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WO1996002466A1 - Composes stratifies reticulaires et stabilisateurs les contenant pour masses polymeres halogenees - Google Patents

Composes stratifies reticulaires et stabilisateurs les contenant pour masses polymeres halogenees Download PDF

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Publication number
WO1996002466A1
WO1996002466A1 PCT/EP1995/002716 EP9502716W WO9602466A1 WO 1996002466 A1 WO1996002466 A1 WO 1996002466A1 EP 9502716 W EP9502716 W EP 9502716W WO 9602466 A1 WO9602466 A1 WO 9602466A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
hydroxides
hydrogen
phosphite
acid
Prior art date
Application number
PCT/EP1995/002716
Other languages
German (de)
English (en)
Inventor
Michael Schiller
Paul Ebner
Klaus Dolleschal
Karoline Pacher
Christina Summerer
Original Assignee
Metallgesellschaft Aktiengesellschaft
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 Metallgesellschaft Aktiengesellschaft filed Critical Metallgesellschaft Aktiengesellschaft
Priority to BR9508284A priority Critical patent/BR9508284A/pt
Priority to EP95926855A priority patent/EP0771311A1/fr
Priority to JP8504681A priority patent/JPH10508281A/ja
Priority to AU31093/95A priority patent/AU3109395A/en
Publication of WO1996002466A1 publication Critical patent/WO1996002466A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • C01B13/363—Mixtures of oxides or hydroxides by precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/006—Compounds containing tin, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing zinc, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type

