CN1126788C - Non-toxic polyvinyl chloride composition and its preparing process - Google Patents
Non-toxic polyvinyl chloride composition and its preparing process Download PDFInfo
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Abstract
The present invention provides a nontoxic polyvinyl chloride composition. Besides the composition contains PVC, the composition also contains 20 to 100 parts by weight of small molecule plasticizers, 2 to 8 parts by weight of stabilizers, 1 to 8 parts by weight of lubricating agents, 0.5 to 5 parts by weight of antibacterial agents and 0.2 to 2 parts by weight of antimildew agents on the basis of 100 parts by weight of PVC. The present invention also provides a preparation method for the nontoxic polyvinyl chloride composition. Soft polyvinyl chloride plastics which are made by the present invention have the characteristics of sanitation, innocuity, antibacterium, mildew resistance, etc.
Description
Technical field
The present invention relates to a kind of nontoxic polychloroethylene composition, particularly extrude polychloroethylene composition that makes and preparation method thereof by mixing by New-type adjuvants such as inorganic antiseptic, organic class antiseptic-germicide, mould inhibitor and non-toxic stabilizers.
Background technology
Polyvinyl chloride (PVC) is one of the most frequently used resin of people, and the total flow of 97 years China reaches more than 2,620,000 tons, is widely used in fields such as building materials, household electrical appliances, automobile, packing.Because the singularity of structure, polyvinyl chloride system in actual applications must comprise components such as stablizer, lubricant.Traditional stablizer is a Pb stabilizer, because lead salt has thermotolerance, electrical insulating property, good weatherability, and also cheap.But because the environmental pollution of Pb stabilizer is serious day by day, considered the safety issue of PVC simultaneously in recent years, the wholesomeness of thermo-stabilizer has caused people's attention, has set up " Japanese polyvinyl chloride food sanitation association (JHPA) " as Japan at this point.With the raising of people to hygienic requirements, the Western European countries begun to forbid with the polrvinyl chloride product of human body or Food Contact in use lead salt stabilizer.Extraordinary goods have been begun to consider to use some occasion people with special sanitation performance.US5359011 in 1994 discloses DMG company and has developed the polyvinyl chloride (PVC) stabilizer Stab2211 and the Stab2212 of the special uses of health level goods, US5455319 discloses the health grade PVC composition Apex-90-A71R-NT of Teknor Apex company preparation, for hygienic articles such as application such as blood bag, kidney dialysis tube.The spy of rising sun electrochemical industry opens flat 4-59851 and discloses " used for packing foods PVC based resin composition ", has reported a kind of polychloroethylene composition that Japanese polyvinyl chloride food sanitation association requires that meets.Release health grade PVC composition though united states, japan and other countries is developed one after another, these compositions only are to have replaced deleterious stablizer, and it is more suitable to be used for the hygienic articles that short-term uses, but when the need life-time service material still president bacterium and mould.Aspect agricultural polychloroethylene, there is the new function kind of antibacterial and mouldproof to occur, as the spy open flat 4-18457 Japan chemical company is disclosed can be by adding in polyvinyl chloride that agricultural chemicals obtained for the polyvinyl chloride resin of field usage mildew-resistant pest control, but because what add is that deleterious agricultural chemicals can't use and occasion with human body or Food Contact.At present the use field of polyvinyl chloride is expanded greatly, as is used to prepare and is applied in moistening occasion and goods human body or Food Contact, resembles the sealed strip, water pipe of refrigerator etc.These materials had both needed nontoxic, wished to have antibacterial and antimildew function again.
Summary of the invention
The present invention avoided generally using in traditional igelite with the poisonous stabilising system of lead salt as representative, overcome the polyvinyl chloride soft material and be subjected to the bacterium erosion easily, the problem of going mouldy, the use non-toxic stabilizer is provided, and the new prescription of the nontoxic antibacterial and mouldproof flexible PVC of preparation of interpolation antiseptic-germicide and mould inhibitor and new preparation technology, the soft polyvinyl chloride plastic that makes has characteristics such as health is nontoxic, antibacterial and mouldproof.
The invention provides a kind of nontoxic polychloroethylene composition, except that containing PVC, also contain the small molecules softening agent of 20-100 weight part in the said composition, preferred 30-80 weight part based on the PVC of 100 weight parts; The stablizer of 2-8 part, preferred 3-5 weight part; The lubricant of 1-8 weight part, preferred 2-5 weight part; 0.5-5 the antiseptic-germicide of weight part, preferred 1-3 weight part; 0.2-2 the mould inhibitor of weight part.
