WO2022268122A1 - Organic-inorganic mixture for preventing copper or silver oxidation, manufacturing method therefor, and application thereof - Google Patents

Organic-inorganic mixture for preventing copper or silver oxidation, manufacturing method therefor, and application thereof Download PDF

Info

Publication number
WO2022268122A1
WO2022268122A1 PCT/CN2022/100464 CN2022100464W WO2022268122A1 WO 2022268122 A1 WO2022268122 A1 WO 2022268122A1 CN 2022100464 W CN2022100464 W CN 2022100464W WO 2022268122 A1 WO2022268122 A1 WO 2022268122A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic
copper
composition
inorganic
silver
Prior art date
Application number
PCT/CN2022/100464
Other languages
French (fr)
Chinese (zh)
Inventor
王奕中
Original Assignee
新和兴业股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 新和兴业股份有限公司 filed Critical 新和兴业股份有限公司
Publication of WO2022268122A1 publication Critical patent/WO2022268122A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

Definitions

  • the invention relates to an organic-inorganic compound for preventing oxidation of copper or silver, which comprises 1-5 wt% of organic components and 95-99 wt% of inorganic components.
  • the above-mentioned organic-inorganic hybrid for preventing copper or silver oxidation can be applied in the field of manufacturing antibacterial polyester fibers.
  • the present invention provides an organic-inorganic hybrid.
  • the organic-inorganic hybrid has the technical function of preventing copper or silver from oxidizing, and is especially suitable for application in the antibacterial fiber industry.
  • the first purpose of the present invention is to disclose an organic-inorganic compound for preventing oxidation of copper or silver, which comprises 1-5 wt% of organic components and 95-99 wt% of inorganic components, the organic components comprising three Alkyl phosphite, dialkyl thioester, bishydrazide, phosphonate, or any combination thereof; and the inorganic composition includes at least one transition metal salt.
  • the trialkyl phosphite is triisodecyl phosphite
  • the dialkyl thioester is dilauryl thiodipropionate
  • the bishydrazide is N,N'-bis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
  • the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
  • the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: carbonate (CO 3 2 ⁇ ), nitric acid Root (NO3 - ), Sulfate (SO 4 2- ), Sulfide ion (S 2- ) and Oxygen ion (O 2- ).
  • the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  • the second object of the present invention is to provide the aforementioned method for producing the organic-inorganic hybrid for preventing oxidation of copper or silver, which specifically includes the following steps.
  • Step 1 wet grinding the mixture to obtain a sludge, the mixture contains 1-5wt% of organic components and 95-99wt% of inorganic components.
  • the organic composition contains trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; the inorganic composition contains at least one transition metal salt.
  • the sludge contains a powder with a particle size distribution (d50) between 200 nm and 500 nm.
  • Step 2 Perform a drying procedure to make the mud into a solid.
  • Step 3 dry grinding the solid, thereby obtaining the organic-inorganic hybrid for preventing oxidation of copper or silver, the organic-inorganic hybrid for preventing oxidation of copper or silver has a particle size distribution (d50) of 2 ⁇ 3 micron powder.
  • the trialkyl phosphite is triisodecyl phosphite
  • the dialkyl thioester is dilauryl thiodipropionate
  • the bishydrazide is N,N'-bis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
  • the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
  • the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: carbonate (CO 3 2 ⁇ ), nitric acid (NO3 - ), sulfate (SO 4 2- ), sulfide (S 2- ) and oxygen ions (O 2- ), and the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  • M represents a transition metal
  • X is an anion corresponding to M, which is selected from one or a combination of the following groups: carbonate (CO 3 2 ⁇ ), nitric acid (NO3 - ), sulfate (SO 4 2- ), sulfide (S 2- ) and oxygen ions (O 2- )
  • the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  • the third object of the present invention is to provide a method for manufacturing antibacterial polyester fiber, which specifically includes the following steps.
  • Step 1 Perform a mixing procedure to obtain a composition, based on the total weight of the composition, the composition includes 14 to 20 wt% of the organic-inorganic hybrid for preventing copper or silver oxidation according to claim 1 , 1-5wt% copper compound and 75-85wt% polyester.
  • Step 2 Execute the granulation procedure to make the composition an antibacterial polyester masterbatch.
  • Step 3 Execute the silk spinning procedure to make the antibacterial polyester masterbatch into the antibacterial polyester fiber.
  • the composition comprises a powder having a particle size distribution (d50) of 2-3 microns.
  • the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
  • the polyester is polyethylene terephthalate, polybutylene terephthalate, or combinations thereof.
  • the organic-inorganic hybrid provided by the present invention has the following technical features and effects.
  • the organic-inorganic hybrid is a micron-sized powder made of 1-5wt% organic antioxidant composition and 95-99wt% inorganic composition, which has the advantages of large body surface area and easy dispersion in polyester.
  • the organic-inorganic hybrid can prevent the oxidation of copper or silver during spinning or weaving, and is especially suitable for use in the polyester fiber industry.
  • the antibacterial polyester fiber made of the organic-inorganic hybrid of the present invention has good antibacterial activity, and will not cause inactivation of antibacterial activity during dyeing or other post-processing procedures.
  • Fig. 1 is the XPS spectrum of Cu 2p of copper PET master batch, and solid line is that this organic-inorganic composition is the copper PET master batch that the weight ratio of copper is 3.5; Dotted line is that this organic-inorganic composition is to the weight ratio of copper is 2.0 made of copper PET masterbatch.
  • Fig. 2 is the XPS spectrum of the O 1s of copper PET master batch, and solid line is that this organic-inorganic composition is the copper PET master batch that the weight ratio of copper is 3.5; Dotted line is that this organic-inorganic composition is to the weight ratio of copper is 2.0 made of copper PET masterbatch.
  • Figure 3 is the Cu 2pXPS spectrum of the copper PET masterbatch, in which the weight ratio of inorganic composition to copper is 3.5.
  • Figure 4 is the Cu 2p XPS spectrum of copper PET masterbatch, in which the weight ratio of organic composition to copper is 3.5.
  • Fig. 5 is the flowchart of the manufacturing method of antibacterial polyester fiber of the present invention.
  • Fig. 6 is the inhibitory effect diagram of the antibacterial polyester fiber of the present invention to Trichophyton mentatrophytes fungus.
  • the present invention provides an organic-inorganic hybrid.
  • the organic-inorganic mixture is powder, and has the technical effect of preventing copper or silver oxidation, and is especially suitable for application in the manufacture of copper or silver antibacterial polyester fiber industry.
  • the above-mentioned organic-inorganic hybrid is an organic-inorganic hybrid for preventing oxidation of copper or silver, and its composition includes 1-5 wt% of organic components and 95-99 wt% of inorganic components, the organic The composition comprises trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; and the inorganic composition comprises at least one transition metal salt.
  • the trialkylphosphite is triisodecylphosphite.
  • dialkylthioester is dilaurylthiodipropionate.
  • the bishydrazide is N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
  • the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
  • the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: Carbonate (CO 3 2 ⁇ ) , Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
  • the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  • Another embodiment of the present invention is to provide the method for manufacturing the organic-inorganic hybrid for preventing oxidation of copper or silver as described in the first embodiment, which includes the following steps.
  • Step 1 wet grinding the mixture to obtain a sludge, the mixture contains 1-5wt% of organic components and 95-99wt% of inorganic components.
  • the organic composition contains trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; the inorganic composition contains at least one transition metal salt.
  • the sludge contains a powder with a particle size distribution (d50) between 200 nm and 500 nm.
  • Step 2 Perform a drying procedure to make the mud into a solid.
  • Step 3 dry grinding the solid, thereby obtaining the organic-inorganic hybrid for preventing oxidation of copper or silver, the organic-inorganic hybrid for preventing oxidation of copper or silver has a particle size distribution (d50) of 2 ⁇ 3 micron powder.
  • the trialkylphosphite is triisodecylphosphite.
  • dialkylthioester is dilaurylthiodipropionate.
  • the bishydrazide is N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
  • the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
  • the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: Carbonate (CO 3 2 ⁇ ) , Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
