CN1274749C - Thermoplastic articles exhibiting high surface-available silver - Google Patents

Thermoplastic articles exhibiting high surface-available silver Download PDF

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Publication number
CN1274749C
CN1274749C CNB028249771A CN02824977A CN1274749C CN 1274749 C CN1274749 C CN 1274749C CN B028249771 A CNB028249771 A CN B028249771A CN 02824977 A CN02824977 A CN 02824977A CN 1274749 C CN1274749 C CN 1274749C
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silver
antibacterial agent
carboxylate salt
containing antibacterial
thermoplastic article
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CN1604785A (en
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E·拉里敦
G·哈斯
R·丹克尔
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Milliken and Co
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Milliken and Co
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Priority claimed from US10/015,305 external-priority patent/US20030108608A1/en
Priority claimed from US10/015,872 external-priority patent/US6641842B2/en
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/42—Phosphorus; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/38—Silver; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Polymers & Plastics (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Inorganic Chemistry (AREA)
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  • Pharmacology & Pharmacy (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Improvements in increasing the amount of surface-available silver in thermoplastic articles comprising certain silver-containing antimicrobial agents. Such an invention requires the incorporation of a sufficient amount of a carboxylic acid salt within the thermoplastic article simultaneously with the necessary silver-containing antimicrobial agent. Certain carboxylic acid salts are standard acid scavengers and lubricants for certain thermoplastic applications; however, the amounts required within this inventive thermoplastic article are in excess of that commonly added within such articles, and the types of acid scavengers possibly added within such target thermoplastic articles are preferably neutralized hydrotalcite compounds, thereby permitting the carboxylic acid salt to function in the inventive manner. Surprisingly, such a high amount of such standard salts, as well as potentially other non-standard salts, present within the target thermoplastic cause the release of greater amounts of silver to the target article's surface, thereby permitting a greater degree of antimicrobial activity, among other potential benefits for such an increase in surface-available silver. Methods of producing such inventive thermoplastics are also encompassed within this invention.

Description

Contain the effectively thermoplastic article of silver of exhibiting high surface
Invention field
The present invention relates to improve the effectively innovative approach of silver content of surface in the thermoplastic article that comprises some silver-containing antibacterial agent.This invention need add capacity carboxylate salt and essential silver-containing antibacterial agent in the thermoplastic article simultaneously.Some carboxylate salt is standard acid scavenger and the lubricant that is used for some thermoplasticity Application Areas; Yet, amount required in the thermoplastic article of the present invention is more than the amount that adds this based article usually, and the kind that can add the acid scavenger of this class target thermoplastic article is preferably the neutral water talc compound, and carboxylate salt can be played a role in the method for the invention.It is shocking, the like this a large amount of this standard salt that exists in the target thermoplastic goods and other non-standard salt that may exist, make more silver be discharged into the target product surface, in for other the potential benefit that increases the effective silver in surface, produce anti-microbial activity thus than hard intensity.The present invention also comprises the method for making this thermoplastics.
Prior art is discussed
In recent years, the harm of the bacterial contamination that is caused by potential daily contact has obtained a large amount of concerns.The noticeable example of this respect comprises: the lethal effect of the food poisoning that is caused by the intestinal bacteria of some bacterial strain that exists in the unseasoned beef in the fast-food restaurant; By the salmonella-polluted disease that causes in the under-done and unwashed poultry food; And the disease and the skin infections that cause because of streptococcus aureus, yeast and other unicellular organism body.Along with the increase of human consumer to this field interest, manufacturers has begun to introduce antiseptic-germicide in various household product and goods.
Develop the silver-containing inorganic microbicide recently, and it has been used in many different grounds as antiseptic-germicide and the surface is gone up and is used in these grounds and the surface.Particularly, made this microbicide be suitable for adding in plastics composite and the fiber, thereby the houseware and the consumer's goods that itself have anti-microbial property are provided.Although this money base reagent provides suitable anti-microbial property for the goods of thermoplastic article and other kind, still there is some limitation in the potential antibacterial efficacy for these analog thermoplastic goods.These limitation obviously are because effectively the content of silver is relatively low in these analog thermoplastic goods and/or at this based article upper surface.Be not limited to any specific scientific theory, the complete silver compound that this low surperficial significant quantity of silver is considered to capacity can not be moved to thermoplastic surface's result.Can observe this result to the standard thermoplastic plastics that contain silver-containing antibacterial agent.Therefore, need provide the silver-containing antibacterial agent of significant quantity in thermoplastic compounds, it contains and is difficult to the effective silver compound in high-load surface that obtains before this, other potential ideal performance that more effective anti-microbial activity is provided thus and therefore produces.
