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EP1654317A1 - Preparation de pigments destinee a des matieres plastiques - Google Patents

Preparation de pigments destinee a des matieres plastiques

Info

Publication number
EP1654317A1
EP1654317A1 EP04741081A EP04741081A EP1654317A1 EP 1654317 A1 EP1654317 A1 EP 1654317A1 EP 04741081 A EP04741081 A EP 04741081A EP 04741081 A EP04741081 A EP 04741081A EP 1654317 A1 EP1654317 A1 EP 1654317A1
Authority
EP
European Patent Office
Prior art keywords
pigment
pigment preparation
carrier material
copolymers
preparation according
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP04741081A
Other languages
German (de)
English (en)
Inventor
Manfred Kieser
Emil F. Aust
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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 Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1654317A1 publication Critical patent/EP1654317A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints

Definitions

  • the present invention relates to pigment preparations for pigmenting plastics, characterized in that one or more platelet-shaped effect pigments with an at least partially polar
  • US Pat. No. 6,451,102 proposes the coating of pearlescent pigments with waxes, preferably with polyethylene wax.
  • the pearlescent pigments coated with these waxes show good flow behavior and can be used to produce masterbatches.
  • pearlescent pigments coated with polyethylene wax are only suitable for incorporation into non-polar plastics, e.g. Polyolefins are suitable. This also applies to the masterbatches described there. With these coated pearlescent pigments, polar plastics are difficult to pigment.
  • Width of the polar plastics covers easily.
  • the compatibility problems can also cause difficulties in masterbatch production itself. If, for example, the melt viscosity drops significantly during the transition from natural material to masterbatch, this can lead to a strand break during extrusion, which is extremely problematic for the manufacturer.
  • the invention therefore relates to a pigment preparation for pigmenting plastics, one or more platelet-shaped effect pigments being mixed with an at least partially polar carrier material.
  • the present invention furthermore relates to a process for producing the pigment preparation according to the invention, in which one or more platelet-shaped effect pigments are mixed with an at least partially polar carrier material under the influence of heat.
  • Pigment preparation for pigmenting plastics and for producing masterbatches is also the subject of this invention.
  • the pigment preparation according to the invention based on platelet-shaped effect pigments and an at least partially polar carrier material has proven to be particularly advantageous for incorporation into plastics, in particular for polar plastics. Due to the only partially polar character of the carrier material, an adaptation for incorporation into non-polar plastics can also be achieved. This variability cannot be achieved by pigment preparations from the prior art and is an essential advantage of the present invention. The user is thus given the opportunity to pigment several different plastics with only one pigment preparation according to the invention which has been selected accordingly.
  • the pigment preparations according to the invention are not dusty and very easy to pour, which reduces the outlay in terms of apparatus for their processing.
  • the throughput depending on the conditions, can be increased by at least a factor of 2-5 compared to the unprepared pigment.
  • masterbatches with an effect pigment content of up to 40% by weight, based on the masterbatch can be produced on a single-screw extruder using the pigment preparation according to the invention.
  • the at least partially polar carrier material can be a partially polar copolymer and / or a mixture of two or more waxes, at least one of the waxes being polar.
  • the partially polar carrier material is preferably a partially polar copolymer and / or a mixture of two polar waxes.
  • Copolymers are understood to be polymers which have arisen from more than one type of monomer.
  • bi-, tri- or quaterpolymers are also suitable alternating, statistical, gradient, block or graft copolymers.
  • copolymers which are at least partially polar are suitable, that is to say that at least one monomer of the copolymer is polar.
  • Suitable partially polar copolymers are, for example, copolymers and terpolymers with vinyl acetate, acrylate or acrylic acid comonomers, polyvinyl alcohol
  • Copolymers polyvinyl ether copolymers, polyvinyl pyrrolidone copolymers, polyethylene oxide copolymers, acrylonitrile copolymers, methyl methacrylate copolymers, polyacetai copolymers, but also polyamide copolymers and / or polyurethane copolymers.
  • copolymers that can be used are ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers or ethylene-vinyl alcohol copolymers.