  • the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  • Another embodiment of the present invention is to provide a method for manufacturing antibacterial polyester fiber, which includes the following steps.
  • Step 1 Perform a mixing procedure to obtain a composition, based on the total weight of the composition, the composition includes 14-20 wt% of the organic-inorganic hybrid for preventing copper or silver oxidation according to claim 1 , 1-5wt% copper compound and 75-85wt% polyester.
  • Step 2 Execute the granulation procedure to make the composition an antibacterial polyester masterbatch.
  • Step 3 Execute the silk spinning procedure to make the antibacterial polyester masterbatch into the antibacterial polyester fiber.
  • the composition comprises a powder having a particle size distribution (d50) of 2-3 microns.
  • the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
  • the polyester is polyethylene terephthalate, polybutylene terephthalate, or combinations thereof.
  • the manufacturing process of the above-mentioned antibacterial polyester fiber is as follows.
  • the mud contains particles with a particle size distribution (d50) of 200nm to 500nm
  • the powder 1 in between, and finally dry the mud and then dry grind to obtain the powder 1.
  • the copper compound is wet-ground to another sludge, which contains a powder 2 with a particle size distribution (d50) between 200 nm and 5 ⁇ m, and the other sludge is dried and then dry-milled to obtain a powder 2 .
  • the weight ratio of the powder 1 to the powder 2 is greater than or equal to 3.5.
  • the above-mentioned powder 1, powder 2 and polyester are made into polyester masterbatch by a twin-screw granulator, and then the spinning process is carried out to obtain antibacterial polyester staple fiber or antibacterial polyester long fiber, and finally the antibacterial efficacy test is carried out.
  • the organic and non-agent mixtures are separately wet milled, thereby obtaining a first slurry comprising a powder having a particle size analysis (d50) between 200 nm and 500 nm. dry grinding said slurry after drying, thereby obtaining a first solid or powder; and wet grinding said copper compound, thereby obtaining a second slurry comprising a particle size analysis (d50) of 200 nm to 5 Powder between microns, the copper compound is copper powder, cuprous oxide, cuprous chloride, cuprous bromide or cuprous iodide, after drying, dry grind the above-mentioned second slurry, thereby obtaining the second solid or powder.
  • d50 particle size analysis
  • the above-mentioned first solid or powder, second solid or powder and polyester are mixed to obtain a mixture, wherein the weight ratio of the organic agent-free mixture to copper is equal to or greater than 3.5.
  • the weight ratio of the organic agent-free mixture plus the copper compound to the polyester is between 5:95 and 20:80.
  • the weight ratio of the organic and non-agent compound plus the copper compound to the polyester is between 6.75:93.25 and 11.25:88.75.
  • the antibacterial polyester masterbatch is obtained by performing the granulation procedure, and the silk spinning procedure is thereby obtained to obtain the antibacterial polyester fiber.
  • the preparation method of the organic-inorganic hybrid for preventing copper or silver oxidation of the present invention is as follows. First, wet grinding inorganic composition and organic antioxidant to mud, the inorganic composition contains 5wt% zinc carbonate, 20wt% magnesium carbonate and 75wt% titanium dioxide; the composition of the inorganic composition can also be zinc nitrate, zinc sulfate, nitric acid Magnesium, magnesium sulfate, aluminum or iron oxide.
  • the organic antioxidant is bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium or N,N'-bis[3-(3,5-di-tert-butyl-4- Hydroxyphenyl) propionyl] hydrazine, the weight ratio of the inorganic composition to the organic antioxidant is 98:2, and the above-mentioned mud contains a particle size distribution (d50) that is a powder of 200nm to 5 microns; drying the mud to obtain a solid , then dry grind the solid into a powder, when the particle size distribution (d50) of the powder is 3 microns after dry grinding, the preparation of the organic-inorganic mixture for preventing copper or silver oxidation of the present invention is completed .
  • d50 particle size distribution
  • the appearance color of the antibacterial fiber product made is light yellow and is still stable in the air without discoloration, indicating that The copper contained in it is not oxidized.
  • the appearance color of the semi-product during the spinning process is pink and will gradually turn gray, indicating that the copper contained therein is gradually oxidized.
  • the appearance color of the antibacterial fiber product is black, which means that the copper contained in it has been completely oxidized during the spinning process, which also reduces the final antibacterial fiber product. The antibacterial effect of the product.
  • the oxidation state of copper embedded in the copper PET masterbatch was measured by XPS analysis, as shown in Figure 1 and Figure 2.
  • the weight ratio of the organic-inorganic mixture of the present invention to copper is 3.5
  • the binding energy of Cu 2p falls on 931.8 electron volts (eV) on the XPS spectrum, where the electron volts corresponds to copper metal or cuprous ((Cu (0) ) or Cu (I) (Cu 2 O)) (as shown by the solid line).
  • the binding energy of Cu 2p falls on 932.7 electron volts (eV) on the XPS spectrum, where electron volts corresponds to divalent copper (Cu ( II) ), that is, copper oxide (CuO) (as shown by the dotted line).
  • Cu ( II) divalent copper
  • CuO copper oxide
  • the binding energy of O1s is at 532.9 electron volts, but when the weight ratio of the organic-inorganic hybrid of the present invention to copper is equal to 2, the binding energy of O1s produces a blue shift to 532.1 electron volts (as shown by the dotted line), which is relatively Low binding energy indicates the presence of lattice oxygen, that is, when the weight ratio of organic-inorganic hybrid to copper is equal to 2 to make polyester fiber, the copper in it will be oxidized, causing the final polyester fiber to discolor and reduce its antibacterial properties efficacy.
  • this experiment example only uses the inorganic composition of the organic-inorganic hybrid of the present invention, as the experimental control group, the weight ratio of the inorganic composition to copper is 3.5.
  • XPS analysis of the prepared copper PET masterbatch shows that the binding energy of Cu 2p3 has shifted to 933.09 electron volts (eV), which indicates that copper oxidation has occurred.
  • the XPS analysis experiment of copper PET masterbatch clearly proves that the organic-inorganic mixture of the present invention has a synergistic effect on preventing copper oxidation, and neither a single inorganic composition nor an organic composition can effectively prevent copper from being deposited in the fiber manufacturing process. oxidation.
  • the antibacterial efficacy evaluation results of copper antibacterial polyester fibers made of the organic-inorganic mixture provided by the present invention are shown in Table 1 and Table 2.
  • the evaluation method is based on JIS 1902L:2015.
  • the weight ratio of the organic-inorganic mixture to copper is 3.5
  • the antibacterial activity of the copper antibacterial polyester fiber made is obviously better than that of the copper antibacterial polyester fiber made by the weight ratio of 2.
  • the reason is that when the weight ratio of the organic-inorganic mixture to copper of the present invention is 2, in the manufacturing process of the copper antibacterial polyester fiber, the copper will deteriorate due to oxidation, thereby affecting its antibacterial activity.
  • the organic-inorganic mixture of the present invention when the organic-inorganic mixture of the present invention is making copper antibacterial polyester fibers, its weight ratio for copper must be greater than or equal to 3.5, thereby reaching to prevent copper from oxidative deterioration in the manufacture process of antibacterial polyester fibers, and simultaneously It also makes the antibacterial polyester fiber have good antibacterial activity.
  • the antibacterial activity of the copper antibacterial PET polyester fiber made when the weight ratio of the organic-inorganic mixture of the present invention to copper is 3.5 is shown in Table 3 As shown, the antibacterial evaluation method is based on JIS 1902L:2015.
  • Table 4 shows the antibacterial activity of the copper antibacterial PET spun yarn prepared when the weight ratio of the organic-inorganic mixture to copper of the present invention is 3.5.
  • the antibacterial evaluation method is based on JIS1902L:2015.
  • the antibacterial effect of the copper antibacterial PET fiber prepared when the weight ratio of the organic-inorganic compound of the present invention to copper is 3.5 is shown in FIG. 6 .
  • the present invention provides an innovative organic-inorganic hybrid.
  • the weight ratio of the organic-inorganic hybrid to copper or silver is greater than or equal to 3.5, it has the technical effect of preventing copper or silver from oxidizing, and is especially suitable for use in Manufacture of antibacterial polyester fiber related industries.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Artificial Filaments (AREA)