The polymeric plasticizer that preferably also contains the 0-40 weight part in the composition of the present invention, preferred 10-25 weight part; The CaCO of 0-100 weight part
3, preferred 15-60 weight part.
The K value of above-mentioned PVC is preferably the various products of 68-73.
Above-mentioned small molecules softening agent refers to that molecular weight is below 1000, has the material that polymeric system plasticity is increased, be preferably dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP), dinoctyl phthalate (DnOP), dipropyl phthalate (DPP), diethyl phthalate (DEP), dimixo-octyl phthalate (DIOP), Di Iso Decyl Phthalate (DIDP), dioctyl phthalate dioctyl ester in the last of the ten Heavenly stems (DOS), Dinonylphthalate (DNP), the phthalic acid mixed ester, epoxy soybean oil, the epoxyoleic acid butyl ester, butyl oleate, the oleic acid monooctyl ester, N, the N-dibutyl oleamide, diisodecyl adipate, beta-diketon or two or more mixture in them.
Above-mentioned polymeric plasticizer refers to molecular weight at the material that has plastification more than 2500, is preferably powder nbr (NBR), chlorinated polyvinyl chloride (CPVC), chlorinatedpolyethylene (CPE), polyvinyl acetate (PVA) (EVA), styrene-butadiene-styrene (SBS) rubber or two or more mixture in them.
Above-mentioned stablizer only limits to acute toxicity test LD as a result
50Greater than the non-toxic stabilizer of 10000mg/kg, be preferably rare-earth stabilizer, Zn-Ca liquid stabilisers, Zn-Ca powder stablizer or two or more mixture etc. in them.
The material of flowability when above-mentioned lubricant refers to help to improve the system moulding, be preferably paraffin, stearic acid, Zinic stearas, calcium stearate, barium stearate, polyethylene wax, lauryl alcohol, butyl stearate, N, N '-ethylene bis stearamide or two or more mixture in them.
Above-mentioned antiseptic-germicide refers to suppress the material of frosting bacterial growth and breeding, is preferably with Ag
+For the silver-based inorganic antibacterial agent of effective antipathogenic composition, with Zn
2+Be the zine series inorganic germicide of effective antipathogenic composition, 3-hydroxyl three chlorodiphenyl ethers or two or more mixture in them.
Above-mentioned mould inhibitor refers to suppress the material of material surface fungus growth, is preferably 10, and 10 '-oxidation diphenol is disliked pyrrole (OBPA), epoxyeicosatrienoic acid zinc, hydroxybenzoate, epoxyeicosatrienoic acid quaternary ammonium salt, epoxyeicosatrienoic acid sodium phenolate or two or more mixture in them.
The invention provides a kind of preparation method of nontoxic polychloroethylene composition, comprise the steps:
(1) by weight with 100 parts PVC, the stablizer of 2-8 part, the lubricant of 1-8 part, the CaCO of 0-100 part
3, the antiseptic-germicide of 0.5-5 part and the mould inhibitor thorough mixing of 0.2-2 part;
(2) the small molecules softening agent of adding 20-100 weight part when the temperature of mixture reaches 60-70 ℃ fully stirs discharging when thing temperature to be mixed reaches 105-110 ℃;
(3) said mixture is extruded granulation at 140-180 ℃.
In the step (2) of aforesaid method, after thing temperature to be mixed reaches 105-110 ℃ of discharging, it can also be cooled to 10-50 ℃, this mixture and the polymeric plasticizer that is not higher than 40 weight parts are mixed; Then resulting mixture is extruded granulation at 140-180 ℃.
In the method for the invention, the amount of employed small molecules softening agent is preferably the 30-80 weight part; Stablizer is preferably the 3-5 weight part; Lubricant is preferably the 2-5 weight part; Antiseptic-germicide is preferably the 1-3 weight part; Polymeric plasticizer is preferably the 10-25 weight part; CaCO
3Be preferably the 15-60 weight part.
The K value of employed PVC is preferably the various products of 68-73.