  • Suitable waxes for the mixture of two or more waxes are all waxes known to the person skilled in the art, which can be natural, chemically modified or synthetic waxes.
  • At least one of the waxes in a mixture of two or more waxes is polar. It is preferably a mixture of two polar waxes, e.g. Montan waxes and their derivatives as well as amide waxes, which can also have a non-polar portion, e.g. Components with alkyl chains, but are polar overall.
  • two polar waxes e.g. Montan waxes and their derivatives as well as amide waxes
  • amide waxes which can also have a non-polar portion, e.g. Components with alkyl chains, but are polar overall.
  • partially polar copolymers are used as the carrier material.
  • Preferred copolymers are, in particular, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers.
  • Mixtures of montan waxes and their derivatives with amide waxes are also particularly preferred as the carrier material, the ratio of montan waxes to amide waxes being 2: 1 to 1: 2, in particular the ratio being 1: 1.
  • the platelet-shaped effect pigments and the partially polar carrier material are mixed together.
  • the platelet-shaped Effect pigment at least partially or completely coated or coated by the carrier material.
  • a complete coating and "gluing" of the flaky effect pigment with the carrier material is very particularly preferred.
  • the melting range of the at least partially polar carrier material should be between 70 and 200 ° C., preferably between 80 and 160 ° C. and very particularly preferably between 90 and 140 ° C.
  • the platelet-shaped effect pigments in the present invention can be pearlescent pigments, metallic effect pigments, multilayer pigments with transparent, semitransparent and / or opaque layers, holographic pigments, BiOCI and / or LCP pigments.
  • Pearlescent pigments, metallic effect pigments or multilayer pigments with transparent, semitransparent and / or opaque layers that can be used according to the present invention are based in particular on carriers, which is preferably platelet-shaped.
  • carriers which is preferably platelet-shaped.
  • platelet-shaped TiO 2 synthetic or natural, are suitable
  • the metal platelets can consist of aluminum, titanium, bronze, steel or silver, preferably aluminum and / or titanium.
  • the metal platelets can be passivated by appropriate treatment. In a preferred one
  • the carrier can be coated with one or more transparent semitransparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
  • Metal nitride, metal oxynitride layers or the mixtures thereof can be low (refractive index ⁇ 1.8) or high refractive index (refractive index> 1.8).
  • Metal oxides and metal oxide hydrates are all metal oxides or metal oxide hydrates known to the person skilled in the art, such as, for.
  • the titanium suboxides can be used as metal suboxides.
  • metals for example, chromium, aluminum, nickel, silver, gold, titanium, copper or alloys are suitable as metals, for example magnesium fluoride is suitable as metal fluoride.
  • the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used as metal nitrides or metal oxynitrides.
  • Metal oxide, metal, metal fluoride and / or metal oxide hydrate layers are preferably applied and very particularly preferably metal oxide and / or metal oxide hydrate layers are applied to the carrier.
  • multilayer structures made of high and low refractive metal oxide, metal oxide hydrate, metal or metal fluoride layers can also be present, with high and low refractive layers alternating.
  • Layer packages consisting of a high and a low refractive index layer are particularly preferred, it being possible for one or more of these layer packages to be applied to the support.
  • the order of the high and low refractive index layers can be adapted to the carrier in order to include the carrier in the multilayer structure.
  • the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers can be mixed or doped with colorants or other elements.
  • Suitable colorants or other elements are, for example, organic or inorganic color pigments such as colored metal oxides, for example magnetite, chromium oxide or color pigments such as Berlin blue, ultramarine, bismuth vanadate, thenards blue, or else organic color pigments such as indigo, azo pigments, phthalocyanines or carmine red or
  • the outer layer on the carrier is a high-index metal oxide.
  • This outer layer can additionally be part of a layer package on the above-mentioned layer packages or in the case of high-index supports and, for example, of Ti0 2 , titanium suboxides, Fe 2 0 3) Sn0 2 , ZnO, Zr0 2 , Ce 2 0 3 , CoO, Co 3 0 4 > V 2 0 5 , Cr 2 0 3 and / or mixtures thereof, such as, for example, llmenite or pseudobrookite. Ti0 2 is particularly preferred.