Definitions

  • the invention relates to layered lattice compounds of the general formula a Me I, b . 2 .Me III 2 + i (OH) 4 + 2b A- 2 / I1 * mH 2 O (I) wherein
  • Me Mg, Ca, Zn and / or Sn 2+ Me 1 " Al and / or Fe 3+
  • a n ' is an anion of the valence n or a mixture of anions and the
  • the invention further relates to a method for producing the layered grid connections and stabilizers for halogen-containing polymer compositions containing the layered grid connections.
  • a halogen-containing thermoplastic polymer e.g. Polyvinyl chloride (PVC) changes into a polyene structure when melt deformation is carried out, hydrochloric acid being eliminated and the polymer discolored.
  • PVC Polyvinyl chloride
  • metal carboxylates as stabilizers into the polymer mass.
  • metal burning which causes the polymer to blacken
  • a costabilizer e.g. Polyols (such as pentaerythritol)
  • ERSA ⁇ ZBLA ⁇ T add organic phosphorous acid esters (such as triphenyl phosphite), epoxy compounds (such as epoxidized soybean oil).
  • ERS ⁇ ZBL ⁇ T for halogen-containing polymers, especially PVC, proposed.
  • These substances are inferior to stabilizer mixtures with hydrotalcites in terms of their effect on the heat stability and the transparency of the polymer compositions stabilized thereby.
  • the use of such hydrate-containing substances can cause problems during incorporation into halogen-containing polymer compositions by the elimination of the water of crystallization (see M. Meyn "Double hydroxides and hydroxide double salt c - synthesis, properties and anion exchange behavior", dissertation, Kiel 1991.)
  • EP- A-0 256 872 is therefore proposed to remedy this disadvantage by adding very finely divided magnesium oxide.
  • the documents DE 41 03 916 and DE 41 06 403 disclose basic hydroxy compounds from divalent and trivalent metal ions which are defined as "not of the hydrotalcite type", i.a. for use as PVC stabilizers. These substances are also inferior in their stabilizing action to mixtures with hydrotalcites in terms of heat stability and the transparency of the products stabilized with them. Furthermore, problems of incorporation into halogen-containing polymer compositions can also arise here when using such substances by dqs hydrate water due to the elimination of the water of crystallization.
  • the invention has for its object to provide new layered grid compounds and a process for their preparation, which are classified in particular as non-toxic and which are particularly suitable as stabilizers for halogen-containing polymers without having the disadvantages of the known stabilizers mentioned above.
  • this object is achieved by layered lattice compounds of the general formula
  • a n is a selected anion of valence n or a mixture of anions and the indices are in the range of
  • soluble lithium compounds which are used as stabilizers in halogen-containing polymer compositions, increase the water absorption capacity of these resins.
  • the insulating effect deteriorates and in pressurized water pipes, the load capacity due to the internal water pressure is reduced.
  • Lithium carbonate has no stabilizing effect, but lithium hydroxide has a good stabilizing effect, although the initial color and the color gradient are adversely affected.
  • Lilhium oxide shows similar stabilizer properties on halogen-containing polymer compositions such as lithium hydroxide, but here too the hydrophilicity is disadvantageous. Stabilizer mixtures containing lithium oxide are not stable on storage.
  • Lithium salts with fatty acids, in particular stearic acid are also known as PVC stabilizers.
  • Document DE-A-1 115 460 describes a combination of lithium stearate and glycerol mono- (acetylricinoleate) for use as a PVC stabilizer.
  • these stabilizers have no commercial importance.
  • a melting reaction of lithium stearate is difficult to do (melting point of lithium stearate: 200 to 215 ° C)
  • lithium salts such as e.g. the hydroxide or the chloride are needed, both of which
  • REPLACEMENT BLA ⁇ (RULE 26) are comparatively expensive.
  • stabilizers such as hydrated lime, magnesium and lithium hydroxide
  • the compounds according to the invention do not take up carbon dioxide from the air.
  • lithium hydroxide the products according to the invention are sparingly soluble.
  • hydrotalcites they have a significantly reduced hydrophilicity, which is reflected in a lower moisture absorption from the air.
  • the substances according to the invention give halogen-containing, thermoplastic polymer compositions and the parts produced therefrom a higher heat stability compared to hydrotalcites or hydrocalumites.
  • the substances according to the invention prevent discoloration in the production of e.g. Hard PVC extrudates. Both the color gradient and the weathering stability of the test specimens stabilized with the substances according to the invention are better than those test specimens which do not contain the substances according to the invention.
  • the transparency of transparent halogen-containing resins is not impaired by the use of the compounds according to the invention.
  • the invention further relates to a process for the preparation of the substances according to the invention, in particular layered grid compounds, which is characterized in that lithium hydroxide, oxide and / or its compounds which can be converted into hydroxide, metal (H) hydroxides, oxides and / or their compounds which can be converted into hydroxides of the metals mentioned and aluminum and / or iron (III) hydroxides and / or their compounds which can be converted into hydroxides and acids and / or their salts or mixtures thereof at a pH of 8 to 10 and reacted with one another at temperatures of 20 to 250 ° C. and the solid reaction product obtained is separated off.
  • layered grid compounds which is characterized in that lithium hydroxide, oxide and / or its compounds which can be converted into hydroxide, metal (H) hydroxides, oxides and / or their compounds which can be converted into hydroxides of the metals mentioned and aluminum and / or iron (III) hydroxides and / or their compounds which can be converted into hydroxides and acids and / or their
  • the reaction product obtained directly from the above-described reaction can be separated from the aqueous reaction medium by known processes, preferably by filtration.
  • the separated reaction product is also worked up in a manner known per se, for example by washing the filter cake with water and drying the washed residue at temperatures of, for example, 60 to 150 ° C., preferably 90 to 120 ° C.
  • both finely divided, active metal (III) hydroxide in combination with sodium hydroxide and NaAlO 2 can be used for the reaction.
  • Lithium or one of the metal (II) compounds mentioned can be used in the form of finely divided lithium oxide or hydroxide or mixtures thereof or of finely divided metal (II) oxide or hydroxide or mixtures thereof.
  • the corresponding acid anions can be used in differently concentrated form, for example directly as an acid or as a salt.
  • reaction temperatures are preferably between about 20 to 250 ° C, more particularly between about 60 and 180 ° C. No catalysts or accelerators are required.
  • the water of crystallization can be removed in whole or in part by thermal treatment.