Abstract

An organic-inorganic mixture for preventing copper or silver oxidation, a manufacturing method therefor, and an application thereof. The composition of the organic-inorganic mixture for preventing copper or silver oxidation comprises 1-5 wt% of an organic composition and 95-99 wt% of an inorganic composition. The organic composition comprises a trialkyl phosphite, a dialkyl thioester, a bishydrazide, a phosphonate, or any combination thereof; and the inorganic composition comprises at least one transition metal salt. In particular, the organic-inorganic mixture for preventing copper or silver oxidation can be applied in the field of manufacturing of antibacterial polyester fibers.

Description

一种用于防止铜或银氧化的有机无机混成物、其制造方法和应用An organic-inorganic hybrid for preventing oxidation of copper or silver, its production method and application 技术领域technical field
本发明是关于一种用于防止铜或银氧化的有机无机混成物，其组成包含1～5wt％的有机组成物和95～99wt％的无机组成物。特别地，上述的用于防止铜或银氧化的有机无机混成物能应用在抗菌聚酯纤维的制造领域。The invention relates to an organic-inorganic compound for preventing oxidation of copper or silver, which comprises 1-5 wt% of organic components and 95-99 wt% of inorganic components. In particular, the above-mentioned organic-inorganic hybrid for preventing copper or silver oxidation can be applied in the field of manufacturing antibacterial polyester fibers.
背景技术Background technique
在现有习知的纤维加工领域，为了赋予纤维具有抗菌的性能，常常是加入金属，如纳米银粒子到纤维母粒中，再借由纺纱，抽丝等加工程序制成具有抗菌功能的织品。但在上述抗菌织品的加工制程中的抽丝、纺丝、纺纱、织造程序常导致加入的金属氧化变质，导致制成的纤维容易出现断裂、粗糙、粗细不均和产生黑点的品质瑕疵，更大幅降低了最后抗菌纤维的抑菌效果。In the known field of fiber processing, in order to endow fibers with antibacterial properties, metals, such as nano-silver particles, are often added to fiber masterbatches, and then processed into fibers with antibacterial functions by spinning, spinning, etc. fabric. However, the spinning, spinning, spinning, and weaving procedures in the processing of the above-mentioned antibacterial fabrics often lead to the oxidation and deterioration of the added metals, resulting in quality defects such as breakage, roughness, uneven thickness, and black spots in the produced fibers. , which greatly reduces the antibacterial effect of the final antibacterial fiber.
综上所述，在现今聚酯纤维产业，对于开发防止金属在纤维制造过程中氧化的添加剂，并且能应用在制造抗菌聚酯纤维实为一亟待解决和研发的重要课题。In summary, in today's polyester fiber industry, it is an important issue to be solved and developed to develop additives to prevent metal oxidation during the fiber manufacturing process and to be able to apply them in the manufacture of antibacterial polyester fibers.
发明内容Contents of the invention
基于先前的技术背景，为了符合未来产业的需求，本发明提供一种有机无机混成物。特别地，该有机无机混成物具有防止铜或银氧化的技术功效，特别适合应用在抗菌纤维产业。Based on the previous technical background, in order to meet the needs of future industries, the present invention provides an organic-inorganic hybrid. In particular, the organic-inorganic hybrid has the technical function of preventing copper or silver from oxidizing, and is especially suitable for application in the antibacterial fiber industry.
本发明的第一目的在于揭示一种用于防止铜或银氧化的有机无机混成物，其组成包含1～5wt％的有机组成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；和该无机组成物包含至少一种过渡金属盐类。The first purpose of the present invention is to disclose an organic-inorganic compound for preventing oxidation of copper or silver, which comprises 1-5 wt% of organic components and 95-99 wt% of inorganic components, the organic components comprising three Alkyl phosphite, dialkyl thioester, bishydrazide, phosphonate, or any combination thereof; and the inorganic composition includes at least one transition metal salt.
具体地，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。Specifically, the trialkyl phosphite is triisodecyl phosphite, the dialkyl thioester is dilauryl thiodipropionate, and the bishydrazide is N,N'-bis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
具体地，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是对应于M的阴离子，其选自下列群组之一或其组合：碳酸根(CO 3 2-)、硝酸根 (NO3 -)、硫酸根(SO 4 2-)、硫离子(S 2-)和氧离子(O 2-)。 Specifically, the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: carbonate (CO 3 2− ), nitric acid Root (NO3 - ), Sulfate (SO 4 2- ), Sulfide ion (S 2- ) and Oxygen ion (O 2- ).
具体地，该过渡金属是镁、铝、锰、锌、钛、铁或镍。In particular, the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
本发明的第二目的在于提供前述的用于防止铜或银氧化的有机无机混成物的制造方法，具体包含如下步骤。The second object of the present invention is to provide the aforementioned method for producing the organic-inorganic hybrid for preventing oxidation of copper or silver, which specifically includes the following steps.
步骤一：湿式研磨混合物得到泥状物，该混合物包含1～5wt％的有机组成物和95～99wt％的无机组成物。Step 1: wet grinding the mixture to obtain a sludge, the mixture contains 1-5wt% of organic components and 95-99wt% of inorganic components.
具体地，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；该无机组成物包含至少一种过渡金属盐类。Specifically, the organic composition contains trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; the inorganic composition contains at least one transition metal salt.
更具体地，该泥状物含有粒径分布(d50)是在200纳米至500纳米之间的粉末。More specifically, the sludge contains a powder with a particle size distribution (d50) between 200 nm and 500 nm.
步骤二：执行干燥程序，使该泥状物成为固体。Step 2: Perform a drying procedure to make the mud into a solid.
步骤三：干式研磨该固体，借此得到所述的用于防止铜或银氧化的有机无机混成物，该用于防止铜或银氧化的有机无机混成物是粒径分布(d50)为2～3微米的粉体。Step 3: dry grinding the solid, thereby obtaining the organic-inorganic hybrid for preventing oxidation of copper or silver, the organic-inorganic hybrid for preventing oxidation of copper or silver has a particle size distribution (d50) of 2 ~3 micron powder.
具体地，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。Specifically, the trialkyl phosphite is triisodecyl phosphite, the dialkyl thioester is dilauryl thiodipropionate, and the bishydrazide is N,N'-bis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
具体地，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是对应于M的阴离子，其选自下列群组之一或其组合：碳酸根(CO 3 2-)、硝酸根(NO3 -)、硫酸根(SO 4 2-)、硫离子(S 2-)和氧离子(O 2-)，该过渡金属是镁、铝、锰、锌、钛、铁或镍。 Specifically, the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: carbonate (CO 3 2− ), nitric acid (NO3 - ), sulfate (SO 4 2- ), sulfide (S 2- ) and oxygen ions (O 2- ), and the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
本发明的第三目的在于提供一种抗菌聚酯纤维的制造方法，具体包含如下步骤。The third object of the present invention is to provide a method for manufacturing antibacterial polyester fiber, which specifically includes the following steps.
步骤一：执行混合程序，借此得到组成物，以该组成物的总重量计，该组成物包含14～20wt％的如权利要求1所述的用于防止铜或银氧化的有机无机混成物、1～5wt％的铜化合物和75～85wt％的聚酯。Step 1: Perform a mixing procedure to obtain a composition, based on the total weight of the composition, the composition includes 14 to 20 wt% of the organic-inorganic hybrid for preventing copper or silver oxidation according to claim 1 , 1-5wt% copper compound and 75-85wt% polyester.
步骤二：执行造粒程序，使该组成物成为抗菌聚酯母粒。Step 2: Execute the granulation procedure to make the composition an antibacterial polyester masterbatch.
步骤三：执行绢纺程序，使该抗菌聚酯母粒成为所述的抗菌聚酯纤维。Step 3: Execute the silk spinning procedure to make the antibacterial polyester masterbatch into the antibacterial polyester fiber.
具体地，该组成物包含粒径分布(d50)是2～3微米的粉末。Specifically, the composition comprises a powder having a particle size distribution (d50) of 2-3 microns.
具体地，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。Specifically, the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
具体地，该聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二酯或其组合。Specifically, the polyester is polyethylene terephthalate, polybutylene terephthalate, or combinations thereof.