  • the thickness of the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers or a mixture thereof is usually 3 to 300 nm and in the case of the metal oxide, metal oxide hydrate, metal suboxide, metal fluoride, metal nitride , Metal oxynitride layers or a mixture thereof, preferably 20 to 200 nm.
  • the thickness of the metal layers is preferably 4 to 50 nm.
  • Platelet-shaped supports coated with metal fluoride generally have a thickness between 0.05 and 5 ⁇ m, in particular between 0.1 and 4.5 ⁇ m.
  • the extension in length or width is usually between 1 and 250 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 2 and 100 ⁇ m.
  • the proportion of the platelet-shaped effect pigments in the pigment preparation according to the invention is generally between 60 and 85% by weight, preferably between 65 and 75% by weight, based on the pigment preparation. The optimum proportions are easy to determine for the person skilled in the art and essentially depend on the particle size of the effect pigments used, the shape factor of the effect pigments and the type of pigment structure.
  • the particles not only have to be coated with the carrier material, they also have to be glued to one another to form a free-flowing, coarse “powder”.
  • the pigment preparation can contain further additives and / or auxiliary substances, as are customary for use in plastics.
  • additives and / or auxiliaries can be lubricants, release agents, stabilizers, antistatic agents, flame retardants, colorants, flexibilizers and plasticizers, adhesion promoters, blowing agents, antioxidants, UV absorbers, organic polymer-compatible solvents and / or surfactants, such as, for example, diisoocytphthalate, phenol derivatives, mineral oils.
  • surfactants such as, for example, diisoocytphthalate, phenol derivatives, mineral oils.
  • the pigment preparation according to the invention can be easily produced.
  • the present invention therefore also relates to Process for the preparation of the pigment preparation according to the invention, wherein one or more platelet-shaped effect pigments are mixed with an at least partially polar carrier material under the influence of heat.
  • the platelet-like effect pigments that can be used or the partially polar carrier material have already been mentioned in advance in the description of the pigment preparation.
  • the effect pigment is presented and mixed with the carrier material or the solution of the carrier material. If the carrier material is added in the form of a solution, the effect pigment can also be dispersed in this solution and the solvent can be evaporated off.
  • the choice of the solvent is made in an obvious manner, taking into account the solubilities of the pigments used and in particular the one used
  • the carrier material can precipitate out of an aqueous dispersion by changing the pH.
  • the pigment preparation can furthermore be produced by melting the carrier material. Melting of the carrier material is particularly preferred in the present invention because it can avoid the use of solvents.
  • the pigment preparation according to the invention is produced by melting at temperatures of 70 to 240 ° C.
  • the process is preferably carried out at temperatures above the melting point of the carrier material. In this way, particularly good mixing of pigment and carrier material is achieved.
  • the pigment preparation After removal of the solvent or after cooling of the carrier material applied during melting, the pigment preparation is in the form of a free-flowing, coarse-particle powder which can be easily processed further.
  • the pigment preparation according to the invention is incorporated directly into the plastic by mixing the plastic granulate and / or powder with the pigment preparation.
  • the plastic pigmented with the pigment preparation according to the invention is then deformed under the action of heat.
  • further additives and pigments can optionally be added to the plastic granulate and / or powder when the pigment preparation is incorporated. Examples of such additives are described in advance in the description of
  • Pigment preparation has been called. All inorganic or organic pigments known to the person skilled in the art are suitable as pigments.
  • the plastic granulate and / or powder / pigment mixture is generally produced in such a way that in a suitable mixer, e.g. Tumble or high-speed mixer, the plastic granulate and / or powder presented, wetted with any additives and then the pigment preparation is added and mixed.
  • a suitable mixer e.g. Tumble or high-speed mixer
  • thermoplastics are suitable for the use of the pigment preparation according to the invention.
  • the plastics are preferably polar Plastics, but non-polar (olefinic) plastics can also be used with appropriately selected carrier materials. Examples of suitable plastics can be found, for example, in Saechtling, Kunststoff Taschenbuch, 27th edition, Carl Hanser Verlag.
  • the pigment preparation according to the invention can also be used advantageously for the production of masterbatches. In this way, the highest requirements for pigment dispersion can be met.