Employed small molecules softening agent refers to that molecular weight is below 1000, have the polymeric system of making and mould (DBP), dinoctyl phthalate (DnOP), dipropyl phthalate (DPP), diethyl phthalate (DEP), dimixo-octyl phthalate (DIOP), Di Iso Decyl Phthalate (DIDP), dioctyl phthalate dioctyl ester in the last of the ten Heavenly stems (DOS), Dinonylphthalate (DNP), the phthalic acid mixed ester, epoxy soybean oil, the epoxyoleic acid butyl ester, butyl oleate, the oleic acid monooctyl ester, N, the N-dibutyl oleamide, diisodecyl adipate, beta-diketon or two or more mixture in them.
Employed polymeric plasticizer refers to molecular weight at the material that has plastification more than 2500, is preferably powder nbr (NBR), chlorinated polyvinyl chloride (CPVC), chlorinatedpolyethylene (CPE), polyvinyl acetate (PVA) (EVA), SBS rubber or two or more mixture in them.
Employed stablizer only limits to acute toxicity test LD as a result
50Greater than the non-toxic stabilizer of 10000mg/kg, be preferably rare-earth stabilizer, Zn-Ca liquid stabilisers, Zn-Ca powder stablizer or two or more mixture etc. in them.
The material of flowability when employed lubricant refers to help to improve the system moulding, be preferably paraffin, stearic acid, Zinic stearas, calcium stearate, barium stearate, polyethylene wax, lauryl alcohol, butyl stearate, N, N '-ethylene bis stearamide or two or more mixture in them.
Employed antiseptic-germicide refers to suppress the material of frosting bacterial growth and breeding, is preferably with Ag
+For the silver-based inorganic antibacterial agent of effective antipathogenic composition, with Zn
2+Be the zine series inorganic germicide of effective antipathogenic composition, 3-hydroxyl three chlorodiphenyl ethers or two or more mixture in them.
Employed mould inhibitor refers to suppress the material of material surface fungus growth, is preferably 10, and 10 '-oxidation diphenol is disliked pyrrole (OBPA), epoxyeicosatrienoic acid zinc, hydroxybenzoate, epoxyeicosatrienoic acid quaternary ammonium salt, epoxyeicosatrienoic acid sodium phenolate or two or more mixture in them.
The polychloroethylene composition that the antibacterial and mouldproof that the present invention makes is nontoxic has the good mechanical performance, and its index sees Table 1.
The polychloroethylene composition material mechanical performance that table 1 antibacterial and mouldproof is nontoxic
| Performance | Unit | Index |
| Tensile strength | MPa | ＞10 |
| Elongation at break | ％ | ＞250 |
| Hardness | ShearA | 74±5 |
| Tearing toughness | MPa | ＞3 |
| The compression rebound rate | ％ | ＞65 |
| Ion migration (336hr, 70 ± 4 ℃) | g | ＜0.15 |
The polychloroethylene composition that the antibacterial and mouldproof that the present invention makes is nontoxic has good restraining and killing action to bacteriums such as intestinal bacteria, subtilis, streptococcus aureus, Sarcina lutea, prunosus red coccus, and its bacteriostasis rate can reach more than 95%.
The nontoxic polychloroethylene composition of the antibacterial and mouldproof that the present invention makes to aspergillus niger, flavus, Penicillium citrinum, terreus, Mucor racemosus, Aureobasidium pullulans, penicillium funiculosum, viride, etc. good inhibitory effect is all arranged, it suppresses grade can reach 0 grade.
The polychloroethylene composition toxicity that the antibacterial and mouldproof that the present invention makes is nontoxic meets the food product pack requirement of GB9689-98, residue on evaporation less than 20mg/L, potassium permanganate consumption less than 2mg/L, heavy metal content less than 1mg/L.Per os acute toxicity LD
50Greater than 10000mg/Kg.Hemolytic test is less than 1, and the whole body acute toxicity test meets the ISO10993 standard.
The polychloroethylene composition that the antibacterial and mouldproof that the present invention makes is nontoxic has good colour stability, measures according to GB/T7921-1997, and through 200hr standard ultraviolet lamp accelerated deterioration experiment, its result shows difference DELTA E≤4 of the aberration of its aberration and corresponding base material.
