EP4146726A1 - Procédé de production d'un composé à mouler - Google Patents

Procédé de production d'un composé à mouler

Info

Publication number
EP4146726A1
EP4146726A1 EP21722103.5A EP21722103A EP4146726A1 EP 4146726 A1 EP4146726 A1 EP 4146726A1 EP 21722103 A EP21722103 A EP 21722103A EP 4146726 A1 EP4146726 A1 EP 4146726A1
Authority
EP
European Patent Office
Prior art keywords
plasticizer
weight
citrate
adipyl
phthalate
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.)
Pending
Application number
EP21722103.5A
Other languages
German (de)
English (en)
Inventor
Denise Schneider
Mathias Belzner
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.)
Staedtler Se
Original Assignee
Staedtler Mars GmbH and Co KG
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 Staedtler Mars GmbH and Co KG filed Critical Staedtler Mars GmbH and Co KG
Publication of EP4146726A1 publication Critical patent/EP4146726A1/fr
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016Plasticisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/18Plasticising macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/203Solid polymers with solid and/or liquid additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/11Esters; Ether-esters of acyclic polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/12Esters; Ether-esters of cyclic polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06Homopolymers or copolymers of vinyl chloride

Definitions

  • the invention relates to a method for producing a molding compound.
  • Plastic molding compounds for designing objects and processes for their production are known in principle.
  • the design of objects can be done manually or by machine in industrial use.
  • Molding compounds are also to be understood as meaning so-called clays or, in the case of polymer-containing compounds, so-called polymer clays. Such molding compounds have an extremely wide range of uses in everyday life today.
  • molding compounds in the form of modeling compounds are selected from the prior art.
  • DE 2515757 C3 discloses a plastic, hand-deformable and hardenable mass.
  • Such a mass consists essentially of polyvinyl chloride (PVC), fillers and phthalate-containing plasticizers.
  • DE 102005059143 A1 also discloses modeling compounds which do not use phthalate-containing plasticizers.
  • the powdery raw materials are mixed with the plasticizer at temperatures between 20 and 30 ° C.
  • a plasticizer uptake of 25-30% by weight is achieved.
  • individual PVC agglomerates disintegrate, which in turn generates a need for plasticizers because the surface of the PVC grains has increased.
  • the object of the invention is therefore to create a method for producing a molding compound that does not have the disadvantages mentioned at the outset and, in particular, to minimize the aging process when storing PVC-containing molding compounds in the uncured state and thus to ensure greater storage stability represents a special consumer benefit.
  • the object can be achieved with the method according to the invention for producing a molding compound by subjecting the binder (PVC powder) and a quantity of plasticizer with possibly other additives and / or additives to a mixing process, the mixing process at a mixing temperature of 55 to 70 ° C. is preferred from 58 to 65 ° C.
  • the molding compound contains 20-68% by weight of binder as components
  • a preferred embodiment of the molding compound in the process contains 40-68% by weight of binder
  • a particularly preferred embodiment of the molding compound contains 45-63% by weight of binder
  • the molding compositions that are produced by the method according to the invention consist of binders, the binder being present as a plastisol, the plastisol being composed essentially of PVC and plasticizer and, if necessary, further additives and / or additives.
  • the molding compound can, for example, have at least one filler as a further additive and / or additive other deposits in the gaps between the solid particles that a "kneadable resistance" is formed. If the plasticizer content is too low, i.e. the plasticizer only accumulates on the surface of the solid particles without additionally being present in the interstices, the mass is too hard or very difficult to shape, regardless of whether the Molding compound takes place.
  • the resulting molding compound would flow too strongly and thus no longer be designed to be moldable in a controlled manner.
  • modeling compounds were used for the description in order to clearly illustrate the invention in relation to the prior art, which relates to modeling compounds.
  • heat In order to convert the shaped / modeled objects and objects into a permanently solid state, heat must be supplied.
  • oven hardening responsible for the hardening process is the plasticizer or the plasticizer content, which causes the compound to harden due to interactions with the PVC.
  • the plasticizer is already in storage Room temperature has a certain affinity for the PVC grain or PVC solid particles and ensures that the PVC grain, which partly consists of agglomerates, disintegrates and thus new surfaces / surface areas are generated. Through these newly created surfaces, the plasticizer, which was stored in the interstices, migrates to these newly created surfaces. As a result, the hardness of the molding compound increases, since the moldability decreases due to the lack of liquid components of plasticizer in the interstices.
  • the increased proportion / content of plasticizer in the molding compound has shown that the gelling ability in the system is improved in the hardening process and thus a higher elasticity results after hardening.
  • the binder used which is essentially in the form of PVC, and the added plasticizer form a plastisol.