  • the dried layered lattice compounds according to the invention split off no water or another gas at the processing temperatures of 160 to 200 ° C. customary for rigid PVC, so that no disruptive blistering occurs in the molds.
  • the anion in the general formula IA n ' can be sulfate, sulfite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrogen phosphate, hydrogen phosphite, carbonate, halides, nitrate, nitrite, hydrogen sulfate, hydrogen carbonate, hydrogen sulfite, hydrogen sulfide, dihydrogen phosphate, dihydrogen phosphate ions, and monohydrogen phosphate ions, such as monohydrogen phosphate ions Benzoate, amide, azide, hydroxide,
  • ERS ⁇ ZBL ⁇ T (RULE 26) Hydroxylamide. Hydrazide, acetylacetonate. Phenolate, pseudohalides, halogenites, halogenates, perhalogenates, I 3 " , permanganate, dianions of dicarboxylic acids such as phthalate, oxalate, maleate or fumarate, bisphenolatec, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of tricarboxylic acids such as citrate, trisphenolates and the like, and its be Among them, hydroxide, carbonate, phosphite and maleate are preferred.
  • a higher fatty acid e.g. Stearic acid, an anionic surfactant, a silane coupler, a titanate coupler, a glycerin fatty acid ester.
  • the substances of the formula I according to the invention are suitable as stabilizers for halogen-containing thermoplastic polymer compositions.
  • examples of such polymer compositions are PVC, polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated
  • Ethylene / vinyl acetate copolymer Ethylene / vinyl acetate copolymer.
  • the layered lattice compounds according to the invention are particularly suitable as stabilizers for polymer compositions of the PVC type, i.e. Vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
  • co-stabilizers can also advantageously be used, e.g. Metal carboxylates (group a).
  • 1,3-diketo compounds, organic esters of phosphorous acid, polyols and amino acid derivatives (group b) lead to a significant improvement in the initial color.
  • the addition of at least one substance (group c) selected from the group of the antioxidants and the epoxy compounds can lead to a significant improvement in the color gradient.
  • Examples of the metal carboxylates (group a) are the salts of higher fatty acids, naphthenic acid of metals of the second group of the periodic table of the elements.
  • suitable metals of the second group are magnesium, calcium, strontium, barium, zinc.
  • Such salts of higher fatty acids, such as stearic, palmitic, myristic, lauric, ricinoleic acid, are particularly advantageous.
  • Zinc salts are particularly effective for the color gradient. Therefore, at least part of a zinc salt of a higher fatty acid is preferably used.
  • the above metal carboxylates can be used individually, the effect can be increased by using two or more metal carboxylates.
  • 1,3-diketone compounds are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, myristoylbenzoylmethane, lauroybenzoylmethane, benzoylacetone, acetylacetone, tribenzoylmethane, diacetylacetobenzene, p-methoxysteaacetylacetoaceto-aceto-aceto-aceto-aceton-aceton-aceton-aceton-aceton-aceto-aceton-aceton-aceton-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceto-aceton-ac-aceto-aceton-ac-aceto-aceton-ac-aceto-aceton-ac-aceto-aceton-a
  • esters of phosphorous acid examples include triaryl phosphites such as triphenyl phosphite, tris (p-nonylphenyl) phosphite (TNPP); Alkylaryl phosphites such as monoalkyl diphenyl phosphites, e.g.
  • polyols examples include trismethylolpropane, di (trismethylolpropane), erythritol, pentaerythritol, dipentaerythritol, sorbitol, mannitol.
  • amino acid derivatives are glycine, alanine, lysine, tryptophan, acetylmethionine, pyrrolidonecarboxylic acid, ⁇ -aminocrotonic acid, ⁇ -aminoacrylic acid, ⁇ -aminoadipic acid and the corresponding esters.
  • the alcohol components of these esters include monohydric alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ⁇ -ethylhexanol, octyl alcohol, i-octyl alcohol, lauryl alcohol, stearyl alcohol, and also polyols, such as ethylene glycol, propylene glycol, 1, 3-butanediol, 1 , 4-Butanediol, Glycerol, Diglycerol, Trismelhylolpropane, Pentaerythritol, Dipentaerythritol, Erythrithol, Sorbitol, Mannitol.
  • monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ⁇ -ethylhexanol, octyl alcohol, i-oct
  • antioxidants examples include 2,5-di-tert-butyl-hydroquinone, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-tert .-Butyl-phenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), stearyl-3- (3 '-5' -di-tert-butyl-4'-hydroxyphenyl) propionate .
  • the epoxy compounds include various animal or vegetable oils, such as epoxy soybean oil, epoxy rapeseed oil, epoxidized fatty acid esters, such as epoxidized epoxymethyl oleate, epoxy butyl oleate, epoxidized alicyclic substances, glycidyl ethers, such as bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether; Glycid esters, such as glycidyl acrylate, glycidyl methacrylate, their polymers, copolymers; and epoxidized polymers such as epoxidized polybutadiene, epoxidized acrylic acid-butadiene-styrene terpolymer (ABS).
  • glycidyl ethers such as bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether
  • Glycid esters such as glycidyl acrylate, glycidyl meth
  • Preferred dosage amounts (in parts by weight per 100 parts by weight of resin) for the substances of the formula I according to the invention are 0.1 to 5, preferably 0.5 to 3.
  • Preferred dosage amounts for the co-stabilizers are:
  • halogen-containing thermoplastic polymer compositions stabilized according to the invention can furthermore contain the additives known to the person skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers.
  • additives known to the person skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers.
  • plasticizer is particularly common.
  • DOP dioctyl phthalate
  • aliphatic dibasic acid trimellitic acid
  • phosphate phosphate
  • fatty acid esters epoxy plasticizers
  • polyester plasticizers chlorinated paraffin and similar plasticizers
  • chlorinated paraffin chlorinated paraffin and similar plasticizers
  • Calendering, extrusion, injection molding, blow molding or other processes can be mentioned as shaping processes with which the halogen-containing thermoplastic polymer compositions stabilized according to the invention can be processed.
  • thermoplastic polymer compositions containing halogen is increased by adding the substances of the formula I according to the invention, in particular together with metal carboxylates (group a) and preferably also together with costabilizers (group b) or / and (group c) specified amounts significantly improved.
  • the polymer compositions stabilized according to the invention have no plate-out phenomenon during calendering and allow extrusion in long-term operation. In addition, the resulting products are free from discoloration.
  • the present invention is therefore a remarkable contribution to the processing of PVC and other halogen-containing thermoplastic polymer compositions.
  • the batch is filled up to a volume of three liters and pressure treated in a BUCHI laboratory autoclave for six hours at 10 bar and around 182 ° C.
  • the reaction product is filtered off and washed three times with two liters of water.
  • the filter cake is dried in vacuo at 130 ° C. for 14 hours. Crystal-clear crystals are obtained after the pressure treatment.
  • MTT MATHIS thermal oil test
  • VDE residual stability (Congo red value)
  • YI 0 yellowness index 0 min