综上，本发明提供的有机无机混成物具有如下的技术特征和功效。(1)该有机无机混成物是由1～5wt％的有机抗氧化剂组成物和95～99wt％的无机组成物制成的微米级粉末，具有体表面积大，容易分散在聚酯中的优点。(2)该有机无机混成物能够防止铜或银在纺纱或织造过程中氧化，特别适合应用在聚酯纤维工业。(3)应用本发明的有机无机混成物制成的抗菌聚酯纤维具有良好的抗菌活性，在染色或其他后加工程序时都不会导致抗菌活性失活。In summary, the organic-inorganic hybrid provided by the present invention has the following technical features and effects. (1) The organic-inorganic hybrid is a micron-sized powder made of 1-5wt% organic antioxidant composition and 95-99wt% inorganic composition, which has the advantages of large body surface area and easy dispersion in polyester. (2) The organic-inorganic hybrid can prevent the oxidation of copper or silver during spinning or weaving, and is especially suitable for use in the polyester fiber industry. (3) The antibacterial polyester fiber made of the organic-inorganic hybrid of the present invention has good antibacterial activity, and will not cause inactivation of antibacterial activity during dyeing or other post-processing procedures.
附图的简要说明Brief description of the drawings
图1是铜PET母粒的Cu 2p的XPS图谱，实线是该有机无机组成物对铜的重量比例是3.5制成的铜PET母粒；虚线是该有机无机组成物对铜的重量比例是2.0制成的铜PET母粒。Fig. 1 is the XPS spectrum of Cu 2p of copper PET master batch, and solid line is that this organic-inorganic composition is the copper PET master batch that the weight ratio of copper is 3.5; Dotted line is that this organic-inorganic composition is to the weight ratio of copper is 2.0 made of copper PET masterbatch.
图2是铜PET母粒的O 1s的XPS图谱，实线是该有机无机组成物对铜的重量比例是3.5制成的铜PET母粒；虚线是该有机无机组成物对铜的重量比例是2.0制成的铜PET母粒。Fig. 2 is the XPS spectrum of the O 1s of copper PET master batch, and solid line is that this organic-inorganic composition is the copper PET master batch that the weight ratio of copper is 3.5; Dotted line is that this organic-inorganic composition is to the weight ratio of copper is 2.0 made of copper PET masterbatch.
图3是铜PET母粒的Cu 2pXPS图谱，其中无机组成物对铜的重量比例是3.5。Figure 3 is the Cu 2pXPS spectrum of the copper PET masterbatch, in which the weight ratio of inorganic composition to copper is 3.5.
图4是铜PET母粒的Cu 2p XPS图谱，其中有机组成物对铜的重量比例是3.5。Figure 4 is the Cu 2p XPS spectrum of copper PET masterbatch, in which the weight ratio of organic composition to copper is 3.5.
图5是本发明抗菌聚酯纤维的制造方法的流程图。Fig. 5 is the flowchart of the manufacturing method of antibacterial polyester fiber of the present invention.
图6是本发明抗菌聚酯纤维对于Trichophyton mentagrophytes真菌的抑制效果图。Fig. 6 is the inhibitory effect diagram of the antibacterial polyester fiber of the present invention to Trichophyton mentatrophytes fungus.
实现发明的最佳方式The best way to realize the invention
根据本发明第一实施例，本发明提供一种有机无机混成物。该有机无机混成物是粉体，并具有防止铜或银氧化的技术功效，特别适合应用在制造铜或银抗菌聚酯纤维产业。According to the first embodiment of the present invention, the present invention provides an organic-inorganic hybrid. The organic-inorganic mixture is powder, and has the technical effect of preventing copper or silver oxidation, and is especially suitable for application in the manufacture of copper or silver antibacterial polyester fiber industry.
在一实施例，上述的有机无机混成物是一种用于防止铜或银氧化的有机无机混成物，其组成包含1～5wt％的有机组成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；和该无机组成物包含至少一种过渡金属盐类。In one embodiment, the above-mentioned organic-inorganic hybrid is an organic-inorganic hybrid for preventing oxidation of copper or silver, and its composition includes 1-5 wt% of organic components and 95-99 wt% of inorganic components, the organic The composition comprises trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; and the inorganic composition comprises at least one transition metal salt.
在一具体实施例，该三烷基亚磷酸酯是三异癸基亚磷酸酯。In a specific embodiment, the trialkylphosphite is triisodecylphosphite.
在一具体实施例，该二烷基硫酯是硫代二丙酸二月桂酯。In a specific embodiment, the dialkylthioester is dilaurylthiodipropionate.
在一具体实施例，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼。In a specific embodiment, the bishydrazide is N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
在一具体实施例，该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。In a specific embodiment, the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
在一实施例，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是对应于M的阴离子，其选自下列群组之一或其组合：碳酸根(CO 3 2-)、硝酸根(NO3 -)、硫酸根(SO 4 2-)、硫离子(S 2-)和氧离子(O 2-)。 In one embodiment, the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: Carbonate (CO 3 2− ) , Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
在一具体实施例，该过渡金属是镁、铝、锰、锌、钛、铁或镍。In a specific embodiment, the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
本发明的另一实施例在于提供如第一实施例所述的用于防止铜或银氧化的有机无机混成物的制造方法，其包含如下步骤。Another embodiment of the present invention is to provide the method for manufacturing the organic-inorganic hybrid for preventing oxidation of copper or silver as described in the first embodiment, which includes the following steps.
步骤一：湿式研磨混合物得到泥状物，该混合物包含1～5wt％的有机组成物和95～99wt％的无机组成物。Step 1: wet grinding the mixture to obtain a sludge, the mixture contains 1-5wt% of organic components and 95-99wt% of inorganic components.
具体地，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；该无机组成物包含至少一种过渡金属盐类。Specifically, the organic composition contains trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; the inorganic composition contains at least one transition metal salt.
更具体地，该泥状物含有粒径分布(d50)是在200纳米至500纳米之间的粉末。More specifically, the sludge contains a powder with a particle size distribution (d50) between 200 nm and 500 nm.
步骤二：执行干燥程序，使该泥状物成为固体。Step 2: Perform a drying procedure to make the mud into a solid.
步骤三：干式研磨该固体，借此得到所述的用于防止铜或银氧化的有机无机混成物，该用于防止铜或银氧化的有机无机混成物是粒径分布(d50)为2～3微米的粉体。Step 3: dry grinding the solid, thereby obtaining the organic-inorganic hybrid for preventing oxidation of copper or silver, the organic-inorganic hybrid for preventing oxidation of copper or silver has a particle size distribution (d50) of 2 ~3 micron powder.
在一具体实施例，该三烷基亚磷酸酯是三异癸基亚磷酸酯。In a specific embodiment, the trialkylphosphite is triisodecylphosphite.
在一具体实施例，该二烷基硫酯是硫代二丙酸二月桂酯。In a specific embodiment, the dialkylthioester is dilaurylthiodipropionate.
在一具体实施例，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼。In a specific embodiment, the bishydrazide is N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
在一具体实施例，该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。In a specific embodiment, the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
在一实施例，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是对应于M的阴离子，其选自下列群组之一或其组合：碳酸根(CO 3 2-)、硝酸根(NO3 -)、硫酸根(SO 4 2-)、硫离子(S 2-)和氧离子(O 2-)。 In one embodiment, the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is an anion corresponding to M, which is selected from one or a combination of the following groups: Carbonate (CO 3 2− ) , Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
在一具体实施例，该过渡金属是镁、铝、锰、锌、钛、铁或镍。In a specific embodiment, the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
本发明的又一实施例在于提供一种抗菌聚酯纤维的制造方法，其包含如下步骤。Another embodiment of the present invention is to provide a method for manufacturing antibacterial polyester fiber, which includes the following steps.
步骤一：执行混合程序，借此得到组成物，以该组成物的总重量计， 该组成物包含14～20wt％的如权利要求1所述的用于防止铜或银氧化的有机无机混成物、1～5wt％的铜化合物和75～85wt％的聚酯。Step 1: Perform a mixing procedure to obtain a composition, based on the total weight of the composition, the composition includes 14-20 wt% of the organic-inorganic hybrid for preventing copper or silver oxidation according to claim 1 , 1-5wt% copper compound and 75-85wt% polyester.
步骤二：执行造粒程序，使该组成物成为抗菌聚酯母粒。Step 2: Execute the granulation procedure to make the composition an antibacterial polyester masterbatch.
