece with the length of 120 mm, the width of 70 mm and the thickness of 0.5 mm (the test piece used here is a hard plastic test piece prepared without adding a plasticizer, and the hardness is higher compared with a soft plastic test piece prepared by adding a plasticizer, and the hard plastic test piece is represented here, subsequent property tests, hereinafter referred to as plastic coupons) are performed.
TABLE 1 melting ratio of materials in plastic test piece
Next, using plastic test pieces containing different amounts of oyster shell calcined powder, an antibacterial property test was performed. The antibacterial test of the plastic test piece adopts Japanese industrial standard method JIS Z2801 (same with CNS 15823, plastic and non-porous surface antibacterial test method), and comprises the following specific steps: firstly, cleaning a plastic test piece with 75% alcohol, and then inoculating 0.4 ml of escherichia coli culture solution; subsequently, the membrane was covered and placed in a petri dish for 24 hours. After the incubation was completed, the plastic test piece was washed with 10 ml of the culture medium. Finally, the culture medium washed by each plastic test piece group is coated on a proper culture medium, after culturing for 16 to 24 hours, the number of colonies growing in the culture medium corresponding to the culture medium of each plastic test piece is counted, and the antibacterial ratio (%) of each example is calculated by using comparative example 1 as a control, and the results are shown in table 2 below.
TABLE 2 results of the antibacterial property test of plastic test pieces containing calcined oyster Shell powder
The results in Table 2 show that when the amount of oyster shell calcined powder added was 1phr, the number of colonies of Escherichia coli measured on the plastic test pieces was increased as compared with the comparative example in which no oyster shell calcined powder was added, that is, the antibacterial ratio of the plastic test pieces in which the amount of oyster shell calcined powder added was 1phr was not increased as compared with the comparative example. However, when the amount of the calcined oyster shell powder is increased to 3phr or more (including 3phr), 99.9% of the antibacterial activity can be achieved. That is, the proportion of the calcined oyster shell powder is at least 3phr, so that the plastic test piece can achieve 99.9% antibacterial rate.
Physical Property test of Plastic
In order to analyze the properties of the plastic test piece and the preparation process after adding the calcined oyster shell powder, polyvinyl chloride and additives (organic tin, glycerol monostearate, stearic acid, calcium carbonate and acrylate copolymer A (acrylic copolymer with molecular weight of 100-200 ten thousand, obtained by copolymerizing 80% of methyl methacrylate and 20% of butyl acrylate) or acrylate copolymer B (acrylic copolymer with molecular weight of 350-700 thousand, obtained by copolymerizing 60% of methyl methacrylate, 20% of butyl acrylate and 20% of butyl methacrylate)) are added as an aggregate according to the formulation in Table 3 and in a manner similar to that in Table 2, and the kneaded aggregate is prepared into a plastic test piece, and the processability of the plastic test piece in the aggregate kneading process is analyzed, The releasability when the plastic test piece was separated from the roll, and the yellowness, gas stain degree, Heat Distortion Temperature (HDT), and flexural modulus (rigidity) of the obtained plastic test piece, the results are shown in table 3 below.
In addition, the conventional antibacterial agents used in the hard plastic test pieces are relatively rare, and in order to compare the effect of the addition of the oyster shell calcined powder with the antibacterial agents in the conventional plastic test pieces on the physical properties of the plastic, table 3 shows that the conventional commercially available liquid antibacterial agents added to the soft plastic are used as comparative examples (comparative examples 2 to 4).
TABLE 3 results of physical Properties test of Plastic test pieces comprising calcined oyster Shell powder
*: processability: when the plastic test piece is kneaded, the rolling degree of the material is decreased with the fraction, which means that the rolling is smoother and the processability is better (that is, the processability is improved as the fraction is decreased from (5) to (1)).
**: release property: and placing the smelted finished product between two rollers, and pressing the smelted finished product by the relative rolling of the two rollers to prepare the plastic test piece on the surface of the roller. And then, stretching the plastic test piece in a natural and non-special force applying manner to separate the plastic test piece from the roller, and recording the length of the plastic test piece, wherein the shorter the length of the plastic test piece is, the less the plastic test piece is easy to adhere to the roller, and the better the release property of the plastic test piece is.
***: degree of gas spots: the degree of gas spotting was assessed visually and recorded as different grades of score (1) to score (5), reflecting an increase in gas spotting as the score increased.