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compounds Of Iron (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Des composés stratifiés réticulaires répondent à la formule générale (I) LiaMeIIb-2aMeIII2+a(OH)4+2bAn-2/n*mH2O, dans laquelle MeII désigne Mg, Ca, Zn et/ou Sn?2+; MeIII¿ désigne Al et/ou Fe3+; An- désigne un anion sélectionné de valence n ou un mélange d'anions; et les indices sont compris dans les plages suivantes: 0 < a < (b-2)/2, 1 < b < 6 et m = 0 à 5, à condition que b-2a > 2. L'invention concerne également un procédé de production de ces composés stratifiés réticulaires et des stabilisateurs contenant ces composés stratifiés réticulaires pour masses polymères halogénées.
PCT/EP1995/002716 1994-07-16 1995-07-12 Composes stratifies reticulaires et stabilisateurs les contenant pour masses polymeres halogenees WO1996002466A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9508284A BR9508284A (pt) 1994-07-16 1995-07-12 Compostos de grade em camada e estabilizadores contendo os mesmos para massas de polímeros halogenados
EP95926855A EP0771311A1 (fr) 1994-07-16 1995-07-12 Composes stratifies reticulaires et stabilisateurs les contenant pour masses polymeres halogenees
JP8504681A JPH10508281A (ja) 1994-07-16 1995-07-12 層状格子化合物と、この化合物を含むハロゲン含有ポリマー用安定剤
AU31093/95A AU3109395A (en) 1994-07-16 1995-07-12 Lattice layer compounds and halogenated polymer mass stabilisers containing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4425275A DE4425275A1 (de) 1994-07-16 1994-07-16 Schichtgitterverbindungen und diese enthaltende Stabilisatoren für halogenhaltige Polymermassen
DEP4425275.7 1994-07-16