  • the masterbatches can be produced continuously or batchwise, preferably continuously, e.g. by using twin screw extruders.
  • the use of powders or semolina of the respective plastics is advantageous in the production of masterbatches.
  • the throughput depending on the conditions, can be increased by at least a factor of 2-5 compared to the unprepared pigment.
  • masterbatches with a pigment content of up to 40% by weight, based on the masterbatch can be produced on a single-screw extruder using the pigment preparation according to the invention.
  • the pigment preparation according to the invention is preferably used for the production of masterbatches.
  • both polar and non-polar plastics are suitable as a masterbatch basis.
  • graft copolymers which can be used as carrier material in effect pigment preparations according to the invention both in polar and in nonpolar (olefinic) plastics.
  • ethylene-acrylic acid copolymers are suitable for use in polar as well as for use in non-polar plastics.
  • a homogeneous mixture of 15 wt .-% of a Montanesterwachses (Hostalub ® WE 40, Clariant AG) and 15 wt .-% of an amide wax (Hostalub ® FA 1, Clariant AG) is mixed with 70 wt .-% Iriodin ® Brilliant Pearl at a Temperature of approx. 150 ° C in a mixer until uniform distribution and combination of pigment and carrier material mixed.
  • the percentages by weight relate to the total mixture.
  • the pigment preparation obtained no longer dustes, trickles well and can be processed on a single-screw extruder to masterbatches with up to about 40% by weight of pigment, based on the total amount.
  • the throughput with this preparation can be increased by at least a factor of 2-5 on a twin-screw extruder with the same proportion of pigments (compared to the unprepared pigment).
  • the preparation can be easily incorporated into various polar plastics (PA, PC, PMMA, PS, ABS, etc.).
  • AC 400 A Low molecular weight ethylene vinyl acetate copolymer
  • Iriodin ® Brilliant Pearl 70% by weight of Iriodin ® Brilliant Pearl at a temperature of approx.
  • the pigment preparation obtained no longer dustes, trickles well and can be made into masterbatches of up to approx. 40 on a single-screw extruder Process% by weight of pigment, based on the total amount.
  • the throughput with this preparation can be increased by at least a factor of 2-5 on a twin-screw extruder with the same proportion of pigments (compared to the unprepared pigment).
  • the preparation can be easily incorporated into various polar plastics (PA, PC, PMMA, PS, ABS, etc.).
  • Example 3 A homogeneous mixture of 20 wt .-% of a low molecular weight ethylene vinyl acetate copolymer (AC 400 A, Honeywell Allied Signal) are mixed with 80 wt .-% Iriodin ® Red 504 at a temperature of about 150 ° C in a mixer until mixed for even distribution and combination of pigment and carrier material. The percentages by weight relate to the total mixture.
  • the pigment preparation obtained no longer dustes, trickles well and can be processed on a single-screw extruder to masterbatches with up to about 40% by weight of pigment, based on the total amount.
  • the throughput with this preparation can be increased by at least a factor of 2-5 on a twin-screw extruder with the same proportion of pigments (compared to the unprepared pigment).
  • the preparation can be easily incorporated into various polar plastics (PA, PC, PMMA, PS, ABS, etc.).
  • the percentages by weight relate to the total mixture.
  • the pigment preparation obtained no longer dustes, trickles well and can be processed on a single-screw extruder to masterbatches with up to about 40% by weight of pigment, based on the total amount.
  • the throughput with this preparation can be increased by at least a factor of 2-5 on a twin-screw extruder with the same proportion of pigments (compared to the unprepared pigment).
  • the preparation can be easily incorporated into various polar plastics (PA, PC, PMMA, PS, ABS etc.) as well as into non-polar (olefinic) plastics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne des préparations de pigments destinées à la pigmentation de matières plastiques. L'invention est caractérisée en ce qu'au moins un pigment à effet en forme de plaquettes est mélangé à au moins une matière support partiellement polaire. L'invention concerne un procédé de production de ces préparations de pigments et leur utilisation pour la pigmentation de matières plastiques ainsi que la production de mélanges maîtres.
EP04741081A 2003-08-13 2004-07-16 Preparation de pigments destinee a des matieres plastiques Withdrawn EP1654317A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10337188A DE10337188A1 (de) 2003-08-13 2003-08-13 Pigmentpräparation für Kunststoffe
PCT/EP2004/007937 WO2005019327A1 (fr) 2003-08-13 2004-07-16 Preparation de pigments destinee a des matieres plastiques