步骤三：执行绢纺程序，使该抗菌聚酯母粒成为所述的抗菌聚酯纤维。Step 3: Execute the silk spinning procedure to make the antibacterial polyester masterbatch into the antibacterial polyester fiber.
在一具体实施例，该组成物包含粒径分布(d50)是2～3微米的粉末。In one embodiment, the composition comprises a powder having a particle size distribution (d50) of 2-3 microns.
在一具体实施例，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。In a specific embodiment, the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
在一具体实施例，该聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二酯或其组合。In a specific embodiment, the polyester is polyethylene terephthalate, polybutylene terephthalate, or combinations thereof.
在一代表实施例，请参照图5，上述的抗菌聚酯纤维的制造流程如下所述。In a representative embodiment, please refer to FIG. 5 , the manufacturing process of the above-mentioned antibacterial polyester fiber is as follows.
混合1-5wt％的有机抗氧化剂和95-99wt％的无机组成物形成组成物，然后湿式研磨该组成物至一泥状物，该泥状物包含粒径分布(d50)为200nm到500nm之间的粉末1，最后干燥该泥状物后再干式研磨得到粉体1。Mixing 1-5wt% of organic antioxidants and 95-99wt% of inorganic components to form a composition, and then wet grinding the composition to a mud, the mud contains particles with a particle size distribution (d50) of 200nm to 500nm The powder 1 in between, and finally dry the mud and then dry grind to obtain the powder 1.
湿式研磨铜化合物至另一泥状物，其包含粒径分布(d50)为200nm到5μm之间的粉末2，干燥该另一泥状物后再干式研磨得到粉体2。The copper compound is wet-ground to another sludge, which contains a powder 2 with a particle size distribution (d50) between 200 nm and 5 μm, and the other sludge is dried and then dry-milled to obtain a powder 2 .
混合粉体1和粉体2，该粉体1对该粉体2的重量比例是大于或等于3.5。Mixing powder 1 and powder 2, the weight ratio of the powder 1 to the powder 2 is greater than or equal to 3.5.
将上述的粉体1、粉体2和聚酯以双螺杆造粒机制成聚酯母粒，然后进行纺纱程序得到抗菌聚酯短纤或抗菌聚酯长纤，最后再进行抗菌效能检验。The above-mentioned powder 1, powder 2 and polyester are made into polyester masterbatch by a twin-screw granulator, and then the spinning process is carried out to obtain antibacterial polyester staple fiber or antibacterial polyester long fiber, and finally the antibacterial efficacy test is carried out.
在另一代表实施例，分别湿式研磨所述的有机无剂混成物，借此得到第一泥浆，该第一泥浆包含粒径分析(d50)为200纳米到500纳米之间的粉末。干燥后干式研磨上述的泥浆，借此得到第一固体或粉末；和湿式研磨所述的铜化合物，借此得到第二泥浆，该第二泥浆包含粒径分析(d50)为200纳米到5微米之间的粉末，该铜化合物是铜粉、氧化亚铜、氯化亚铜、溴化亚铜或碘化亚铜，干燥后干式研磨上述的第二泥浆，借此得到第二固体或粉末。然后混合上述的第一固体或粉末、第二固体或粉末和聚酯，借此得到混合物，其中该有机无剂混成物对铜的重量比例是等于或大于3.5。该有机无剂混成物加上铜化合物对于聚酯的重量比例是在5:95到20：80之间。较佳地，该有机无剂混成物加上铜化合物对于聚酯的重量比例是在6.75:93.25到11.25：88.75之间。执行造粒程序借此得到抗菌聚酯母粒，和执行绢纺程序，借此得到所述的抗菌聚酯纤维。In another representative embodiment, the organic and non-agent mixtures are separately wet milled, thereby obtaining a first slurry comprising a powder having a particle size analysis (d50) between 200 nm and 500 nm. dry grinding said slurry after drying, thereby obtaining a first solid or powder; and wet grinding said copper compound, thereby obtaining a second slurry comprising a particle size analysis (d50) of 200 nm to 5 Powder between microns, the copper compound is copper powder, cuprous oxide, cuprous chloride, cuprous bromide or cuprous iodide, after drying, dry grind the above-mentioned second slurry, thereby obtaining the second solid or powder. Then, the above-mentioned first solid or powder, second solid or powder and polyester are mixed to obtain a mixture, wherein the weight ratio of the organic agent-free mixture to copper is equal to or greater than 3.5. The weight ratio of the organic agent-free mixture plus the copper compound to the polyester is between 5:95 and 20:80. Preferably, the weight ratio of the organic and non-agent compound plus the copper compound to the polyester is between 6.75:93.25 and 11.25:88.75. The antibacterial polyester masterbatch is obtained by performing the granulation procedure, and the silk spinning procedure is thereby obtained to obtain the antibacterial polyester fiber.
以下以具体实验例阐述本发明。The present invention is described below with specific experimental examples.
在一实验例，本发明的用于防止铜或银氧化的有机无机混成物的制备 方法如下所述。首先，湿式研磨无机组成物和有机抗氧化剂至泥浆，该无机组成物含有5wt％碳酸锌，20wt％碳酸镁和75wt％的二氧化钛；该无机组成物的组成也可以是硝酸锌、硫酸锌、硝酸镁、硫酸镁、三氧化二铝或三氧化二铁。该有机抗氧化剂是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙或N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，该无机组成物对该有机抗氧化剂的重量比例是98：2，和上述的泥浆含有粒径分布(d50)是200nm～5微米的粉末；干燥该泥浆得到固体，然后干式研磨该固体成粉体，当干式研磨到该粉体的粒径分布(d50)是3微米时，即完成本发明的用于防止铜或银氧化的有机无机混成物的制备 。 In an experimental example, the preparation method of the organic-inorganic hybrid for preventing copper or silver oxidation of the present invention is as follows. First, wet grinding inorganic composition and organic antioxidant to mud, the inorganic composition contains 5wt% zinc carbonate, 20wt% magnesium carbonate and 75wt% titanium dioxide; the composition of the inorganic composition can also be zinc nitrate, zinc sulfate, nitric acid Magnesium, magnesium sulfate, aluminum or iron oxide. The organic antioxidant is bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium or N,N'-bis[3-(3,5-di-tert-butyl-4- Hydroxyphenyl) propionyl] hydrazine, the weight ratio of the inorganic composition to the organic antioxidant is 98:2, and the above-mentioned mud contains a particle size distribution (d50) that is a powder of 200nm to 5 microns; drying the mud to obtain a solid , then dry grind the solid into a powder, when the particle size distribution (d50) of the powder is 3 microns after dry grinding, the preparation of the organic-inorganic mixture for preventing copper or silver oxidation of the present invention is completed .
在一实验例，当本发明的有机无机混成物对铜的重量比例是大于或等于3.5时，所制成的抗菌纤维产品的外观颜色是淡黄色且在空气中仍是稳定不会变色，表示其中所含的铜没有氧化。但是当本发明的有机无机混成物对铜的重量比例是2时，在纺纱过程中半产品的外观颜色是粉红色，且会逐渐变成灰色，表示其中所含的铜逐渐氧化。在另一完全没有添加本发明所述的有机无机混成物的实验对照组的抗菌纤维产品的外观颜色则是黑色，表示表示其中所含的铜在纺纱过程中已经完全氧化，也降低了最终产品的抗菌效果。In an experimental example, when the weight ratio of the organic-inorganic mixture of the present invention to copper is greater than or equal to 3.5, the appearance color of the antibacterial fiber product made is light yellow and is still stable in the air without discoloration, indicating that The copper contained in it is not oxidized. But when the weight ratio of the organic-inorganic mixture of the present invention to copper is 2, the appearance color of the semi-product during the spinning process is pink and will gradually turn gray, indicating that the copper contained therein is gradually oxidized. In another experimental control group that does not add the organic-inorganic hybrid of the present invention, the appearance color of the antibacterial fiber product is black, which means that the copper contained in it has been completely oxidized during the spinning process, which also reduces the final antibacterial fiber product. The antibacterial effect of the product.
铜PET母粒的XPS分析实验XPS Analysis Experiment of Copper PET Masterbatch