The plastics composite that contains silver-containing antibacterial agent and the goods in past comprise the United States Patent (USP) 5 of authorizing people such as Ohsumi, 405,644 (they comprise some triazole of adding), authorize late people's such as Niira United States Patent (USP) 4,938,955 (also comprising the benzotriazole stablizer), authorize people's such as Nosu United States Patent (USP) 5,750,609, it discloses and can add multiple composition (for example film, fiber, makeup, or the like) ultraviolet protecting agent, this protective agent contains the zinc-base hydrotalcite that serves as UV light absorber separately.Yet, these ad hoc approach and plastics have proved cost too high (at first be because benzotriazole expensive), particularly because need the high price stable compound of relative higher concentration, and can not provide the raising of any effective silver that can discover on the surface of these goods.Similarly, because these stablizers are not heat-staple, they have increased the complicacy of handling.Strictly speaking, relate to the effectively required innovative approach of silver compound content of increase surface on target thermoplastic without any theory or reasonable suggestions in the prior art.
Invention is described
Therefore, the purpose in the present invention ground is to improve the effectively content of silver of the middle surface of actual thermoplastic article (container, sheet material, film, fiber, and analogue).Another object of the present invention is to obtain above-mentioned raising by desirable the buied component that employing is used for the thermoplasticity prescription.Another purpose of the present invention provides the thermoplastic article with very effective germ resistance.A further object of the present invention provides the method that a kind of effective silver content of this class target invention plastics upper surface of raising to one's profit also reduces active silver-colored residual volume in the target resin itself thus.
Therefore, the present invention includes a kind of thermoplastic article, these goods contain at least a silver-containing antibacterial agent, optional at least a acid scavenger compound and except or surpass 0.1wt% to 1.25wt% the described optional at least a acid scavenger compound, be preferably about 0.2 to about 1.0%, more preferably about 0.2 to about 0.5%, most preferably is at least a carboxylate salt component of about 0.3wt%.In addition, the present invention also comprises a kind of method of making thermoplastic article, this method comprises the following steps: to provide a kind of thermoplastic polymer, add at least a silver-containing antibacterial agent, compound is removed in optional at least a acid, with except or surpass 0.1wt% to 1.25wt% the described optional at least a acid scavenger compound, be preferably about 0.2 to about 1.0%, more preferably about 0.2 to about 0.5%, most preferably is at least a carboxylate salt component of about 0.3wt%, with the described polymkeric substance that makes, the mixture melt of silver-containing antibacterial agent and at least a carboxylate salt, and described molten mixture is cooled to the thermoplastic article of desired shape.Similarly, the present invention includes a kind of polyolefin articles, these goods contain at least a silver-containing antibacterial agent, and record by the salt test of carrying that at room temperature continues 24 hours, the surperficial significant quantity of the silver on described surface be at least 0.25 microgram silver/square decimeter (or the effectively silver-colored content in a kind of surface is the styrenic thermoplastic goods of at least 0.80 microgram silver/square decimeter).Also do not have in the prior art open, adopt or advised reasonably that this specific plastics or its manufacture method had these desirable thermoplastic articles that increases surperficial effective silver-colored characteristic with manufacturing.
Term " surface effectively silver " is meant can detect on the surface of target product and has the effectively phenomenon of silver, and no matter it is as metal or ion, or may be from this surface very near but imbed wherein up to relatively easily extracting.Detection in this case realizes by a kind of ad hoc approach, and is as implied above, wherein at room temperature with product sample at extraction solution, for example, be dipped into few 24 hours in the mixed salt solution (being potassium-sodium phosphates buffered soln in this case).After this, by, for example but be not limited to, inductively coupled plasma spectrometry method (after this being called ICP) is analyzed the situation that exists of silver in this extraction solution, and these silver are removed from the target thermoplastic goods in this extraction process.Therefore, the detection of this silver has been shown that silver is at product surface or in the validity of this near surface and therefore relevant with active raising, this active raising is relevant with the validity of silver in this method.
Immediate technology all is included in and has silver-containing antibacterial agent in the thermoplastics, does not increase this desirable the surface effectively needs or the possibility of silver compound but all relate to.This class prior art above has been discussed.