Publications (1)

Publication Number Publication Date
EP1654317A1 true EP1654317A1 (fr) 2006-05-10

Family

ID=34177513

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04741081A Withdrawn EP1654317A1 (fr) 2003-08-13 2004-07-16 Preparation de pigments destinee a des matieres plastiques

Country Status (12)

Country Link
US (1) US20060223932A1 (fr)
EP (1) EP1654317A1 (fr)
JP (1) JP2007501880A (fr)
KR (1) KR20060056986A (fr)
CN (1) CN1836001A (fr)
AR (1) AR045453A1 (fr)
AU (1) AU2004267177A1 (fr)
BR (1) BRPI0413516A (fr)
DE (1) DE10337188A1 (fr)
RU (1) RU2355717C2 (fr)
TW (1) TW200514808A (fr)
WO (1) WO2005019327A1 (fr)

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DE102004051104A1 (de) * 2004-10-19 2006-04-27 Merck Patent Gmbh Opake Kunststoffe
GB0625890D0 (en) * 2006-12-23 2007-02-07 Colormatrix Holdings Inc Polymeric materials
DE102008020442A1 (de) 2008-04-23 2009-10-29 Merck Patent Gmbh Pigmentpräparationen
ITTO20080348A1 (it) * 2008-05-12 2009-11-13 Biopaint S R L Nuovi agenti antiadesione microbica ecologicamente compatibili per vernici antivegetative
DE102008064202A1 (de) 2008-12-22 2010-06-24 Merck Patent Gmbh Pigmentgranulate
DE102008064201A1 (de) 2008-12-22 2010-06-24 Merck Patent Gmbh Pigmentgranulate
RU2590541C2 (ru) * 2010-09-15 2016-07-10 Мерк Патент Гмбх Пигментные гранулы
KR101474802B1 (ko) 2011-12-30 2014-12-22 제일모직 주식회사 열가소성 수지 조성물
DE102012102165A1 (de) * 2012-03-14 2013-10-02 Eckart Gmbh Kompositpartikel, Verfahren zu deren Herstellung und Verwendung derselben
US9732211B2 (en) 2013-10-30 2017-08-15 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition having improved weather resistance
IT201600109323A1 (it) * 2016-10-28 2018-04-28 Giovanni Broggi Preparazioni pigmentarie universali per colorare e rinforzare materie plastiche
CN106380936A (zh) * 2016-11-04 2017-02-08 南平博士达节能科技有限公司 合成革涂饰剂用水性纳米色浆及其制备方法
CN109503922B (zh) * 2018-11-19 2021-11-19 深圳免喷材料科技有限公司 一种颜料功能母粒的制备方法及其产品和应用
US20220153997A1 (en) * 2019-04-11 2022-05-19 Basf Se Yellow pigment composition
CN111925676A (zh) * 2020-08-04 2020-11-13 浙江晋椿精密工业股份有限公司 一种散钉着色配合溶液及散钉着色方法
CN114702790B (zh) * 2022-03-15 2024-03-15 金发科技股份有限公司 一种颜色均匀稳定可控的有色塑料复合材料及其制备方法和应用
KR20240061156A (ko) 2022-10-31 2024-05-08 장성현 정수기의 분리형 필터캡

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Also Published As

Publication number Publication date
TW200514808A (en) 2005-05-01
WO2005019327A1 (fr) 2005-03-03
JP2007501880A (ja) 2007-02-01
BRPI0413516A (pt) 2006-10-10
RU2355717C2 (ru) 2009-05-20
US20060223932A1 (en) 2006-10-05
RU2006107449A (ru) 2007-09-20
CN1836001A (zh) 2006-09-20
KR20060056986A (ko) 2006-05-25
DE10337188A1 (de) 2005-03-10
AU2004267177A1 (en) 2005-03-03
AR045453A1 (es) 2005-10-26

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