EP1356005A1 - Siloxane separating agent for producing derived timber products - Google Patents

Siloxane separating agent for producing derived timber products

Info

Publication number
EP1356005A1
EP1356005A1 EP02704654A EP02704654A EP1356005A1 EP 1356005 A1 EP1356005 A1 EP 1356005A1 EP 02704654 A EP02704654 A EP 02704654A EP 02704654 A EP02704654 A EP 02704654A EP 1356005 A1 EP1356005 A1 EP 1356005A1
Authority
EP
European Patent Office
Prior art keywords
pressing
optionally
organopolysiloxane
mixture
polyisocyanate
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Withdrawn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
EP02704654A
Other languages
German (de)
French (fr)
Inventor
Theodore Frick
Ernst-Martin Hoppe
Donald-Richard Larimer
Andreas Pielasch
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.)
Covestro Deutschland AG
Original Assignee
Bayer AG
Bayer MaterialScience AG
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 Bayer AG, Bayer MaterialScience AG filed Critical Bayer AG
Publication of EP1356005A1 publication Critical patent/EP1356005A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/083—Agents for facilitating separation of moulds from articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • 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
    • C09D183/00—Coating 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
    • C09D183/04—Polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31989—Of wood

Definitions

  • Siloxane release agent for the manufacture of wood-based materials
  • the invention relates to a ner process for the production of wood-based materials by hot pressing of lignocellulose-containing materials glued with binder, in which a mixture of organosilicon compounds is applied to the surfaces of the pressing tool facing the material to be pressed.
  • polyisocyanates in particular polymeric diphenylmethane diisocyanate (pMDI) are mainly used as binders in the middle class. If pMDI is used in the top layer, problems arise when separating the wood material from the press tool or a disruptive layer of release agent and wood material residues builds up on the surfaces of the press tool, especially when working at higher press temperatures (EP-A 634 433, EP-A 1 038 898).
  • Aqueous emulsions of organopolysiloxane A), methylhydrogenpolysiloxane B), organopolysiloxane C), inhibitor D), emulsifiers and / or thickeners E) are preferably used. Additional components F) can be added to components A), B) and / or C) before the emulsification or after the emulsification. Suitable aggregates for achieving a particle size sufficient for the stability of the emulsion are e.g. High pressure homogenizers, colloid mills or similar
  • the release agents according to the invention can also be used in mixed binder systems (mixed gluing) made of pMDI and the aqueous solutions of condensation products of formaldehyde with urea and / or melamine and / or phenol which have been predominantly used in the wood-based panel industry.
  • a mixing ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, can be maintained without the separation effect of the separation system deteriorating.
  • the organopolysiloxane A) having at least 2 unsaturated hydrocarbon groups in the sense of the invention is preferably a cyclic, linear or branched polysiloxane, the units of the general formula
  • R 1 monovalent, saturated, optionally substituted hydrocarbon radicals having up to 10 carbon atoms from the group of substituted and unsubstituted alkyl, aryl and arylalkyl radicals, where a and b are integers within the following limits: 0 ⁇ a ⁇ 3 and 0 ⁇ b ⁇ 3 and 0 ⁇ a + b ⁇ 4 and each individual R or R 1 within the molecule can be the same or different.
  • R 1 examples are methyl, ethyl, propyl, isopropyl, butyl, octyl, etc., cyclobutyl, cyclopentyl, cyclohexyl, etc., phenyl, tolyl, xylyl, naphthyl, etc. benzyl, phenylethyl, phenylpropyl.
  • some or all of the hydrogen atoms alkyl, aryl and arylalkyl radicals R 1 are substituted by fluorine and / or chlorine, bromine or iodine atoms and / or cyano radicals.
  • R 1 corresponds, for example, to chloromethyl, trifiuoropropyl, chlorophenyl, dibromophenyl, ⁇ -cyanoethyl, ⁇ -cyanopropyl or ⁇ -cyanopropyl radicals.
  • at least 90% of the radicals R 1 are preferably methyl.
  • a is 0 or 1.
  • the molar proportion of unsaturated radicals of type R can be chosen as desired.
  • the molar proportion of unsaturated radicals of the type R should preferably be 0.01 to 10 mmol / g, particularly preferably 0.05 to 1 mmol / g and very particularly preferably 0.1 to 0.7 mmol / g Component A).