X: indicating that no data is available. Specifically, the plastic test piece was strongly adhered to the roller, and the releasability was very poor, so that the plastic test piece could not be separated from the roller, and thus data of other physical property tests (yellowness, gas stain degree, heat distortion temperature, flexural modulus) could not be obtained. In addition, since the accumulated material cannot be plasticized into a plastic test piece separable from the roll and has no workability, the workability field is also exemplified by X.
Workability
The workability reflects the difficulty of the accumulated material for subsequent processing, and is obtained by analyzing the rolling degree of the accumulated material during the mixing of the accumulated material, and the better the rolling degree of the accumulated material (the lower the fraction), the better the workability.
Table 3 shows that when the liquid antimicrobial agent was added to the plastic test piece (comparative examples 2 to 4 in table 3), the plastic test piece was not separated by adhering to the roll as the amount of the liquid antimicrobial agent was increased, and thus was not used for the subsequent processing, and the processability was lost (comparative examples 3 and 4 in table 3).
When the calcined oyster shell powder was added to the plastic test pieces (examples 1 to 3 in table 3), the rolling of the accumulated material became irregular as the amount of the calcined oyster shell powder was increased, and the processability of the plastic test pieces was lowered. However, when the amount of the acrylic copolymer A added was increased from 1phr to 2phr (examples 3 to 4 in Table 3), the smoothness of the rolling of the accumulated material was improved, and the problem of poor processability after the addition of the oyster shell calcined powder to the plastic test piece was improved. In addition, if the acrylic copolymer B is added additionally instead of increasing the addition amount of the acrylic copolymer a (1phr of the acrylic copolymer B, example 5), the problem of poor processability of the plastic test piece after the addition of the calcined oyster shell powder can be improved, and even better processability can be achieved compared with the group in which the addition amount of the acrylic copolymer a is increased (2phr of the acrylic copolymer a, example 4): further, as the amount of the acrylic copolymer B added was increased (2phr of the acrylic copolymer B, example 6), the processability was also increased.
Release property
The release property reflects the separable degree between the plastic test piece and the preparation tool (such as a roller), and the length of the plastic test piece is obtained by recording the length of the plastic test piece when the plastic test piece is separated from the roller in a natural and non-special force applying mode, wherein the shorter the length of the plastic test piece is, the less the plastic test piece is adhered to the roller, the better the release property of the plastic test piece is.
Table 3 shows that when the liquid antimicrobial agent was added to the plastic test piece (comparative example 2 in table 3), the length of the plastic test piece was increased and the releasability was significantly reduced. Furthermore, as the amount of the liquid antimicrobial agent added increases (comparative examples 3 and 4 in table 3), the plastic test piece adheres to the roller, the release property is very poor, and even the plastic test piece cannot be separated from the roller, and the data of the release property cannot be obtained according to the length of the plastic test piece.
When calcined oyster shell powder was added to the plastic test pieces (examples 1 to 3 in table 3), the releasability of the plastic test pieces was not affected. Further, when the amount of the acrylic copolymer a added was increased from 1phr to 2phr (examples 3 to 4 in table 3), the releasability of the plastic test piece was improved. In addition, if the acrylic copolymer B is added additionally instead (1phr of the acrylic copolymer B, example 5), the addition amount of the acrylic copolymer a is not increased, the release property of the plastic test piece can also be improved: further, as the amount of the acrylic copolymer B added was increased (2phr of the acrylic copolymer B, example 6), the releasability was also increased.
Yellowness index
The yellowness is obtained by analyzing the color change of a plastic test piece through a spectrophotometer, and is generally caused by the fact that the molecular structure itself is affected by environmental factors (such as heat or light), so that the molecular structure itself is changed to be yellowed, or an additive reacts with a plastic raw material (such as polyvinyl chloride in an embodiment) so that the plastic test piece is yellowed. Therefore, the yellowness can reflect the thermal stability of the plastic test piece, and the higher the yellowness, the better the thermal stability is.
Table 3 illustrates that when a liquid antimicrobial agent is added to the plastic test piece (comparative example 2 of table 3), the yellowness of the plastic test piece is significantly increased. In addition, as the addition amount of the liquid antimicrobial agent was increased (comparative examples 3 and 4 in table 3), the plastic test piece could not be separated by the roller and the plastic test piece could not be analyzed, and thus the yellowness data of the group with the increased addition amount of the liquid antimicrobial agent could not be obtained.