  • the PVC can be present, inter alia, as an emulsifier-containing or emulsifier-free emulsion PVC, suspension PVC and microbead suspension PVC or a mixture of the individual PVC types. Phthalate-free and / or phthalate-containing plasticizers can be used as plasticizers.
  • the total content of plasticizer is between 32 and 60% by weight, in a preferred embodiment between 35 and 55% by weight and in a particularly preferred embodiment between 38 and 53% by weight.
  • the phthalate-free plasticizer is based on citric acid, adipic acid and / or benzoate ester.
  • the phthalate-free plasticizer is e.g. B. acetyl tributyl citrate, tri- (2-ethylhexyl) - actyl citrate, trioctyl citrate, tridecyl citrate, tributyl citrate, trihexyl citrate, triethyl citrate, dioctyl adipate, diisodecyl adipate, diisononyl adipate, diisononyl adipate, diisononyl adipate, ethyl acetate or benzoic acid hexylate, bis (2-ethylisonic acid, bis (2-ethyl isonate), bis (2-ethyl isoic acid), bis (2-ethyl isonylhexyl adipate, benzylhexyl acid ester, benzylhexylhexyl ester, benzylhexyl
  • the plasticizer can also belong to the group of benzoates or benzoate esters. Examples include its 2,2,4-triethyl-1,3-pentanediyl dibenzoate and derivatives thereof, triethylene glycol dibenzoate, diethylene glycol dibenzoate, diethylene glycol monobenzoate and / or propylene glycol dibenzoate. Any mixtures of all of the aforementioned plasticizers are possible.
  • di-2-ethylhexyl phthalate, ditrdecyl phthalate and dibutyl phthalate may be mentioned by way of example.
  • plasticizers consisting of phthalate-free and phthalate-containing plasticizers.
  • a preferred embodiment of the inventive method is the production of molding compositions which are free from phthalate-containing plasticizers.
  • a stabilizer improves the PVC stability, ie it prevents, among other things, the elimination of hydrogen chloride.
  • inorganic and organic salts of the metals calcium, zinc, tin, magnesium, sodium and potassium are used for this purpose, e.g. B. calcium stearate, sodium stearate, potassium stearate, Zinc stearate, magnesium stearate, tin stearate and / or mixtures of the metal salts.
  • the fillers used are essentially inorganic and organic fillers, e.g. B. kaolin, chalk, silica, talc, aluminum hydroxide and / or powdered clay, which have a grain size ⁇ 250 gm, preferably less than 100 gm.
  • Metal glitter, glitter powder and glitter flakes or mixtures of these substances can be present as further fillers in order to achieve special optical effects, for example.
  • Light fillers can also be used as fillers or other fillers mentioned can be added.
  • lightweight fillers are hollow spheres, in particular hollow glass microspheres, e.g. B. from 3M or Lehmann & Voss.
  • a desired density can be set, which is advantageously in the range from 0.3 to 1.1 g / ml.
  • the size of commercially available lightweight fillers can also be freely selected, their size preferably being in a range from 10 to 400 ⁇ m.
  • filler based on polymers can also be used.
  • examples of this group include PAMA, PMMA and / or polyethylene.
  • Pigments can be present as colorants in pure form, as powder pigments, preferably as azo-free color pigment, effect pigment and / or azo-free laked dye.
  • a selection of a large number of possible color pigments are Pigment Yellow 14 (Cl 21095), Pigment Red 254 (CI 56110), Pigment Orange 34 (Cl 21110), Pigment Red 122 (Cl 73915), Pigment Green 7 (Cl 74260), Pigment White 6 ( Cl 77891), Pigment Black 7 (Cl 77266), Pigment Red 101 (Cl 77491), Pigment Violet 23 (Cl 51319), Pigment Blue 29 (Cl 77007), Pigment Yellow 185 (Cl 56290), Pigment Yellow 1 (Cl11680) , Pigment Red 48: 2 (Cl 15865: 2), Pigment Red 53: 1 (Cl 15585: 1), Pigment Orange 34 (Cl 21115), Pigment Yellow 83 (Cl 21108) and Pigment Blue 15 (Cl 74160).
  • Pearlescent pigments mica iron metal luster pigments, polyester glitter pigments and luminescent pigments may be mentioned as further colorants.
  • differently colored molding compounds can also be mixed, mixed or kneaded with one another as required, thereby achieving a marbling effect.
  • the invention is to be illustrated in more detail with the aid of a framework example and some recipe examples with the aid of molding compounds.
  • Framework example 2 preferred composition 40-68% by weight of binder
  • Stabilizers, co-stabilizers, colorants and / or fillers are examples of other additives that may be used.
  • plasticizer based on ATBC 6% by weight stabilizer 0.5% by weight filler 0.5% by weight Pigment Yellow 83
  • Formulation example 2 Molding compound, transparent after hardening, 48% by weight E-PVC and S-PVC 52% by weight plasticizer based on ATBC
  • the phthalate-free plasticizer that is preferably used is based on citric acid and / or based on adipic acid.
  • a desired consistency of the mass can easily be adjusted by varying the binder content and / or plasticizer content.
  • Table 1 Increase in hardness of the uncured mass as a function of time at 40 ° C.
  • Molding compositions produced according to the invention are used in automobile construction, household items, medical equipment, toys and the food industry, as well as accessories for the aforementioned uses.
  • Articles and objects which have been formed with molding compositions produced according to the invention are made by after molding Hardened under the influence of heat.
  • the process for the production of molding compounds at least consisting of binder and plasticizer, the binder and the plasticizer being designed as plastisol, the plastisol being composed essentially of PVC and plasticizer, is carried out by adding the PVC powder and the amount of plasticizer possibly other additives and / or additives are subjected to a mixing process, the mixing process taking place at a mixing temperature of or between 55 and 70 ° C.