  • the viscosity of component A) at 25 ° C. is preferably 10 to 100,000 mPas, particularly preferably 50 to 10,000 mPas.
  • the organopolysiloxanes described in DE-A 43 28 657 are used as component A), since these are branched, the ratio of the number of diorganosiloxy units (D units) to the number of branching points is on average 15 and 40, at least a triorganosiloxy unit (M unit) and a maximum of half of all M units are free of unsaturated residues, the remaining M units each carry only one unsaturated residue, and the content of unsaturated residues is 0.1 to 1 mmol / g.
  • branching points of component A) are preferably monoorganosiloxy units, ie, trifunctional siloxy units (T units), but some of these can also be replaced by tetrafunctional siloxy units (SiO 4/2 units, Q units).
  • the end groups of the branched organopolysiloxane that are free of unsaturated residues perform the function of an internal plasticizer.
  • the flexibility of the crosslinked film can be controlled via the number of end groups (M units) free of unsaturated residues.
  • Examples of the preferred component A) are compounds of the formulas T 5 D 200 M vi 5 M 2 , T 7 D 28 oM Vi 5 M 4 , T 6 D 180 D vi 2 M vi 4 M 4 and or T 8 D 250 M vi 7 M 3 .
  • Branched, at least 2 unsaturated hydrocarbon groups containing organopolysiloxanes A) can be prepared by conventional methods, such as. B. by hydrolysis of chlorosilanes and subsequent polymerization with low molecular weight cyclic diorganopolysiloxanes.
  • the methylhydrogenpolysiloxane B) preferably contains units of the general formula
  • R 2 monovalent, saturated, optionally substituted hydrocarbon radicals having up to 10 carbon atoms from the group of substituted and unsubstituted alkyl, aryl, arylalkyl and / or C 2 -C 8 alkenyl radicals, where
  • c and d are integers with 0 ⁇ d ⁇ 3 and 0 ⁇ c ⁇ 2 and 0 ⁇ c + d ⁇ 4, preferably 0 ⁇ c ⁇ 1.
  • the methylhydrogenpolysiloxanes B) are preferably linear. At least half of the D units preferably have hydrogen atoms (H (CH 3 ) SiO groups) bonded directly to silicon. The number of groups having hydrogen atoms bonded directly to silicon is preferably between 70 and 85% of the difunctional units.
  • the molar proportion of hydrogen atoms directly bonded to a silicon atom in component B) can - in the context of the abovementioned. structural restrictions - can be chosen arbitrarily.
  • the molar proportion of hydrogen atoms bonded directly to a silicon atom is preferably 0.01 to 17 mmol, particularly preferably 0.1 to 17 mmol and very particularly preferably 1 to 17 mmol per gram of component B).
  • Components A) and B) are preferably present in a quantity ratio such that the molar ratio of hydrogen atoms (SiH) in component B) bonded directly to a silicon atom to the unsaturated radicals (Si-vinyl) in component A) is 0, 05 to 20, particularly preferably 0.5 to 10 and very particularly preferably 1 to 3.
  • the organopolysiloxane C) in the sense of the present invention is preferably a polysiloxane, the units of the general formula
  • R 1 are monovalent, saturated, optionally hydrocarbon radicals substituted with up to 10 carbon atoms from the group of substituted and unsubstituted alkyl, aryl and arylalkyl radicals which can be the same or different within the molecule and e are integers between 0 and 3 can accept.
  • Component C) is preferably a linear polydimethylsiloxane end-terminated with trimethylsiloxy groups, as is sold, for example, by Bayer AG under the name Baysilone oils M.
  • the use of such Baysilone ® oils M with a viscosity between 50 mmV 1 and 5000 mmV is particularly preferred.
  • the term inhibitor D) in the sense of the invention includes all inhibitors known according to the prior art, such as. B. maleic acid and its derivatives, amines, alkyl isocyanurates and acetylenically unsaturated alcohols, in which the OH group is bound to a carbon atom adjacent to the CC triple bond, as z. B. are described in more detail in US-A 3,445,420.
  • Component D) is preferably 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol and / or ( ⁇ ) 3-phenyl-1-butyn-3-ol.
  • the amount of component D) in the mixture is preferably 0.0001 to
  • Component E basically includes all emulsifiers and / or thickeners suitable for the formation and stabilization of emulsions (see e.g. Mc Cutcheon's Detergents
  • Emulsiliers International Edition.