Has embodiment
Embodiment 1
With the 1000gK value 68 polyvinyl chloride powder, 50g rare-earth stabilizer, 10g paraffin, 10g stearic acid, 10g Zinic stearas, 5g polyethylene wax, 5g butyl stearate, 600gCaCO
3, 50g zinc series antibacterial agent and 2gOBPA add in the homogenizer beginning heating machine.Earlier use stirring at low speed 2min, using high-speed stirring then, measure material temperature simultaneously.When temperature arrives 65 ℃, open the observation port of homogenizer, slowly add the DIDP of DOP, 100g epoxy soybean oil and the 100g of 400g, stop heating from observation port.When arriving 110 ℃, opens temperature of charge the pulp cutlet of homogenizer; mixture is put into naturally cools to 10-50 ℃ in the preprepared container; join mixture and 150g powder nbr in the homogenizer simultaneously then; with stirring at low speed mixture and polymeric plasticizer are stirred; then from the pulp cutlet blowing in container; extrude with single screw extrusion machine, pelletizing on dicing machine promptly obtains nontoxic antibacterial and mouldproof soft polyvinyl chloride of the present invention.Require to measure tensile strength of material and elongation at break according to GB/T1040, require to measure the hardness of material according to GB2411, require to measure the tearing toughness of material according to QB/T1130, measure the compression rebound rate according to GB/T14694, require to measure the ion migration of material according to QB/T1294, measure the fungicidal properties of material according to GB2423, toxicity, residue on evaporation, potassium permanganate consumption, the heavy metal of measuring material according to GB9689 contains, LD
50According to ISO10993 standard test hemolytic test and whole body acute toxicity test, according to the colour stability of GB mensuration material, the anti-microbial property of material carries out according to " antimicrobial prod antibacterial ability evaluation test method (1998 editions) " that Japanese anti-biotic material is formulated.Its test result sees Table 2.
Embodiment 2
With the 1000gK value 73 polyvinyl chloride powder, 50gZn-Ca liquid stabilisers, 5g paraffin, 8g stearic acid, 10g calcium stearate, 5g lauric acid, 5gN, N '-ethylene bis stearamide, 20g silver-series antibacterial agent and 2g epoxyeicosatrienoic acid zinc, 5g sodium phenolate add in the homogenizer, the beginning heating machine.Earlier use stirring at low speed 2min, using high-speed stirring then, measure material temperature simultaneously.When temperature arrives 65 ℃, open the observation port of homogenizer, slowly add the DOS of 200g, stop heating from observation port.When arriving 110 ℃, opens temperature of charge the pulp cutlet of homogenizer; mixture is put into naturally cools to below 50 ℃ in the preprepared container; extrude with single screw extrusion machine, pelletizing on dicing machine promptly obtains nontoxic antibacterial and mouldproof soft polyvinyl chloride of the present invention.Material property detects and is undertaken by embodiment 1.Detected result sees Table 2.
Embodiment 3
With the 1000gK value is 71 polyvinyl chloride powder, 80g rare-earth stabilizer, 10g paraffin, 8g stearic acid, 7g calcium stearate, 5g butyl stearate, 5gN, N '-ethylene bis stearamide, 300gCaCO
3, 20g3-hydroxyl three chlorodiphenyl ethers and 6g hydroxybenzoate, 5g epoxy quaternary ammonium salt add in the homogenizer beginning heating machine.Earlier use stirring at low speed 2min, using high-speed stirring then, measure material temperature simultaneously.When temperature arrives 65 ℃, open the observation port of homogenizer, slowly add 400g beta diketone, 200g epoxyoleic acid butyl ester and 400gDBP, stop heating from observation port.When arriving 110 ℃, opens temperature of charge the pulp cutlet of homogenizer; mixture is put into naturally cools to below 50 ℃ in the preprepared container; join mixture and 400gCPE in the homogenizer simultaneously then; with stirring at low speed mixture and polymeric plasticizer are stirred; then from the pulp cutlet blowing in container; extrude with single screw extrusion machine, pelletizing on dicing machine promptly obtains nontoxic antibacterial and mouldproof soft polyvinyl chloride of the present invention.Material property detects and is undertaken by embodiment 1.Detected result sees Table 2.