利用XPS分析测量嵌入铜PET母粒中的铜的氧化态，请参照图1和图2所示。当本发明的有机无机混成物对铜的重量比例是3.5，Cu 2p3的束缚能在XPS光谱上是落在931.8电子伏特(eV)，此处电子伏特对应的是铜金属或亚铜((Cu (0))或Cu (I)(Cu 2O))(如实线所示)。当本发明的有机无机混成物对铜的重量比例是小于3.5时，Cu 2p3的束缚能在XPS光谱上是落在932.7电子伏特(eV)，此处电子伏特对应的是二价铜(Cu (II))，也就是氧化铜(CuO)(如虚线所示)。在束缚能940～948电子伏特之间出现了振动激发峰群(shake-up excitation)，此现象更明确证实在分析的表面结构中存在氧化铜(CuO)(如虚线所示)。其次，O1s的束缚能是在532.9电子伏特，但是当本发明的有机无机混成物对铜的重量比例是等于2时，O1s的束缚能产生蓝位移到532.1电子伏特(如虚线所示)，较低的束缚能表示存在晶格氧，也就是在当使用有机无机混成物对铜的重量比例等于2制造聚酯纤维时，其中的铜会被氧化，导致最终的聚酯纤维变色并降低其抗菌效能。 The oxidation state of copper embedded in the copper PET masterbatch was measured by XPS analysis, as shown in Figure 1 and Figure 2. When the weight ratio of the organic-inorganic mixture of the present invention to copper is 3.5, the binding energy of Cu 2p falls on 931.8 electron volts (eV) on the XPS spectrum, where the electron volts corresponds to copper metal or cuprous ((Cu (0) ) or Cu (I) (Cu 2 O)) (as shown by the solid line). When the organic-inorganic hybrid of the present invention is less than 3.5 to the weight ratio of copper, the binding energy of Cu 2p falls on 932.7 electron volts (eV) on the XPS spectrum, where electron volts corresponds to divalent copper (Cu ( II) ), that is, copper oxide (CuO) (as shown by the dotted line). A shake-up excitation appeared between the binding energy of 940-948 eV, which more clearly confirmed the presence of copper oxide (CuO) in the analyzed surface structure (as shown by the dotted line). Secondly, the binding energy of O1s is at 532.9 electron volts, but when the weight ratio of the organic-inorganic hybrid of the present invention to copper is equal to 2, the binding energy of O1s produces a blue shift to 532.1 electron volts (as shown by the dotted line), which is relatively Low binding energy indicates the presence of lattice oxygen, that is, when the weight ratio of organic-inorganic hybrid to copper is equal to 2 to make polyester fiber, the copper in it will be oxidized, causing the final polyester fiber to discolor and reduce its antibacterial properties efficacy.
在另一XPS分析实验例，请参照图3，本实验例仅使用本发明有机无机混成物的无机组成物，作为实验对照组，该无机组成物对铜的重量比例是 3.5。制成的铜PET母粒XPS分析显示Cu 2p3的束缚能位移到933.09电子伏特(eV)，此表示已出现铜氧化的现象。In another XPS analysis experiment example, please refer to Fig. 3, this experiment example only uses the inorganic composition of the organic-inorganic hybrid of the present invention, as the experimental control group, the weight ratio of the inorganic composition to copper is 3.5. XPS analysis of the prepared copper PET masterbatch shows that the binding energy of Cu 2p3 has shifted to 933.09 electron volts (eV), which indicates that copper oxidation has occurred.
在另一XPS分析实验例，请参照图4，本实验例仅使用本发明有机无机混成物的有机组成物，作为实验对照组，该有机组成物对铜的重量比例是3.5。制成的铜PET母粒XPS分析显示Cu 2p3的束缚能位移到932.6电子伏特(eV)，在束缚能940～948电子伏特之间观察到明显的振动激发峰群，且Cu 2p1的相对强度降低，据此证实已出现铜氧化的现象。In another XPS analysis experiment example, please refer to FIG. 4. In this experiment example, only the organic composition of the organic-inorganic hybrid of the present invention is used as the experimental control group. The weight ratio of the organic composition to copper is 3.5. The XPS analysis of the prepared copper PET masterbatch shows that the binding energy of Cu 2p3 is shifted to 932.6 electron volts (eV), and obvious vibration excitation peaks are observed between the binding energy of 940-948 electron volts, and the relative intensity of Cu 2p1 decreases , which confirms that the phenomenon of copper oxidation has occurred.
综上，铜PET母粒的XPS分析实验明确证实本发明的有机无机混成物对于防止铜氧化具有加乘作用，单一的无机组成物或有机组成物都无法有效地防止铜在纤维制造的过程中氧化。In summary, the XPS analysis experiment of copper PET masterbatch clearly proves that the organic-inorganic mixture of the present invention has a synergistic effect on preventing copper oxidation, and neither a single inorganic composition nor an organic composition can effectively prevent copper from being deposited in the fiber manufacturing process. oxidation.
抗菌效能测试Antibacterial Efficacy Test
使用本发明提供的有机无机物混成物制成的铜抗菌聚酯纤维进行抗菌效能评估结果如表一和表二所示。评估法是依据JIS 1902L:2015。当本发明的有机无机物混成物对铜的重量比例是3.5时，所制成的铜抗菌聚酯纤维的抗菌活性明显优于其重量比例是2所制成的铜抗菌聚酯纤维。其原因为当本发明的有机无机物混成物对铜的重量比例是2时，在铜抗菌聚酯纤维的制造过程中，铜因为氧化而导致变质，进而影响其抗菌活性。据此，本发明的有机无机物混成物在制造铜抗菌聚酯纤维时，其对于铜的重量比例必须大于或等于3.5，借此达到防止铜在抗菌聚酯纤维的制造过程中氧化变质，同时也使制成的抗菌聚酯纤维具有良好的抗菌活性。The antibacterial efficacy evaluation results of copper antibacterial polyester fibers made of the organic-inorganic mixture provided by the present invention are shown in Table 1 and Table 2. The evaluation method is based on JIS 1902L:2015. When the weight ratio of the organic-inorganic mixture to copper is 3.5, the antibacterial activity of the copper antibacterial polyester fiber made is obviously better than that of the copper antibacterial polyester fiber made by the weight ratio of 2. The reason is that when the weight ratio of the organic-inorganic mixture to copper of the present invention is 2, in the manufacturing process of the copper antibacterial polyester fiber, the copper will deteriorate due to oxidation, thereby affecting its antibacterial activity. Accordingly, when the organic-inorganic mixture of the present invention is making copper antibacterial polyester fibers, its weight ratio for copper must be greater than or equal to 3.5, thereby reaching to prevent copper from oxidative deterioration in the manufacture process of antibacterial polyester fibers, and simultaneously It also makes the antibacterial polyester fiber have good antibacterial activity.
表一Table I
Figure PCTCN2022100464-appb-000001
Figure PCTCN2022100464-appb-000001
表二Table II
Figure PCTCN2022100464-appb-000002
Figure PCTCN2022100464-appb-000002
Figure PCTCN2022100464-appb-000003
Figure PCTCN2022100464-appb-000003
在另一实验例，本发明的有机无机物混成物对铜的重量比例是3.5时所制成的铜抗菌PET聚酯纤维在染色和有无经过还原洗涤(reduction clean)的抗菌活性如表三所示，抗菌评估法是依据JIS 1902L:2015。In another experimental example, the antibacterial activity of the copper antibacterial PET polyester fiber made when the weight ratio of the organic-inorganic mixture of the present invention to copper is 3.5 is shown in Table 3 As shown, the antibacterial evaluation method is based on JIS 1902L:2015.
表三Table three
Figure PCTCN2022100464-appb-000004
Figure PCTCN2022100464-appb-000004
在另一实验例，表四是本发明的有机无机物混成物对铜的重量比例是3.5时所制成的铜抗菌PET短纤纱的抗菌活性。抗菌评估法是依据JIS1902L:2015。In another experimental example, Table 4 shows the antibacterial activity of the copper antibacterial PET spun yarn prepared when the weight ratio of the organic-inorganic mixture to copper of the present invention is 3.5. The antibacterial evaluation method is based on JIS1902L:2015.
表四Table four
Figure PCTCN2022100464-appb-000005
Figure PCTCN2022100464-appb-000005
在另一实验例，本发明的有机无机物混成物对铜的重量比例是3.5时所制成的铜抗菌PET纤维的抗菌效果如图6所示。在培养皿上没有观察到Trichophyton Mentagrophytes真菌的生长。In another experimental example, the antibacterial effect of the copper antibacterial PET fiber prepared when the weight ratio of the organic-inorganic compound of the present invention to copper is 3.5 is shown in FIG. 6 . No growth of Trichophyton Mentagrophytes fungus was observed on Petri dishes.
综上所述，本发明提供一种创新的有机无机混成物，当该有机无机混成物对铜或银的重量比例大于或等于3.5时，具有防止铜或银氧化的技术功效，特别适合应用在制造抗菌聚酯纤维相关产业领域。In summary, the present invention provides an innovative organic-inorganic hybrid. When the weight ratio of the organic-inorganic hybrid to copper or silver is greater than or equal to 3.5, it has the technical effect of preventing copper or silver from oxidizing, and is especially suitable for use in Manufacture of antibacterial polyester fiber related industries.
以上虽以特定实验例说明本发明，但并不因此限定本发明的范围，只要不脱离本发明的要旨，熟悉本技艺者了解在不脱离本发明的意图及范围下可进行各种变形或变更。此外，摘要部分和标题仅是用来辅助专利文件搜寻之用，并非用来限制本发明的权利范围。Although the present invention has been described above with specific experimental examples, the scope of the present invention is not limited thereto. As long as it does not depart from the gist of the present invention, those skilled in the art understand that various deformations or changes can be made without departing from the intention and scope of the present invention. . In addition, the abstract and the title are only used to assist in the search of patent documents, and are not used to limit the scope of rights of the present invention.