  • the emulsions are used to produce release coatings for the production of wood-based materials used in the food sector, preference is given to those emulsifiers which are mentioned in FDA Regulations 176,170 "Components of Paper and Paperboard”.
  • Emulsifiers and thickeners are particularly preferred, which are mentioned in recommendation XV of the Federal Health Office (BGA) if the wood-based materials are intended for use in transport boxes for food or in truck bodies.
  • emulsifiers and thickeners E are: C 8 -C 22 -alkyldimethyl-benzylammonium chloride, preferably in an amount of at most 1.5% by weight, sodium lauryl sulfate, preferably in an amount of at most 0.5% by weight, Polyethylene glycol ethers of monohydric aliphatic alcohols C 2 -C 20 and C 2 -C 9 A1 alkyl phenols, polyethylene glycol esters of natural fatty acids C 8 -C 22 and vegetable oils, and / or partially acetylated polyvinyl alcohol with less than 20% acetyl groups and a K Value of over 40.
  • Emulsifiers falling under BGA recommendation XV are also carboxymethyl cellulose, digested starch, alginates, casein, hard paraffin and wax dispersions, dispersions based on copolymers of acrylic and methacrylic acid esters, butadiene and styrene, insofar as they comply with recommendation XIV and / or polyalcohol (viscosity of the 4% aqueous solution at 20 ° C at least 4 cP), according to recommendation XIV).
  • Polyvinyl alcohol in combination with sodium lauryl sulfate or alkyldimethylbenzylammonium chloride is particularly preferred.
  • Additives and auxiliary substances F) in the sense of the invention are e.g. B. polysiloxane resins, which are composed of building blocks of the general formulas (I) and (II), fillers, such as diatomaceous earths, finely divided quartz flours, amorphous silicas, pyrogenic and or precipitated silicas with a BET surface area of 50 to 500 m 2 / g , Such fillers can be surface-modified, for example by reaction with organosilicon compounds such as hexamethyldisilazane or 1,3-divinyl-1,3,1-tetramethyldisilazane. The use of fillers is particularly advantageous when the release agent is applied by rolling rather than spraying.
  • Additives and auxiliaries F) in the sense of the invention are also leveling agents which help improve the wetting of the substrate with the emulsion.
  • polyether siloxanes silicon surfactants and / or fluorosurfactants
  • Germ inhibitors e.g. formaldehyde-releasing products are also to be included in the additives and auxiliaries F).
  • the amount of component F) or the sum of components F) is preferably less than 5% by weight, based on the total mixture.
  • Aqueous emulsions with the following constituents are preferably used according to the invention: as component A): T 8 D 250 M vi 7 M 3 as methylhydrogenpolysiloxane B): M 2 D H 30 D ⁇ 0 as organopolysiloxane C): polydimethylsiloxane with a viscosity of 1000 mm 2 / s as inhibitor D): ethinylcyclohexanol as emulsifier and / or Thickener E): Polyvinyl alcohol, optionally in combination with sodium lauryl sulfate as additives and / or auxiliaries F): germ-inhibiting agents and or polyether siloxane
  • the wood-based materials are produced by hot pressing of lignocellulose-containing materials glued with binder containing polyisocyanate.
  • a release agent according to the invention is applied to the press plates or press belts on the surface facing the material to be pressed, for example with the aid of a spraying device or a roller application device.
  • the release agent according to the invention can be applied undiluted, ie generally as an emulsion with a water content of preferably 50 to 60% by weight, particularly preferably 55 to 60% by weight, but is preferred in a ratio of 1:50 diluted to 1: 100 with water. With suitable preconditioning of the press belts, higher dilutions are also possible, for example 1: 150 to 1: 250.
  • the water content in the release agents according to the invention is preferably 50 to 99.85% by weight, particularly preferably 55 to 99.85% by weight.
  • the release agent is then cured at a temperature of 150 ° C to 240 ° C, preferably 180 to 240 ° C.
  • a higher concentration of release agent undiluted to 1:50 in water
  • the release agent is preferably sprayed continuously onto the hot press plates or press belts. Examples
  • Release emulsion III corresponds to EP-A 819 735
  • Isocyanate IN pMDI with a ⁇ CO content of approx. 31.5% by weight (Desmodur ® 44V20 L, Bayer AG)
  • coating layer chips which consisted of a mixture of coniferous wood and deciduous wood and had a moisture content of about 15 wt .-%, were glued with 320 parts by weight of isocyanate IV (Desmodur ® 44V20 L).