Embodiment 4
With the 1000gK value is 71 polyvinyl chloride powder, 40gZn-Ca powder stablizer, 10g paraffin, 20g calcium stearate, 5g lauric acid, 5gN, N '-ethylene bis stearamide, 300gCaCO
3, 40g zinc series antibacterial agent and 5gOBPA add in the homogenizer beginning heating machine.Earlier use stirring at low speed 2min, using high-speed stirring then, measure material temperature simultaneously.When temperature arrives 65 ℃, open the observation port of homogenizer, slowly add 430gDOP and 200gPIOP, stop heating from observation port.When arriving 110 ℃, opens temperature of charge the pulp cutlet of homogenizer; mixture is put into naturally cools to below 50 ℃ in the preprepared container; join mixture and 250gEVA in the homogenizer simultaneously then; with stirring at low speed mixture and polymeric plasticizer are stirred; then from the pulp cutlet blowing in container; extrude with single screw extrusion machine, pelletizing on dicing machine promptly obtains nontoxic antibacterial and mouldproof soft polyvinyl chloride of the present invention.Material property detects and is undertaken by embodiment 1.Detected result sees Table 2.
The polychloroethylene composition material property that table 2 antibacterial and mouldproof is nontoxic
| Performance | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength | MPa | 15 | 12 | 14 | 12 |
| Elongation at break | ％ | 263 | 256 | 290 | 273 |
| Hardness | ShearA | 70 | 78 | 74 | 76 |
| Tearing toughness | MPa | 6.1 | 3.2 | 4.3 | 5.7 |
| The compression rebound rate | ％ | 23 | 43 | 38 | 29 |
| Ion migration | g | 0.09 | 0.06 | 0.10 | 0.08 |
| Aberration Δ E | ≤3 | ≤3 | ≤3 | ≤3 | |
| Bacteriostasis rate | ％ | ≥99 | ≥99 | ≥99 | ≥99 |
| Mildew resistance | 0 grade | 0 grade | 0 grade | 0 grade | |
| Potassium permanganate consumption | mg/L | 0.2 | 0.5 | 0.2 | 0.1 |
| Residue on evaporation | mg/L | 2 | 1 | 4 | 3 |
| The body acute toxicity test | Qualified | Qualified | Qualified | Qualified | |
| Heavy metal content | mg/L | ≤.01 | ≤0.1 | ≤0.1 | ≤0.1 |
| LD 50 | Mg/kg | ≥10000 | ≥10000 | ≥10000 | ≥10000 |
Claims (16)
1. a nontoxic polychloroethylene composition except that containing polyvinyl chloride, also contains the small molecules softening agent of 20-100 weight part in the said composition based on the polyvinyl chloride (PVC) RESINS of 100 weight parts; The stablizer of 2-8 weight part; The lubricant of 1-8 weight part; 0.5-5 the antiseptic-germicide of weight part; Mould inhibitor with the 0.2-2 weight part.
2. according to the described nontoxic polychloroethylene composition of claim 1, wherein said small molecules softening agent is the 30-80 weight part; Stablizer is the 3-5 weight part; Lubricant is the 2-5 weight part; Antiseptic-germicide is the 1-3 weight part.
3. according to the described nontoxic polychloroethylene composition of claim 1, wherein also contain the polymeric plasticizer of 0-40 weight part; The CaCO of 15-100 weight part
3
4. according to the described nontoxic polychloroethylene composition of claim 3, wherein the amount of polymeric plasticizer is the 10-25 weight part; CaCO
3Amount be the 15-60 weight part.
5. according to the described nontoxic polychloroethylene composition of claim 1, wherein said polyvinyl chloride (PVC) RESINS is the product of K value for 68-73; Described small molecules softening agent be dioctyl phthalate (DOP), dibutyl phthalate, dinoctyl phthalate, dipropyl phthalate, diethyl phthalate, dimixo-octyl phthalate, Di Iso Decyl Phthalate, the last of the ten Heavenly stems dioctyl phthalate dioctyl ester, Dinonylphthalate, phthalic acid mixed ester, epoxy soybean oil, epoxyoleic acid butyl ester, butyl oleate, oleic acid monooctyl ester, N, N-dibutyl oleamide, diisodecyl adipate, beta-diketon or two or more mixture in them.
6. according to the described nontoxic polychloroethylene composition of claim 3, wherein said polymeric plasticizer is powder nbr, chlorinated polyvinyl chloride, chlorinatedpolyethylene, polyvinyl acetate (PVA), styrene-butadiene-styrene rubber or two or more mixture in them.