Publications (1)

Publication Number Publication Date
WO1996002466A1 true WO1996002466A1 (fr) 1996-02-01

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PCT/EP1995/002716 WO1996002466A1 (fr) 1994-07-16 1995-07-12 Composes stratifies reticulaires et stabilisateurs les contenant pour masses polymeres halogenees

Country Status (7)

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EP (1) EP0771311A1 (fr)
JP (1) JPH10508281A (fr)
AU (1) AU3109395A (fr)
BR (1) BR9508284A (fr)
CA (1) CA2195245A1 (fr)
DE (1) DE4425275A1 (fr)
WO (1) WO1996002466A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761756A4 (fr) * 1995-03-10 1998-10-14 Fuji Chem Ind Co Ltd Stabilisateur pour resines contenant de l'halogene et son procede de preparation, composition de resine contenant de l'halogene et sel d'hydroxyde composite

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3534918B2 (ja) * 1995-11-22 2004-06-07 旭電化工業株式会社 安定化された塩素含有樹脂組成物
DE19617138A1 (de) * 1996-04-29 1997-11-06 Henkel Kgaa Kationische Schichtverbindungen, deren Herstellung und deren Verwendung als Stabilisatoren für halogenhaltige Kunststoffe
EP0947468A4 (fr) * 1996-10-16 2000-02-23 Fuji Chem Ind Co Ltd Nouveaux sels d'hydroxydes de metaux composites, stabilisant pour resines halogenees, et composition a base de resine halogenee
DE19753758A1 (de) 1997-12-04 1999-06-10 Henkel Kgaa Verfahren zur Herstellung kationischer Schichtverbindungen
ATE240365T1 (de) * 1998-01-16 2003-05-15 Crompton Vinyl Additives Gmbh Stabilisatorsystem für chlorhaltige polymere
JP4636587B2 (ja) * 2004-05-26 2011-02-23 日本化学工業株式会社 亜硝酸イオン型ハイドロタルサイト粉末、その製造方法、防錆剤組成物および防錆塗料組成物
JP5394380B2 (ja) * 2008-07-07 2014-01-22 協和化学工業株式会社 難燃性樹脂組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400431A (en) * 1980-09-04 1983-08-23 The Dow Chemical Company Magnesium aluminum spinels
EP0207811A2 (fr) * 1985-07-05 1987-01-07 The Dow Chemical Company Hydroxydes de métaux mixtes pour épaissir l'eau ou des fluides hydrophiles
WO1992015525A1 (fr) * 1991-02-28 1992-09-17 Bärlocher Gmbh Composes hydroxydes ayant une composition determinee, leur procede de production et leur utilisation
JPH06200103A (ja) * 1992-12-29 1994-07-19 Inoac Corp 塩化ビニル・ポリウレタン複合体及びこれに用いられる塩化ビニル系樹脂粉末組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400431A (en) * 1980-09-04 1983-08-23 The Dow Chemical Company Magnesium aluminum spinels
EP0207811A2 (fr) * 1985-07-05 1987-01-07 The Dow Chemical Company Hydroxydes de métaux mixtes pour épaissir l'eau ou des fluides hydrophiles
WO1992015525A1 (fr) * 1991-02-28 1992-09-17 Bärlocher Gmbh Composes hydroxydes ayant une composition determinee, leur procede de production et leur utilisation
JPH06200103A (ja) * 1992-12-29 1994-07-19 Inoac Corp 塩化ビニル・ポリウレタン複合体及びこれに用いられる塩化ビニル系樹脂粉末組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 94-269583 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761756A4 (fr) * 1995-03-10 1998-10-14 Fuji Chem Ind Co Ltd Stabilisateur pour resines contenant de l'halogene et son procede de preparation, composition de resine contenant de l'halogene et sel d'hydroxyde composite

Also Published As

Publication number Publication date
JPH10508281A (ja) 1998-08-18
BR9508284A (pt) 1998-05-19
CA2195245A1 (fr) 1996-02-01
AU3109395A (en) 1996-02-16
DE4425275A1 (de) 1996-01-18
EP0771311A1 (fr) 1997-05-07

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