Claims (12)

  1. 一种用于防止铜或银氧化的有机无机混成物，其特征在于，其组成包含1～5wt％的有机组成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；和该无机组成物包含至少一种过渡金属盐类。An organic-inorganic hybrid for preventing oxidation of copper or silver, characterized in that its composition comprises 1-5% by weight of an organic composition and 95-99% by weight of an inorganic composition, and the organic composition contains trialkyl phosphorous acid ester, dialkylthioester, bishydrazide, phosphonate, or any combination thereof; and the inorganic composition includes at least one transition metal salt.
  2. 根据权利要求1所述的用于防止铜或银氧化的有机无机混成物，其特征在于，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。The organic-inorganic hybrid for preventing copper or silver oxidation according to claim 1, wherein the trialkyl phosphite is triisodecyl phosphite, and the dialkyl thioester is thiodi dilauryl propionate, the bishydrazide is N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, and the phosphonate is bis(3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium.
  3. 根据权利要求1所述的用于防止铜或银氧化的有机无机混成物，其特征在于，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是选自下列群组之一或其组合：碳酸根、硝酸根、硫酸根、硫离子和氧离子。The organic-inorganic hybrid for preventing copper or silver oxidation according to claim 1, characterized in that, the transition metal salt has the general formula of MX, wherein M represents a transition metal, and X is selected from one of the following groups or combinations thereof: carbonate, nitrate, sulfate, sulfide and oxygen ions.
  4. 根据权利要求3所述的用于防止铜或银氧化的有机无机混成物，其特征在于，该过渡金属是镁、铝、锰、锌、钛、铁或镍。The organic-inorganic hybrid for preventing oxidation of copper or silver according to claim 3, wherein the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  5. 一种用于防止铜或银氧化的有机无机混成物的制造方法，其特征在于，其步骤包含：A method for producing an organic-inorganic hybrid for preventing oxidation of copper or silver, characterized in that the steps include:
    湿式研磨混合物得到泥状物，该混合物包含1～5wt％的有机组Wet grinding mixture to obtain a sludge, the mixture contains 1 to 5% by weight of organic matter
    成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；该无机组成物包含至少一种过渡金属盐类；和该泥状物含有粒径分布(d50)是在200纳米至500纳米之间的粉末；Composition and 95-99wt% inorganic composition, the organic composition contains trialkyl phosphite, dialkyl thioester, bishydrazide, phosphonate or any combination thereof; the inorganic composition contains at least one A transition metal salt; and the mud containing particle size distribution (d50) is a powder between 200 nanometers and 500 nanometers;
    执行干燥程序，使该泥状物成为固体；和performing a drying procedure to render the sludge solid; and
    干式研磨该固体，借此得到所述的用于防止铜或银氧化的有机无机混成物，该用于防止铜或银氧化的有机无机混成物是粒径分布(d50)为2～3微米的粉体。dry grinding the solid, thereby obtaining the organic-inorganic hybrid for preventing oxidation of copper or silver, the organic-inorganic hybrid for preventing oxidation of copper or silver has a particle size distribution (d50) of 2 to 3 microns powder.
  6. 根据权利要求5所述的用于防止铜或银氧化的有机无机混成物的制造方法，其特征在于，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基 硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。The method for producing an organic-inorganic compound for preventing oxidation of copper or silver according to claim 5, wherein the trialkyl phosphite is triisodecyl phosphite, and the dialkyl thioester is Dilauryl thiodipropionate, the bishydrazide is N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, and the phosphonate is Calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester).
  7. 根据权利要求5所述的用于防止铜或银氧化的有机无机混成物的制造方法，其特征在于，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是选自下列群组之一或其组合：碳酸根、硝酸根、硫酸根、硫离子和氧离子。The method for producing an organic-inorganic compound for preventing oxidation of copper or silver according to claim 5, wherein the transition metal salt has a general formula of MX, wherein M represents a transition metal, and X is selected from the following group One or a combination of groups: carbonate, nitrate, sulfate, sulfide and oxygen ions.
  8. 根据权利要求7所述的用于防止铜或银氧化的有机无机混成物的制造方法，其特征在于，该过渡金属是镁、铝、锰、锌、钛、铁或镍。The method for producing an organic-inorganic compound for preventing oxidation of copper or silver according to claim 7, wherein the transition metal is magnesium, aluminum, manganese, zinc, titanium, iron or nickel.
  9. 一种抗菌聚酯纤维的制造方法，其特征在于，其步骤包含：A kind of manufacture method of antibacterial polyester fiber is characterized in that, its step comprises:
    执行混合程序，借此得到组成物，以该组成物的总重量计，该组成物包含14～20wt％的如权利要求1所述的用于防止铜或银氧化的有机无机混成物、1～5wt％的铜化合物和75～85wt％的聚酯；Perform a mixing procedure, thereby obtaining a composition, based on the total weight of the composition, the composition comprises 14 to 20 wt% of the organic-inorganic hybrid for preventing copper or silver oxidation as claimed in claim 1, 1 to 5wt% copper compound and 75-85wt% polyester;
    执行造粒程序，使该组成物成为抗菌聚酯母粒；和performing a granulation procedure so that the composition becomes an antimicrobial polyester masterbatch; and
    执行绢纺程序，使该抗菌聚酯母粒成为所述的抗菌聚酯纤维。Carry out silk spinning procedure, make this antibacterial polyester masterbatch become described antibacterial polyester fiber.
  10. 根据权利要求9所述的抗菌聚酯纤维的制造方法，其特征在于，该组成物包含粒径分布(d50)是2～3微米的粉末。The method for producing antibacterial polyester fiber according to claim 9, characterized in that the composition comprises powder with a particle size distribution (d50) of 2-3 microns.
  11. 根据权利要求9所述的抗菌聚酯纤维的制造方法，其特征在于，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。The manufacture method of antibacterial polyester fiber according to claim 9, is characterized in that, the copper compound is selected from one of the following groups or a combination thereof: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
  12. 根据权利要求9所述的抗菌聚酯纤维的制造方法，其特征在于，聚酯是聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二酯或其组合。The manufacture method of antibacterial polyester fiber according to claim 9, is characterized in that, polyester is polyethylene terephthalate, polybutylene terephthalate or its combination.
PCT/CN2022/100464 2021-06-23 2022-06-22 Organic-inorganic mixture for preventing copper or silver oxidation, manufacturing method therefor, and application thereof WO2022268122A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202163213786P 2021-06-23 2021-06-23
US63/213,786 2021-06-23