7. according to the described nontoxic polychloroethylene composition of claim 1, wherein said stablizer is rare-earth stabilizer, Zn-Ca liquid stabilisers, Zn-Ca powder stablizer or two or more mixture in them; Described lubricant is paraffin, stearic acid, Zinic stearas, calcium stearate, barium stearate, polyethylene wax, lauryl alcohol, butyl stearate, N, N '-ethylene bis stearamide or two or more mixture in them.
8. according to the described nontoxic polychloroethylene composition of claim 1, wherein said antiseptic-germicide is with Ag
+For the silver-based inorganic antibacterial agent of effective antipathogenic composition, with Zn
2+Be the zine series inorganic germicide of effective antipathogenic composition, 3-hydroxyl three chlorodiphenyl ethers or two or more mixture in them; Described mould inhibitor is 10, and 10 '-oxidation diphenol is disliked pyrrole, epoxyeicosatrienoic acid zinc, hydroxybenzoate, epoxyeicosatrienoic acid quaternary ammonium salt, epoxyeicosatrienoic acid sodium phenolate or two or more mixture in them.
9. a preparation method who is used for nontoxic polychloroethylene composition comprises the steps:
(1) by weight with 100 parts polyvinyl chloride (PVC) RESINS, the stablizer of 2-8 part, the lubricant of 1-8 part, the CaCO of 15-100 part
3, the antiseptic-germicide of 0.5-5 part and the mould inhibitor thorough mixing of 0.2-2 part;
(2) the small molecules softening agent of adding 20-100 weight part when the temperature of mixture reaches 60-70 ℃ fully stirs discharging when thing temperature to be mixed reaches 105-110 ℃;
(3) said mixture is extruded granulation at 140-180 ℃.
10. according to the described preparation method of claim 9, wherein, in step (2), after thing temperature to be mixed reaches 105-110 ℃ of discharging, it is cooled to 10-50 ℃, this mixture and the polymeric plasticizer that is not higher than 40 weight parts are mixed; Then resulting mixture is extruded granulation at 140-180 ℃.
11. according to the described preparation method of claim 9, wherein, employed small molecules softening agent is the 30-80 weight part; Stablizer is the 3-5 weight part; Lubricant is the 2-5 weight part; Antiseptic-germicide is the 1-3 weight part; CaCO
3Amount be the 15-60 weight part.
12. according to the described preparation method of claim 10, wherein, the amount of employed polymeric plasticizer is the 10-25 weight part.
13. according to the described preparation method of claim 9, wherein, described polyvinyl chloride (PVC) RESINS is the product of K value for 68-73; Described small molecules softening agent be dioctyl phthalate (DOP), dibutyl phthalate, dinoctyl phthalate, dipropyl phthalate, diethyl phthalate, dimixo-octyl phthalate, Di Iso Decyl Phthalate, the last of the ten Heavenly stems dioctyl phthalate dioctyl ester, Dinonylphthalate, phthalic acid mixed ester, epoxy soybean oil, epoxyoleic acid butyl ester, butyl oleate, oleic acid monooctyl ester, N, N-dibutyl oleamide, diisodecyl adipate, beta-diketon or two or more mixture in them.
14. according to the described preparation method of claim 9, wherein, employed polymeric plasticizer is powder nbr, chlorinated polyvinyl chloride, chlorinatedpolyethylene, polyvinyl acetate (PVA), styrene-butadiene-styrene rubber or two or more mixture in them.
15. according to the described preparation method of claim 9, wherein, described stablizer is rare-earth stabilizer, Zn-Ca liquid stabilisers, Zn-Ca powder stablizer or two or more mixture in them; Described lubricant is paraffin, stearic acid, Zinic stearas, calcium stearate, barium stearate, polyethylene wax, lauryl alcohol, butyl stearate, N, N '-ethylene bis stearamide or two or more mixture in them.
16. according to the described preparation method of claim 9, wherein, described antiseptic-germicide is with Ag
+For the silver-based inorganic antibacterial agent of effective antipathogenic composition, with Zn
2+Be the zine series inorganic germicide of effective antipathogenic composition, 3-hydroxyl three chlorodiphenyl ethers or two or more mixture in them; Described mould inhibitor is 10, and 10 '-oxidation diphenol is disliked pyrrole, epoxyeicosatrienoic acid zinc, hydroxybenzoate, epoxyeicosatrienoic acid quaternary ammonium salt, epoxyeicosatrienoic acid sodium phenolate or two or more mixture in them.
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1999
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