When oyster shell calcined powder is added to the plastic test piece (example 1 to example 3 in table 3), the yellowness of the plastic test piece is increased as the addition amount of the oyster shell calcined powder is increased; in addition, when the yellowness of the oyster shell calcined powder (1phr of oyster shell calcined powder, example 1) and the liquid antibacterial agent (1phr of liquid antibacterial agent, comparative example 2) were compared at the same addition amount, the increase in yellowness of the plastic test piece to which the oyster shell calcined powder was added was small, which indicates that the thermal stability of the plastic test piece is better than that of the plastic test piece to which the oyster shell calcined powder was added. In addition, with respect to the plastic test pieces to which the oyster shell calcined powder and the acrylic copolymer a were added (1phr of the acrylic copolymer a, example 2 in table 3), the yellowness was not significantly affected regardless of whether the amount of the acrylic copolymer a added was increased (2phr of the acrylic copolymer a, example 4 in table 3) or the plastic test pieces to which the acrylic copolymer B was additionally added (examples 5 to 6 in table 3).
Degree of gas spots
The gas spots are the condition that gas is not well removed in the plastic test piece forming process, the gas spot degree in the table 3 is obtained by visual evaluation, and the gas spot degree is increased by increasing the fraction.
Table 3 illustrates that when a liquid antimicrobial agent is added to the plastic test piece (comparative example 2 in table 3), the degree of gas stain of the plastic test piece is significantly increased (see fig. 1A and 1B). In addition, as the amount of the liquid antimicrobial agent added was increased (comparative examples 3 and 4 in table 3), the plastic test piece could not be separated by the roll and the plastic test piece could not be analyzed, and thus the gas spot level data of the plastic test piece could not be obtained.
When oyster shell calcined powder was added to the plastic test pieces (examples 1 to 3 in table 3), the degree of air stain increased as the amount of oyster shell calcined powder added increased. Further, when the amount of the acrylic copolymer A added was increased from 1phr to 2phr (examples 3 to 4 in Table 3), the degree of gas stain in the plastic test piece could be reduced. In addition, if the acrylic copolymer B is added additionally instead (1phr of acrylic copolymer B, example 5), the degree of the gas stain of the plastic test piece can be reduced without increasing the addition amount of the acrylic copolymer a, and the degree of the gas stain is reduced as the addition amount of the acrylic copolymer B is increased (2phr of acrylic copolymer B, example 6) (see fig. 2). Further, it is advantageous that the effect of reducing the gas stain is achieved by only 1phr of the acrylic copolymer B, which is similar to the effect obtained by adding 2phr of the acrylic copolymer A (example 4).
Heat Distortion Temperature (HDT)
The heat distortion temperature is the heat resistance of the plastic test piece, and is obtained by detecting the specific temperature at which the plastic test piece deforms when the applied pressure is 1.82MPa (standard test specification ASTM D648), and the higher the Heat Distortion Temperature (HDT), the higher the heat resistance.
Table 3 illustrates that when a liquid antimicrobial agent is added to the plastic test piece (comparative example 2 of table 3), the HDT of the plastic test piece is not affected. In addition, as the addition amount of the liquid antimicrobial agent was increased (comparative examples 3 and 4 in table 3), the plastic test piece could not be separated by the roller and the plastic test piece could not be analyzed, and thus HDT data of the liquid antimicrobial agent addition amount increase group could not be obtained.
When oyster shell calcined powder was added to the plastic test pieces (examples 1 to 3 in table 3), HDT of the plastic test pieces increased as the amount of oyster shell calcined powder was increased. In addition, no matter the addition amount of the acrylic copolymer a was increased (2phr of the acrylic copolymer a, example 4 of table 3), or the additional addition of the acrylic copolymer B (examples 5 to 6 of table 3), there was no significant effect on the HDT of the plastic test piece.
Flexural modulus of elasticity (rigidity)
The flexural modulus of elasticity is represented by the rigidity of a plastic test piece, which is obtained by placing the plastic test piece on two fixed supporting points (fixed pivots) at a certain distance, pressing the plastic test piece from top to bottom at the midpoint of the two supporting points by a three-point test method at a speed of 15 mm/min until the sample is broken or exceeds a certain limit, and recording the pressure value at the moment (standard test specification ASTM D790), wherein the higher the flexural modulus of elasticity is, the better the rigidity is.