The present invention can use any plastics that can suitably add silver-containing antibacterial agent.Can use among the present invention, for example, but be not limited to, polyolefine (for example polyethylene, polypropylene and polybutene), vinylbenzene (for example polystyrene, ABS and analogue) and polyester (for example polyethylene terephthalate).Preferably, plastics are the thermoplasticss that can be molded into different shapes and size when molding extrudes, and molding wherein contains silver-containing antibacterial agent and required excess carboxylate.Therefore, polyolefine (particularly polypropylene) and vinylbenzene (particularly polystyrene) are preferred.In addition, this plastics are preferably and can paint to satisfy final user's aesthetic requirement.Therefore, these plastics can also contain colorant, for example poly-(oxygen alkylene) colorant, pigment, dye well analogue.Can also there be other additive, comprises static inhibitor, brighten compound, nucleator, finings, lubricant, fire retardant, antioxidant, ultra-violet stabilizer, weighting agent, and analogue.
Preferred silver-containing antibacterial agent is inorganic Ag-containing compound, include but not limited to, the commodity of producing such as Milliken Co. are called ALPHASAN  RC-2000, the mineral compound of the Trisilver phosphate zirconium of RC-5000 and RC-7000, although in plastics of the present invention, (for example can use any silver-containing inorganic antibacterial, as just example, the silver that originates from the commodity ZEOMIC  by name of Shingawa replaces zeolite, originate from the silver-containing glass of the commodity IONPURE  by name of Ishizuka Glass, originate from the commodity AMP  T558 by name of Dupont and the silver-containing glass of MICROFREE , silver-containing glass with the commodity that originate from Johnson Mathey JMAC  by name).Usually, the add-on of this antiseptic-germicide is about 0.01 to 10% of a target plastic composition total weight; More preferably about 0.05 to about 2.0%; Most preferably be about 0.5 to about 2.0%.
Carboxylate salt can be any be C based on monovalence, divalence or trivalent metal ion and carbon chain lengths 1-C 40Salt.Preferably, described at least a carboxylate salt is selected from: with at least a at least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion 1-C 40Carboxylic acid cpd.Described ion includes but not limited to: monovalent ion such as basic metal (for example sodium, potassium, lithium, and analogue), divalent ion such as alkaline-earth metal (for example calcium, barium, strontium, magnesium, cadmium, rubidium, and analogue), zinc, tin (II), iron (II), for example aluminium.As if from the angle and the aesthetic angle of the effective silver compound in surface, divalence and trivalent ion provide best integrated thermoplastic goods, because the problem seemingly bigger for the monovalent ion decolouring.Yet owing to certain undetermined reason, it is even more serious to larger sized monovalent metallic ion (for example, sodium and potassium) to decolour.Resin becomes palm fibre or flavescence to a certain extent although these compounds make the target invention really, but for some reason, these colors also are acceptable, or even want to obtain, therefore the use of these carboxylate salts is not disappointed fully, therefore remains feasible in the present invention.Preferably, required carboxylate salt is preferably selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate (also comprising two and three stearate) and their any mixture (although also can use other chain length, comprise myristate, behenate, oleate, palmitate and analogue, but these stearate and acetate are non-limitative preferred embodiment of the present invention).(although also being nonrestrictive) calcium stearate most preferably, this be since as follows it in the ultimate aim thermoplastic article processing and the advantage aspect the maximum effectiveness.As mentioned above, the add-on of carboxylate salt should be about 0.1wt% to 1.25wt% of whole polymeric constituent weight, is preferably about 0.2 to about 1.0%, more preferably about 0.2 to about 0.5%, most preferably is 0.3%.Any other acid scavenger compound that this add-on contains more than subject polymer itself (and preferably, except purposes of the present invention, not using any carboxylate salt) as acid scavenger.Under any circumstance, this add-on is usually all more than the standard addition of the deacidification of using in thermoplastic article with carboxylate salt (for example calcium stearate).It is shocking, have been found that excessive like this carboxylate salt helps to make the effectively very desirable raising of silver compound acquisition of surface on the target thermoplastic goods that contain silver-containing antibacterial agent.Be not appreciated that fully what adds excess carboxylate and can play this effect; Yet, too many carboxylate salt is (for example greater than above-mentioned maximum, for example all about 1.3wt% of polymeric constituent weight and Geng Gao and in some cases, even the amount in above-mentioned feasible proportional range) shows the rapid reduction of the effective silver compound in this surface and therefore can not suitably play a role (and, in fact can cause the amount of this silver compound to be lower than really only to contain silver-containing antibacterial agent and the content of this silver compound in the thermoplastics contrast of carboxylate-containing not fully).And, do not reckon with that fully this choice criteria of necessary carboxylate salt finally provides and has been considered to germ resistance and obtains very big improved thermoplastic article.
