EP4146732A1 - Matériau de modelage et procédé de production de ce dernier - Google Patents

Matériau de modelage et procédé de production de ce dernier

Info

Publication number
EP4146732A1
EP4146732A1 EP21720997.2A EP21720997A EP4146732A1 EP 4146732 A1 EP4146732 A1 EP 4146732A1 EP 21720997 A EP21720997 A EP 21720997A EP 4146732 A1 EP4146732 A1 EP 4146732A1
Authority
EP
European Patent Office
Prior art keywords
plasticizer
weight
adipate
composition according
citrate
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
EP21720997.2A
Other languages
German (de)
English (en)
Inventor
Denise Schneider
Sabina HERDEGEN
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 EP4146732A1 publication Critical patent/EP4146732A1/fr
Pending 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
    • C08J3/18—Plasticising macromolecular compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08J2327/00—Characterised 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
    • C08J2327/02—Characterised 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
    • C08J2327/04—Characterised 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
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the invention relates to an oven-hardenable modeling compound and a method for producing such modeling compounds.
  • Plastic, oven-hardenable compounds for shaping and modeling objects are known in principle.
  • Modeling compounds are also to be understood as meaning clays or, in the case of compounds containing polymers, polymer clays.
  • DE 2515757 C3 discloses a plastic, hand-deformable and hardenable mass.
  • Such a mass consists essentially of polyvinyl chloride (PVC), filler and phthalate-containing plasticizer.
  • 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 mixed.
  • 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 modeling or molding compound which does not have the disadvantages mentioned at the outset and in particular to minimize the aging process when storing PVC-containing modeling compounds in the uncured state and thus to ensure greater storage stability.
  • Another object of the invention is to increase the flexibility of the modeling compounds after oven hardening and, if necessary, to improve the transparency - up to and including glass clarity - of the hardened compound.
  • the oven-hardenable modeling compound according to the invention consists at least of a binder and a plasticizer, the binder being present as a plastisol, the plastisol being composed essentially of PVC and a plasticizer and, if necessary, further additives and / or additives.
  • the modeling compound can, for example, have at least one filler as a further additive and / or additive.
  • a mass that can be modeled is present when the content of plasticizer in the mixture is set in such a way that the plasticizer is deposited on the one hand on the surface of the PVC particles and on the other hand in the spaces between the solid particles in such a way that a kneadable resistance is achieved is trained. 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 knead.
  • 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 has a certain affinity for the PVC grain or PVC solid particles even when stored at room temperature and ensures that the PVC grain, which partly consists of agglomerates, disintegrates and thus creates 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 modeling clay increases, as the kneadability decreases due to the lack of liquid components of plasticizer in the interstices.
  • Another advantage of the increased proportion / content of plasticizer in the modeling clay is that the gelling ability in the system is improved during the hardening process, resulting in a higher elasticity after oven hardening. It has surprisingly been found that mixing at higher temperatures and the associated plasticizer contents and reducing the use of fillers and / or additives can significantly increase the transparency after oven curing.
  • 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 52% 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, bis (2-ethylhexyl) Diisononyl cyclohexanedicarboxylate, acetic acid ester of monoglycerides, benzoates or a mixture of at least two of these substances.
  • 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.
  • phthalate-containing plasticizers are di-2-ethylhexyl phthalate, ditrdecyl phthalates and dibutyl phthalate.
  • plasticizers consisting of phthalate-free and phthalate-containing plasticizers.
  • a stabilizer improves the PVC stability, i. H. he 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 / or 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.
  • Frame example 1 The invention is to be illustrated in more detail using a framework example and some recipe examples.
  • Frame example 1 The invention is to be illustrated in more detail using a framework example and some recipe examples.
  • Stabilizers are examples of other additives that may be used.
  • Formulation example 1 yellow-colored modeling clay 51% by weight E-PVC and S-PVC 42% by weight plasticizer based on ATBC 6% by weight stabilizer 0.5% by weight filler 0.5% by weight Pigment Yellow 83
  • Formulation example 2 modeling clay, transparent after hardening 48% by weight E-PVC and S-PVC 52% by weight plasticizer based on ATBC State of the art - comparative formulation according to DE 102005059143
  • 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.
  • the mixing process of the individual components in the mass takes place at an elevated temperature of around 55 to 70.degree. C., preferably around 58 to 65.degree.
  • agglomerate disintegration is initiated during the mixing process, as a result of which an increased content of plasticizer is or can be added to the solid phase of the PVC.
  • PVC powder and the amount of plasticizer with any other additives and / or additives are added to the mixing process at a Mixing temperature of about 55 to 70 ° C added.
  • binder 20-68% by weight binder, 32-60% by weight plasticizer, 0-40% by weight fillers and 0-20% by weight other additives
  • the preferred components of the mass in the process contain 40-68% by weight of binder,
  • compositions in the process contain 45-63% by weight of binder
  • composition according to the invention is used in the production of plastic, deformable by hand and hardenable by heating masses, as modeling masses for use by children and for the production of craft and / or industrial objects and the products made from them such.
  • the compound or modeling compound is also used for therapeutic purposes in the medical field, in order to train and rehabilitate haptic abilities.
  • Objects and objects which are produced with a composition according to the invention are cured by the action of heat after shaping for the design of the objects and objects.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un matériau de modelage durcissant au four, constitué au moins d'un liant et d'un assouplissant, le liant et l'assouplissant se présentant sous forme de plastisols, le plastisol étant constitué essentiellement de PVC et d'un assouplissant et la masse ayant une teneur globale en assouplissant de 32 à 60 % en poids.
EP21720997.2A 2020-05-05 2021-04-23 Matériau de modelage et procédé de production de ce dernier Pending EP4146732A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020002686.9A DE102020002686A1 (de) 2020-05-05 2020-05-05 Modelliermasse sowie Verfahren zu deren Herstellung
PCT/EP2021/025152 WO2021223908A1 (fr) 2020-05-05 2021-04-23 Matériau de modelage et procédé de production de ce dernier