  • a 300 x 300 mm size was created on a 2 mm thick steel press plate and covered with a second steel press plate.
  • the two press plates were previously pretreated with the release agent to be tested.
  • the separating emulsion was diluted to the specified dilution with water, sprayed onto the metal sheets in a cloister, and then flashed off at 140 ° C. for two minutes for curing. This process was repeated three times.
  • the molding was pressed at the specified pressing temperature for 100 seconds.
  • the separation behavior after each demoulding was recorded and evaluated as follows:
  • the separating emulsion I shows an excellent separating effect, which is retained even at higher pressing temperatures and does not form any deposits on the pressing tool.
  • Release emulsion II shows no sufficient release effect, neither at 190 ° C nor at 220 ° C.
  • Release emulsion I is effective after a single pretreatment of the sheets over several demolding processes, without the sheets having to be sprayed again after each removal. This offers the manufacturer a certain level of security in the event that the release agent spraying fails during production.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Forests & Forestry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a method for producing derived timber products by hot pressing materials containing lignocellulose and glued together by means of binding agents. According to the inventive method, a mixture of silicon-organic compounds is applied to the surfaces of the pressing tool, facing the material to be pressed.

Description

Siloxan-Trennmittel für die Holzwerkstoff-HerstellungSiloxane release agent for the manufacture of wood-based materials
Die Erfindung betrifft ein Nerfahren zur Herstellung von Holzwerkstoffen durch Heißverpressen von mit Bindemittel beleimten lignocellulosehaltigen Werkstoffen, bei dem auf die dem Pressgut zugewandten Oberflächen des Presswerkzeugs ein Gemisch siliciumorganischer Verbindungen aufgebracht wird.The invention relates to a ner process for the production of wood-based materials by hot pressing of lignocellulose-containing materials glued with binder, in which a mixture of organosilicon compounds is applied to the surfaces of the pressing tool facing the material to be pressed.
Bei der Herstellung von Holzwerkstoffen durch Heißveφressen von mit Bindemittel beleimten lignocellulosehaltigen Werkstoffen werden Polyisocyanate, insbesondere polymeres Diphenylmethandiisocyanat (pMDI), als Bindemittel hauptsächlich in der Mittelschicht angewendet. Wird pMDI in der Deckschicht eingesetzt, treten Probleme bei der Trennung des Holzwerkstoffs vom Presswerkzeug auf oder es baut sich auf den Oberflächen des Presswerkzeugs eine störende Schicht von Trennmittel- und Holzwerkstoff-Rückständen auf, insbesondere wenn bei höheren Presstemperaturen gearbeitet wird (EP-A 634 433, EP-A 1 038 898).In the production of wood-based materials by hot-pressing of lignocellulose-containing materials glued with binder, polyisocyanates, in particular polymeric diphenylmethane diisocyanate (pMDI), are mainly used as binders in the middle class. If pMDI is used in the top layer, problems arise when separating the wood material from the press tool or a disruptive layer of release agent and wood material residues builds up on the surfaces of the press tool, especially when working at higher press temperatures (EP-A 634 433, EP-A 1 038 898).
Es bestand daher ein Bedarf für ein Trennmittel, das für pMDI enthaltende Bindemittelsysteme geeignet ist, bei höheren Presstemperaturen eine ausreichende Trennwirkung zeigt, und auch über längere Produktionszeiten nur einen geringen Trennmittel- bzw. Holzwerkstoff-Rückstand auf dem Presswerkzeug verursacht.There was therefore a need for a release agent that is suitable for binder systems containing pMDI, shows a sufficient release effect at higher pressing temperatures, and also causes only a small release agent or wood-based material residue on the pressing tool even over longer production times.