As described below, the base program of making antibacterial plastic product of the present invention comprises standard plastic formation technology.Two kinds of basic methods that add additive (for example silver-containing antibacterial agent and necessary carboxylate salt) in polymer product are arranged.A kind of method is the mixture of dried blending of polymers, additive, antiseptic-germicide and carboxylate salt; Dry mixture is fused into the fusion formulation, then this formulation is finally cooled off and cut into the ball shape; Then this pellet is added injector or other similar processing units, and finally be cooled to moulded products.Perhaps, traditional resin ball can be mixed with the master batch concentrate that contains antiseptic-germicide and carboxylate salt additive, and molded in traditional mold apparatus.Aforementioned molding step is preferably carried out with injection forming equipment; Yet, also can use other plastic shaping methodology, such as but not limited to, blowing, fiber extrusion, film forming, pressing mold, rotational molding, and analogue.Those of ordinary skill in the art can understand and understand these alternative plastics-forming operation methods well.Then by many different technology, include but not limited to, injection molding, injection blow molding, injection drawing blow, injection rotational molding, extrusion, extrusion blowing, compressing tablet extrude, extrude film forming, cast film extrusion, foam extrusion, thermoforming (for example making film, blown film, biaxially oriented film) thin-walled injection molding, reach similar approach, and said composition is manufactured fabricated product.For vinylbenzene, this program need be used the ball shaped polymer that contains antioxidant, lubricant and analogue usually, and additive adds in advance, sneaks into powdery antiseptic-germicide and carboxylate salt component then therein.In the fusing and molten component blended process before extrusion or other procedure of processing, the solid pellet of making is melted then by heating spiral rod.
Also can use other additive in the composition of the present invention, as long as they do not influence main advantage of the present invention.With these additives or analog structure and silver-containing antibacterial agent and carboxylate salt premix with the fusing point that reduces them and improve dispersion and distribution in the melting process thus, this or even favourable.This class additive is that those of ordinary skill in the art is known, comprises nucleator, softening agent, lubricant, catalyst neutralization agent, antioxidant, light stabilizer, colorant, acid scavenger, reaches analogue.In these additives some can provide useful performance to improve, and comprise improving aesthetic feeling, be easier to process and improve stability to processing or end-use situation.
Especially, acid scavenger master used herein if it were not for increase the effectively required identical carboxylate salt of silver of surface at the target thermoplastic product surface.Therefore, as an example, two hydrotalcites (for example, mainly be, to originate from Kyowa Chemical Industry CO. although be not limited to, Ltd. DHT4-A) be preferred for this purposes, make any carboxylate salt can mainly be used to the aforementioned purpose that forms silver of the present invention thus.
Composition of the present invention is suitable as additive to improve used for cosmetic wrapping material and container material, food product pack, film, thermoplastic article (for example water glass), the heavy wall storage vessel, medical use (syringe, venous pocket, gloves and analogue), food processing plant (conveying belt and analogue) and other class Sihe typically are starved of antibacterial efficacy any other characteristic effectively silver-colored with being starved of the surface of the end-use of anti-bacterial thermoplastic, particularly because they are these films, sheet material or other similar processing thermoplastic goods provide excellent effectiveness and can not produce injurious effects to this physical properties of articles.
The description of preferred implementation
The following example is represented preferred implementation of the present invention:
The manufacturing of antibiotic thermoplastic article
Make thermoplastic article (weight before these composition moldings is 1000 grams) according to following different composition:
The homopolymer polypropylene compositions table
Component Amount
Homopolymer polypropylene (Himont Profax 6301NT is from Basell) to 1000g
Irganox B215, antioxidant (from Ciba Specialty Chemicals) 1500ppm
DHT4-A, acid scavenger 400ppm
Silver-containing antibacterial agent (type is as follows) is as described below
Carboxylate salt (type is as follows) is as described below
The high-density polyethylene composition table
Component Amount
High density polyethylene(HDPE) (DOW 8454N contains polymkeric substance and anti-oxidant
The resin of industry of the prefabricated formulation of agent and acid scavenger) to 1000g
Silver-containing antibacterial agent (type is as follows) is as described below
Carboxylate salt (type is as follows) is as described below
The LLDPE compositions table
Component Amount
LLDPE (DOWLEX 2552-E contains polymkeric substance
Resin of industry with the prefabricated formulation of antioxidant and acid scavenger) to 1000g
Silver-containing antibacterial agent (type is as follows) is as described below
Carboxylate salt (type is as follows) is as described below
The polyphenylacetylene combination table
Component Amount
Polystyrene (DOW Styron 660-71 contains polymkeric substance and antioxygen
Change the resin of industry of the prefabricated formulation of agent and acid scavenger) to 1000g
Silver-containing antibacterial agent (type is as follows) is as described below
Carboxylate salt (type is as follows) is as described below
At first polypropylene fluff and listed other component are mixed the solid mixture of making all these components, make polypropylene articles thus.This solid mixture is added hopper so that further fusion on the heating spiral rod extruding machine of standard then.Thorough mixing molten mixture thus, and before finally being molded as desired shape, make the ball shape, then they are cooled to desired shape with further use, in this example, be tabular.