Publications (1)

Publication Number Publication Date
WO2022268122A1 true WO2022268122A1 (en) 2022-12-29

Family

ID=84545186

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/100464 WO2022268122A1 (en) 2021-06-23 2022-06-22 Organic-inorganic mixture for preventing copper or silver oxidation, manufacturing method therefor, and application thereof

Country Status (2)

Country Link
TW (1) TWI817565B (en)
WO (1) WO2022268122A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054740A (en) * 2007-05-22 2007-10-17 杭州师范大学 Low temperature producing method for nylon fiber
CN101139749A (en) * 2007-07-13 2008-03-12 杭州师范大学 Fine denier or ultra-fine denier nylon fibre and production method thereof
US20080193496A1 (en) * 2005-03-21 2008-08-14 The Cupron Corporation Antimicrobial And Antiviral Polymeric Master Batch, Processes For Producing Polymeric Material Therefrom And Products Produced Therefrom
CN104206418A (en) * 2014-08-07 2014-12-17 蔡惠萍 Preparation method and application of discoloration-preventing powdery silver-containing anti-bacterial agent
CN104592629A (en) * 2015-01-05 2015-05-06 上海纳旭实业有限公司 Preparation method of Cu/ZnO composite antibacterial PP masterbatch
CN112004879A (en) * 2018-05-03 2020-11-27 瑞士新集团有限公司 Antidegradant blends

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3684858A1 (en) * 2017-09-18 2020-07-29 Basf Se Additive mixture

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080193496A1 (en) * 2005-03-21 2008-08-14 The Cupron Corporation Antimicrobial And Antiviral Polymeric Master Batch, Processes For Producing Polymeric Material Therefrom And Products Produced Therefrom
CN101054740A (en) * 2007-05-22 2007-10-17 杭州师范大学 Low temperature producing method for nylon fiber
CN101139749A (en) * 2007-07-13 2008-03-12 杭州师范大学 Fine denier or ultra-fine denier nylon fibre and production method thereof
CN104206418A (en) * 2014-08-07 2014-12-17 蔡惠萍 Preparation method and application of discoloration-preventing powdery silver-containing anti-bacterial agent
CN104592629A (en) * 2015-01-05 2015-05-06 上海纳旭实业有限公司 Preparation method of Cu/ZnO composite antibacterial PP masterbatch
CN112004879A (en) * 2018-05-03 2020-11-27 瑞士新集团有限公司 Antidegradant blends

Also Published As

Publication number Publication date
TWI817565B (en) 2023-10-01
TW202300577A (en) 2023-01-01

Similar Documents

Publication Publication Date Title
Shaheen et al. Durable antibacterial and UV protections of in situ synthesized zinc oxide nanoparticles onto cotton fabrics
Khan et al. A study on the influence of metal (Fe, Bi, and Ag) doping on structural, optical, and antimicrobial activity of ZnO nanostructures
EP2032661B1 (en) Pigment and polymeric materials matted therewith
TWI424960B (en) A hydrotalcite-based compound particle, a resin stabilizer using the same, a halogen-containing resin composition, and an anion-capturing material using the same
JP5136519B2 (en) Titanium dioxide particles and production method thereof
JP2008159495A (en) Positive electrode active material for lithium ion secondary battery and manufacturing method thereof
JP2004299931A (en) Mg-Zn-Al-BASED HYDROTALCITE TYPE PARTICLE POWDER AND RESIN COMPOSITION USING Mg-Zn-Al-BASED HYDROTALCITE TYPE PARTICLE POWDER
AU2016329903B2 (en) Particle surface treatment
WO2022268122A1 (en) Organic-inorganic mixture for preventing copper or silver oxidation, manufacturing method therefor, and application thereof
KR100939633B1 (en) Method for manufacturing artificial nail having antimicrobial and colorless function with nano metal particles treated
JP2021527752A (en) Highly added magnesium oxide treated titanium dioxide pigments, methods of their production, and their use in paper production
JP2015086126A (en) Iron oxide particle powder, coating material and resin composition using the iron oxide particle powder
US20150225531A1 (en) Surface-treated titanium dioxide pigments
WO2008064750A2 (en) Antimicrobial resin materials and method of manufacturing the same
WO2023001076A1 (en) Antibacterial plastic cement masterbatch, preparation method therefor and use thereof
JP2007302798A (en) Cobalt-containing black pigment
JPH03258861A (en) Highly-dispersible titanium dioxide-based pigment
JP2001106530A (en) Iron oxide particle
Nazarzade et al. Synthesis of CuO/Epoxy nanocomposites for the preparation of antifungal coating
JP3511588B2 (en) Iron oxide particles and method for producing the same
CN114230943B (en) Antibacterial edge sealing strip and preparation method and application thereof
CN113881135B (en) Nano cuprous oxide antibacterial and mildewproof master batch, preparation method thereof, plastic product and preparation method thereof
JP6249313B2 (en) Method for producing plate-like α-alumina pearlescent pigment having a large aspect ratio and nanometal-coated pearlescent pigment
JP3641165B2 (en) Iron oxide particles
WO2002004350A1 (en) Particulate zeolite and use thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22827614

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22827614

Country of ref document: EP

Kind code of ref document: A1