Publications (1)

Publication Number Publication Date
EP4146732A1 true EP4146732A1 (fr) 2023-03-15

Family

ID=75659980

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21720997.2A Pending EP4146732A1 (fr) 2020-05-05 2021-04-23 Matériau de modelage et procédé de production de ce dernier

Country Status (10)

Country Link
US (1) US20230167249A1 (fr)
EP (1) EP4146732A1 (fr)
JP (1) JP2023524305A (fr)
KR (1) KR20230006559A (fr)
CN (1) CN115516019A (fr)
AU (1) AU2021267605B2 (fr)
CA (1) CA3175408A1 (fr)
DE (1) DE102020002686A1 (fr)
WO (1) WO2021223908A1 (fr)
ZA (1) ZA202211406B (fr)

Family Cites Families (9)

* 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
DE2515757C3 (de) 1975-04-10 1984-08-02 Eberhard Faber Gmbh, 8430 Neumarkt Verwendung plastischer Massen
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
CN101990560A (zh) * 2007-12-21 2011-03-23 埃克森美孚化学专利公司 助增塑剂体系
TW201605945A (zh) * 2014-07-08 2016-02-16 巴斯夫歐洲公司 包含二羧酸的酯及１，２－環己烷二羧酸的酯之模製化合物
DE102018007756B4 (de) * 2018-10-02 2022-07-07 Staedtler Mars Gmbh & Co. Kg Modelliermasse sowie deren Verwendung und damit hergestellte Gegenstände
EP3696225B1 (fr) * 2019-02-18 2021-11-10 Eftec Nv Composition de plastisol appropriée pour sceller des pièces métalliques

Also Published As

Publication number Publication date
KR20230006559A (ko) 2023-01-10
US20230167249A1 (en) 2023-06-01
AU2021267605A1 (en) 2022-11-17
CN115516019A (zh) 2022-12-23
AU2021267605B2 (en) 2024-03-14
ZA202211406B (en) 2024-02-28
DE102020002686A1 (de) 2021-11-11
CA3175408A1 (fr) 2021-11-11
WO2021223908A1 (fr) 2021-11-11
JP2023524305A (ja) 2023-06-09

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