The manufacturing of polyethylene and modified styrene polymer is as follows: the pellet that takes out ready-formed polymkeric substance (can buy) and other additive got ready except necessary silver-containing antibacterial agent and incidental carboxylate salt.These powdered components are mixed and made into similar solid mixture to carry out further melt extrusion by the worm press that heats and to mix with aforementioned pellet before fusion.This moulded product also is a sheet material, then it is fully cooled off to make the required solid articles that is used for further test and analyzes.
Certainly, although in the preferred embodiment, use screw rod to extrude and molding technology is made this sheet material, obviously also can use any standard technique in the thermoplastic article process industry to make any solid articles of the polymeric object that defines roughly like this.
(PP represents from the homopolymer polypropylene compositions table particular composition that makes at polymer type (as mentioned), HDPE is from the high density polyethylene(HDPE) table, LLDPE is from the LLDPE table, PS comes the self-polystyrene table), the type of silver-containing antibacterial agent (usually but be not restrictive, as mentioned above, the content of RC-2000 is the 1wt% of 10000ppm or polymkeric substance total amount, RC-5000 is an ALPHASAN  Ag-containing compound, and ZEOMIC  is the zeolite based compound) and the type of carboxylate salt (and amount) (CaSt is a calcium stearate, Aldi-St is an aluminium distearate, MgAc is a magnesium acetate, and other tested salt has similar mark) aspect meets the listed details of following table:
The thermoplastic article formula table
Embodiment # Polymer type Contain argentum reagent Carboxylate salt (ppm)
1 PP RC-5000(10000ppm) MgSt(3000ppm)
2 PP RC-5000(10000ppm) CaSt(3000ppm)
3 PP RC-5000(10000ppm) BaSt(3000ppm)
4 PP RC-5000(10000ppm) CdSt(3000ppm)
5 PP RC-5000(10000ppm) Sn(II)St(3000ppm)
6 PP RC-2000(10000ppm) MgSt(3000ppm)
7 PP RC-2000(10000ppm) CaSt(3000ppm)
8 PP RC-2000(10000ppm) BaSt(3000ppm)
9 PP RC-2000(10000ppm) ZnSt(3000ppm)
10 PP RC-2000(10000ppm) CdSt(3000ppm)
11 PP RC-2000(10000ppm) Sn(II)St(3000ppm)
12 PP ZEOMIC(10000ppm) NaSt(3000ppm)
13 PP ZEOMIC(10000ppm) CaSt(3000ppm)
14 PP RC-5000(10000ppm) LiSt(100ppm)
15 PP RC-5000(10000ppm) MgSt(1000ppm)
16 PP RC-5000(10000ppm) MgSt(2431ppm)
17 PP RC-5000(10000ppm) MgSt(10000ppm)
18 PP RC-5000(10000ppm) CaSt(1000ppm)
19 PP RC-5000(10000ppm) CaSt(1514ppm)
20 PP RC-5000(10000ppm) CaSt(10000ppm)
21 PP RC-5000(10000ppm) BaSt(100ppm)
22 PP RC-5000(10000ppm) BaSt(300ppm)
23 PP RC-5000(10000ppm) BaSt(1000ppm)
24 PP RC-5000(10000ppm) BaSt(10000ppm)
25 PP RC-5000(10000ppm) CdSt(100ppm)
26 PP RC-5000(10000ppm) CdSt(300ppm)
27 PP RC-5000(10000ppm) CdSt(1000ppm)
28 PP RC-5000(10000ppm) CdSt(10000ppm)
29 PP RC-5000(10000ppm) Sn(II)St(100ppm)
30 PP RC-5000(10000ppm) Sn(II)St(300ppm)
31 PP RC-5000(10000ppm) Sn(II)St(1000ppm)