Table 3 illustrates that when a liquid antimicrobial agent is added to the plastic test piece (comparative example 2 of table 3), the HDT of the plastic test piece is not affected. In addition, as the amount of the liquid antimicrobial agent added was increased (comparative examples 3 and 4 in table 3), the plastic test piece could not be separated from the roll and the plastic test piece could not be analyzed, and thus the flexural modulus data of the group with the increased amount of the liquid antimicrobial agent could not be obtained.
When the calcined oyster shell powder was added to the plastic test pieces (examples 1 to 3 in table 3), the flexural modulus of the plastic test pieces increased as the amount of the calcined oyster shell powder was increased. In addition, no matter the addition amount of the acrylic copolymer a is increased (2phr of the acrylic copolymer a, example 4 in table 3), or the acrylic copolymer B is additionally added (examples 5 to 6 in table 3), the flexural modulus of the plastic test piece is not significantly affected.
In summary, some embodiments of the present disclosure illustrate that, when the calcined oyster shell powder is added to the plastic, an antibacterial ratio of 99.9% can be achieved with 3phr or more.
If the existing liquid antibacterial agent for soft plastics is used in hard plastics, the release property of the plastics is reduced, even the plastics stick to the roller and cannot be separated from the roller, severe gas stain is generated, and the yellowness is remarkably increased, wherein the Heat Distortion Temperature (HDT) and the rigidity (bending elastic modulus) are not affected.
In some embodiments of the present disclosure, if the calcined oyster shell powder is used as the antimicrobial agent for plastic, in the hard plastic, not only the processability and release property of the plastic are not affected (the release property of the plastic with the liquid antimicrobial agent added is reduced, or even the plastic is stuck), but also the Heat Distortion Temperature (HDT) and the rigidity (bending elastic modulus) of the plastic can be increased, and the degree of increase of yellowness is lower than that of the plastic with the liquid antimicrobial agent added, which means that the degree of thermal stability is better. Further, some embodiments of the present disclosure also show that although the oyster shell calcined powder can increase the degree of air stain, if the amount of the acrylic copolymer a is increased or the acrylic copolymer B is additionally added to the plastic, the air stain caused by the oyster shell calcined powder can be effectively reduced, and the processability and the release property are improved.
Although this summary has described specific details in terms of certain embodiments, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.
Claims (11)
1. A plastic, which is characterized by comprising oyster shell calcined powder, polyvinyl chloride and acrylate copolymer.
2. The plastic of claim 1, wherein the acrylate-based copolymer has a molecular weight in the range of 100 to 700 million.
3. The plastic of claim 1, wherein the oyster shell calcined powder is in an amount of 3 to 10 parts by weight and the acrylic copolymer is in an amount of 0.8 to 10 parts by weight based on 100 parts by weight of polyvinyl chloride.
4. The plastic of claim 1, wherein the acrylate copolymer comprises methyl methacrylate and butyl acrylate.
5. The plastic of claim 4, wherein the weight percent of the acrylates is 100%, the weight percent of the methyl methacrylate is 50% to 99%, and the weight percent of the butyl acrylate is 1% to 50%.
6. The plastic of claim 4, wherein the acrylate-based constituent further comprises butyl methacrylate.
7. The plastic of claim 6, wherein the weight percent of the acrylates is 100%, the weight percent of the methyl methacrylate is 50% to 70%, the weight percent of the butyl acrylate is 10% to 30%, and the butyl methacrylate is 10% to 30%.
8. A method of manufacturing a plastic material, comprising:
providing oyster shells;
calcining the oyster shell to obtain oyster shell calcined powder;
and smelting the oyster shell calcined powder, the polyvinyl chloride and the acrylate copolymer to obtain the plastic.
9. The method as claimed in claim 8, wherein in the step of melting the oyster shell calcined powder, polyvinyl chloride and the acrylate copolymer, the polyvinyl chloride is present in an amount of 3 to 10 parts by weight and the acrylate copolymer is present in an amount of 0.8 to 10 parts by weight, based on 100 parts by weight.
10. A plastic article comprising the plastic of any one of claims 1 through 7.
11. The plastic article of claim 10, wherein the plastic article is a pipe, a packaging material, a stationery material, a decorative material, a building material, or a combination thereof.
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| JP2022136995A (en) | 2022-09-21 |
| TW202235522A (en) | 2022-09-16 |
| JP7479415B2 (en) | 2024-05-08 |
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