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)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne la production de composés à mouler, constitués au moins d'un liant et d'un assouplissant, le liant et l'assouplissant se présentant sous forme de plastisols, le plastisol étant essentiellement constitué de PVC et d'un assouplissant, caractérisé en ce que le procédé de production comprend les étapes suivantes : dans une première étape, mélange de la poudre de PVC et de la quantité d'assouplissant avec éventuellement d'autres mélanges et/ou additifs, et mise en œuvre de l'opération de mélange à une température de mélange d'environ 55 à 70 °C.
EP21722103.5A 2020-05-05 2021-04-23 Procédé de production d'un composé à mouler Pending EP4146726A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020002693.1A DE102020002693A1 (de) 2020-05-05 2020-05-05 Verfahren zur Herstellung einer Formmasse
PCT/EP2021/025151 WO2021223907A1 (fr) 2020-05-05 2021-04-23 Procédé de production d'un composé à mouler

Publications (1)

Publication Number Publication Date
EP4146726A1 true EP4146726A1 (fr) 2023-03-15

Family

ID=75728778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21722103.5A Pending EP4146726A1 (fr) 2020-05-05 2021-04-23 Procédé de production d'un composé à mouler

Country Status (10)

Country Link
US (1) US20230167250A1 (fr)
EP (1) EP4146726A1 (fr)
JP (1) JP2023524161A (fr)
KR (1) KR20230019106A (fr)
CN (1) CN115485323A (fr)
AU (1) AU2021266857B2 (fr)
CA (1) CA3176394A1 (fr)
DE (1) DE102020002693A1 (fr)
WO (1) WO2021223907A1 (fr)
ZA (1) ZA202211408B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020002686A1 (de) * 2020-05-05 2021-11-11 Staedtler Mars Gmbh & Co. Kg Modelliermasse sowie Verfahren zu deren Herstellung

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3700616A (en) * 1969-12-03 1972-10-24 Oneil Paul F Sculpturable molding compositions
DD88658A1 (fr) 1970-12-24 1972-03-12
DE2515757C3 (de) 1975-04-10 1984-08-02 Eberhard Faber Gmbh, 8430 Neumarkt Verwendung plastischer Massen
JPS57205436A (en) * 1981-06-09 1982-12-16 Kanegafuchi Chem Ind Co Ltd Polyvinyl chloride resin paste composition for hot- press molding
KR20010006471A (ko) 1997-04-18 2001-01-26 콘 게리 엠 주조 일체형 광-안정성 덮개를 갖는 자동차 내부의 장식용 외장품 및 제조 공정
DE19723467A1 (de) 1997-06-04 1998-12-10 Huels Troisdorf Verfahren zur Herstellung von Weich-PVC
DE102004056923A1 (de) * 2004-11-25 2006-06-01 J. S. Staedtler Gmbh & Co. Kg Verwendung einer fließfähigen Kunststoffmasse
DE102005059143A1 (de) 2005-12-08 2007-06-14 J. S. Staedtler Gmbh & Co. Kg Modelliermasse sowie deren Verwendung
JP5729552B2 (ja) * 2011-03-23 2015-06-03 日本ゼオン株式会社 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体
EP2907639A1 (fr) * 2014-02-13 2015-08-19 Sika Technology AG Procédé de fabrication de produits semi-finis en PVC plastifié
EP3170641B1 (fr) 2015-11-20 2019-09-25 SMP Deutschland GmbH Dispositif et procédé de fabrication d'une peau de cuisson tridimensionnelle thermoplastique
US20170253724A1 (en) 2016-03-07 2017-09-07 Exxonmobil Chemical Patents Inc. Plasticizers Production and Use
DE102018007756B4 (de) * 2018-10-02 2022-07-07 Staedtler Mars Gmbh & Co. Kg Modelliermasse sowie deren Verwendung und damit hergestellte Gegenstände

Also Published As

Publication number Publication date
CA3176394A1 (fr) 2021-11-11
AU2021266857B2 (en) 2024-08-01
DE102020002693A1 (de) 2021-11-11
ZA202211408B (en) 2024-02-28
AU2021266857A1 (en) 2022-11-17
JP2023524161A (ja) 2023-06-08
KR20230019106A (ko) 2023-02-07
WO2021223907A1 (fr) 2021-11-11
US20230167250A1 (en) 2023-06-01
CN115485323A (zh) 2022-12-16

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