32 PP RC-5000(10000ppm) A1St(100ppm)
33 PP RC-5000(10000ppm) AlSt(300ppm)
34 PP RC-5000(10000ppm) AlSt(1000ppm)
35 PP RC-5000(10000ppm) AlSt(3000ppm)
36 PP RC-5000(10000ppm) Aldi-St(100ppm)
37 PP RC-5000(10000ppm) Aldi-St(300ppm)
38 PP RC-5000(10000ppm) A1di-St(1000ppm)
39 PP RC-5000(10000ppm) Aldi-St(3000ppm)
40 PP RC-5000(10000ppm) Altri-St(100ppm)
41 PP RC-5000(10000ppm) Altri-St(300ppm)
42 PP RC-5000(10000ppm) Altri-St(1000ppm)
43 PP RC-5000(10000ppm) Altri-St(3000ppm)
44 HDPE RC-5000(10000ppm) LiSt(10000ppm)
45 HDPE RC-5000(10000ppm) NaSt(3000ppm)
46 HDPE RC-5000(10000ppm) NaSt(10000ppm)
47 HDPE RC-5000(10000ppm) KSt(10000ppm)
48 HDPE RC-5000(10000ppm) MgSt(3000ppm)
49 HDPE RC-5000(10000ppm) MgSt(10000ppm)
50 HDPE RC-5000(10000ppm) CaSt(3000ppm)
51 HDPE RC-5000(10000ppm) CaSt(10000ppm)
52 HDPE RC-5000(10000ppm) BaSt(3000ppm)
53 HDPE RC-5000(10000ppm) BaSt(10000ppm)
54 HDPE RC-5000(10000ppm) ZnSt(3000ppm)
55 HDPE RC-5000(10000ppm) CdSt(3000ppm)
56 HDPE RC-5000(10000ppm) Sn(II)St(3000ppm)
57 LLDPE RC-5000(10000ppm) LiSt(3000ppm)
58 LLDPE RC-5000(10000ppm) NaSt(3000ppm)
59 LLDPE RC-5000(10000ppm) MgSt(3000ppm)
60 LLDPE RC-5000(10000ppm) CaSt(3000ppm)
61 LLDPE RC-5000(10000ppm) BaSt(3000ppm)
62 LLDPE RC-5000(10000ppm) ZnSt(3000ppm)
63 LLDPE RC-5000(10000ppm) CdSt(3000ppm)
64 LLDPE RC-5000(10000ppm) Sn(II)St(3000ppm)
65 PS RC-5000(10000ppm) CaSt(3000ppm)
At first, after this make every kind of goods with the low speed fusion 5 minutes in a Kenwood mixing tank of original polymer and additive.On the Killion single screw extruder, pass through four heating regions with all samples melting mixing then with about 205 ℃ to 230 ℃ temperature that rises gradually.The melt temperature in extrusion die exit is about 230 ℃.The diameter of this screw rod is that 2.54 centimetres and length/diameter ratio are 32: 1.During fusing, the screen cloth (work output be about 1 kilogram/10 minute, approximately 115rpm) of this molten polymer by one 300 order (48 microns) filtered.Make target polypropylene, HDPE, LLDPE and polystyrene plates respectively by molding on Arburg25 ton injector then.Sheet material has the size of about 50 millimeters * 70 millimeters * 1.00 millimeters (surface-area is about 0.71 square decimeter), and is to make in a model through the politure arrangement.The molding cooling circulating water is controlled at about 30+/-1 ℃.
The surface is the analysis of silver effectively
At room temperature each goods is soaked 24 hours (or longer time, as described below) then in extraction solution.In following each example, the extraction solution of use all is a potassium-sodium phosphates buffered soln, although other salts solution (for example sodium-chlor, calcium chloride reach analogue) also can be as the test extraction solution, as long as can carry out suitable silver extraction with these solution.The test silver-containing antibacterial agent but not the contrast of carboxylate-containing with as a comparison.
Extraction procedures comprises the typical curve of at first making different silver concentrations in salpeter solution with analyzing.At first weigh up 1000ppm silver, add in 100 milliliters of measuring bottles, and 0.5 milliliter of 5% salpeter solution added this measuring bottle to maximum scale (to make 1ppm silver label standard), make the silvery agent thus.The further dilution of 10 grams of this 1ppm preparation is added in 100 milliliters of measuring bottles, add remaining 5%i salpeter solution (to make the 100ppb standard substance) then.Prepare final 500ppb standard substance with 5 gram 100ppb standard substances in a similar manner then.Use the inductively coupled plasma spectrometry method to measure this concentration then and obtain silver content.Then to these results mapping so that compare with the last silver content of following extraction solution.
Extraction solution is the 1X intensity solution (be that about 145 gram sodium phosphates mix with about 71 gram potassiumphosphates at first, with the deionized water dilution, subsequently 100 milliliters of these first solution be diluted to 1000 milliliters with deionized water in a liter flask) of potassium-sodium phosphates solution.The sheet material that to handle is placed on respectively and contains in the sealed plastic bag of capacity extraction liquid with complete submergence sample then.Then sack is placed on the rail mounted vibrator of 140rpm, and at room temperature deposited 24 hours.After this, 9.5 milliliters of extraction solutions that make are put into 15 milliliters of phials that are added with 0.5% 70% nitric acid.Then the test that makes is carried out the ICP spectroscopic analysis with extraction solution and contrast of the measuring result mapping of above-mentioned standard substance silver concentration.The measuring result of above-mentioned sheet material sample is as follows:
Experimental silver extraction table
Embodiment # Detected silver content (3. g/dm 2 )
1 0.25
2 0.33
3 0.29
4 0.52
5 0.32
6 0.90
7 1.10
8 0.92
9 0.78
10 0.92
11 0.63
12 0.82
13 0.90
14 0.19
15 0.22
16 0.23
17 0.21
18 0.26
19 0.34
20 0.50
21 0.25
22 0.27
23 0.22
24 0.32
25 0.26
26 0.25
27 0.33
28 0.41
29 0.21
30 0.23
31 0.25
32 0.22
33 0.21
34 0.26
35 0.25
36 0.27
37 0.26
38 0.30
39 0.27
40 0.29
41 0.25
42 0.26
43 0.25
44 0.23
45 0.30
46 0.33
47 0.40
48 0.54
49 0.31
50 0.81
51 0.73
52 0.36
53 0.31
54 0.57
55 0.70
56 0.44
57 0.31
58 0.29
59 0.37
60 0.85
61 0.34
62 0.45
63 0.52
64 0.26
65 1.09
Contrast (PP) (RC-5000) (1%) 0.17
Contrast (PP) (RC-2000) (1%) 0.69
Contrast (PP) (ZEOMIC) (1%) 0.58
Contrast (HDPE) (RC-5000) (1%) 0.22
Contrast (LLDPE) (RC-5000) (1%) 0.16
Contrast (PS) (RC-5000) (1%) 0.62
Therefore, do not reckon with ground, compare with contrast, goods of the present invention show effective silver content on its surface of raising (in various degree), particularly in polyolefine, for Trisilver phosphate zirconium type (RC-5000, RC-2000) at least 0.25 3. gram/cubic decimeter, be at least 0.75 for silver zeolite, and for vinylbenzene, any silver-containing antibacterial agent is at least 0.80.
Certainly, the present invention also has many alternative embodiments and modification, and they all are included in the scope and scope of appended claims.

Claims (38)

1. polyolefin articles that contains at least a Trisilver phosphate zirconium antiseptic-germicide, this polyolefin articles contains at least a carboxylate salt component of optional at least a acid scavenger compound and 0.1wt% to 1.25wt%, and it is at least 0.25 microgram silver/described surface of square decimeter by the surperficial significant quantity of carrying the silver compound that salt test records of at room temperature carrying out 24 hours.
2. polyolefin articles that contains at least a silver zeolite antiseptic-germicide, this polyolefin articles contains at least a carboxylate salt component of optional at least a acid scavenger compound and 0.1wt% to 1.25wt%, and it is at least 0.75 microgram silver/described surface of square decimeter by the surperficial significant quantity of carrying the silver compound that salt test records of at room temperature carrying out 24 hours.
3. styrenic thermoplastic goods that contain at least a silver-containing antibacterial agent, at least a carboxylate salt component of optional at least a acid scavenger compound of these styrenic thermoplastic goods and 0.1wt% to 1.25wt%, it is at least 0.80 microgram silver/described surface of square decimeter by the surperficial significant quantity of carrying the silver compound that salt test records of at room temperature carrying out 24 hours.
4. styrenic thermoplastic goods as claimed in claim 3, wherein said at least a silver-containing antibacterial agent are a kind of inorganic Ag-containing compounds.
5. vinylbenzene goods as claimed in claim 4, wherein said inorganic silver-containing antibacterial agent are selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture.
6. vinylbenzene goods as claimed in claim 5, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium.
7. thermoplastic article, at least a carboxylate salt component that it contains at least a silver-containing antibacterial agent, optional at least a acid scavenger and accounts for the 0.1wt% to 1.25wt% at least of polymkeric substance.
8. thermoplastic article as claimed in claim 7, the content of wherein said carboxylate salt be polymkeric substance about 0.2 to about 1.0wt%.
9. thermoplastic article as claimed in claim 8, the content of wherein said carboxylate salt be the polymkeric substance total amount about 0.2 to about 0.5wt%.
10. thermoplastic article as claimed in claim 9, the content of wherein said carboxylate salt are about 0.3wt% of polymkeric substance total amount.
11. thermoplastic article as claimed in claim 7, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
12. thermoplastic article as claimed in claim 11, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
13. thermoplastic article as claimed in claim 12, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
14. thermoplastic article as claimed in claim 8, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
15. thermoplastic article as claimed in claim 14, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
16. thermoplastic article as claimed in claim 15, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
17. thermoplastic article as claimed in claim 9, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
18. thermoplastic article as claimed in claim 17, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
19. thermoplastic article as claimed in claim 18, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
20. thermoplastic article as claimed in claim 10, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
21. thermoplastic article as claimed in claim 20, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
22. thermoplastic article as claimed in claim 21, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
23. method that forms thermoplastic article, described method comprises the following steps: to provide a kind of thermoplastic polymer, to wherein adding at least a silver-containing antibacterial agent, optional at least a acid scavenger and accounting at least a carboxylate compounds of the 0.1wt% to 0.75wt% of polymkeric substance total amount, with the mixture melt of the described polymkeric substance that makes, silver-containing antibacterial agent and at least a carboxylate salt, described molten mixture is cooled to required molded thermoplastic goods.
24. method as claimed in claim 23, the content of wherein said carboxylate salt be polymkeric substance about 0.2 to about 0.5wt%.
25. method as claimed in claim 24, the content of wherein said carboxylate salt be the polymkeric substance total amount about 0.2 to about 0.4wt%.
26. method as claimed in claim 25, the content of wherein said carboxylate salt are about 0.3wt% of polymkeric substance total amount.
27. method as claimed in claim 23, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
28. thermoplastic article as claimed in claim 27, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
29. thermoplastic article as claimed in claim 28, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
30. thermoplastic article as claimed in claim 24, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
31. thermoplastic article as claimed in claim 30, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
32. thermoplastic article as claimed in claim 31, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
33. thermoplastic article as claimed in claim 25, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
34. thermoplastic article as claimed in claim 33, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
35. thermoplastic article as claimed in claim 34, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
36. thermoplastic article as claimed in claim 26, wherein said at least a silver-containing antibacterial agent is inorganic Ag-containing compound, and wherein said at least a carboxylate salt is selected from least a C of positively charged ion neutral that is selected from monovalent metallic ion, divalent ion and trivalent metal ion with at least a 1-C 40Carboxylic acid cpd.
37. thermoplastic article as claimed in claim 36, wherein said inorganic silver-containing antibacterial agent is selected from Trisilver phosphate zirconium, silver-colored glass, silver zeolite and their any mixture, and described carboxylate salt is selected from alkali metal acetate, alkali metal stearic acid salt, alkaline-earth metal acetate, alkaline earth metal stearate, Zinic stearas, stearic acid tin (II), aluminum stearate and their any mixture.
38. thermoplastic article as claimed in claim 37, wherein said inorganic silver-containing antibacterial agent is the Trisilver phosphate zirconium, and wherein said carboxylate salt is a calcium stearate.
CNB028249771A 2001-12-12 2002-09-30 Thermoplastic articles exhibiting high surface-available silver Expired - Fee Related CN1274749C (en)

Applications Claiming Priority (4)

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US10/015,305 US20030108608A1 (en) 2001-12-12 2001-12-12 Thermoplastic articles comprising silver-containing antimicrobials and high amounts of carboxylic acid salts for increased surface-available silver
US10/015,872 US6641842B2 (en) 2001-12-12 2001-12-12 Thermoplastic articles exhibiting high surface-available silver
US10/015,872 2001-12-12
US10/015,305 2001-12-12

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