Es wurde nun gefunden, dass sich durch Aushärten eines Gemisches von silicium- organischen Verbindungen ohne zusätzlichen Härtungskatalysator bei Presstemperaturen von 150°C bis 240°C auf den dem Pressgut zugewandten Oberflächen der Pressbleche oder Pressbänder eine diese Anforderungen erfüllende Trennschicht erzeugen lässt. Das zur Herstellung der Trennschicht eingesetzte Gemisch besteht aus:It has now been found that by curing a mixture of organosilicon compounds without an additional hardening catalyst at press temperatures of 150 ° C. to 240 ° C., a separating layer that meets these requirements can be produced on the surfaces of the press plates or press belts facing the material to be pressed. The mixture used to produce the separating layer consists of:
a) mindestens einem mindestens 2 ungesättigte Kohlenwasserstoffgruppen aufweisenden Organopolysiloxan A), b) mindestens einem Methylhydrogenpolysiloxan B), c) mindestens einem unreaktiven Organopolysiloxan C), d) gegebenenfalls einem Inhibitor D), e) gegebenenfalls Emulgatoren und/oder Verdickern E), f) gegebenenfalls Zusatz- und/oder Hilfsstoffen F), g) Wasser als Verdünnungsmittel.a) at least one organopolysiloxane A) having at least 2 unsaturated hydrocarbon groups, b) at least one methylhydrogenpolysiloxane B), c) at least one unreactive organopolysiloxane C), d) optionally an inhibitor D), e) optionally emulsifiers and / or thickeners E), f) optionally additives and / or auxiliaries F), g) water as a diluent.
Ähnliche Gemische, die jedoch stets noch Elemente der Platingruppe aufweisende Katalysatoren enthalten, wurden in EP-A 819 735 zur Beschichtung von Backpapieren vorgeschlagen.Similar mixtures, which however still contain elements of the platinum group, have been proposed in EP-A 819 735 for coating baking papers.
Bevorzugt werden wässrige Emulsionen aus Organopolysiloxan A), Methylhy- drogenpolysiloxan B), Organopolysiloxan C), Inhibitor D), Emulgatoren und/oder Verdickern E) eingesetzt. Zusätzliche Komponenten F) können den Komponenten A), B) und/oder C) vor der Emulgierung oder im Anschluss an die Emulgierung zugefügt werden. Geeignete Aggregate zum Erreichen einer für die Stabilität der Emulsion ausreichenden Teilchengröße sind z.B. Hochdruckhomogenisatoren, Kolloidmühlen o. ä.Aqueous emulsions of organopolysiloxane A), methylhydrogenpolysiloxane B), organopolysiloxane C), inhibitor D), emulsifiers and / or thickeners E) are preferably used. Additional components F) can be added to components A), B) and / or C) before the emulsification or after the emulsification. Suitable aggregates for achieving a particle size sufficient for the stability of the emulsion are e.g. High pressure homogenizers, colloid mills or similar
Die erfindungsgemäßen Trennmittel können auch in gemischten Bindersystemen (Mischverleimung) aus pMDI und den in der Holzwerkstoffindustrie bisher überwiegend eingesetzten wässrigen Lösungen von Kondensationsprodukten aus Formaldehyd mit Harnstoff und/oder Melamin und/oder Phenol eingesetzt werden. Ein Mischungsverhältnis von 1:10 bis 10:1, vorzugsweise 1:5 bis 5:1, kann eingehalten werden, ohne dass sich die Trennwirkung des Trennsystems verschlechtert.The release agents according to the invention can also be used in mixed binder systems (mixed gluing) made of pMDI and the aqueous solutions of condensation products of formaldehyde with urea and / or melamine and / or phenol which have been predominantly used in the wood-based panel industry. A mixing ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, can be maintained without the separation effect of the separation system deteriorating.
Das mindestens 2 ungesättigte Kohlenwasserstoffgruppen aufweisende Organopolysiloxan A) im Sinne der Erfindung ist vorzugsweise ein cyclisches, lineares oder verzweigtes Polysiloxan, das Einheiten der allgemeinen FormelThe organopolysiloxane A) having at least 2 unsaturated hydrocarbon groups in the sense of the invention is preferably a cyclic, linear or branched polysiloxane, the units of the general formula
(R)a(R1)bSiO(4.a.b)/2 (I)(R) a (R 1 ) b SiO (4. a . B) / 2 (I)
aufweist. mit R = C2-C8-Alkenyl und/oder ungesättigte C3-Cιo-Etherreste, wie Vinyl, Allyl, 1-Butenyl, 1-Hexenyl und/oder - CH2-CH2CH2OCH2CH = CH2 etc., bevorzugt Vinyl- oder Allyl, besonders bevorzugt Vinyl;having. with R = C 2 -C 8 alkenyl and / or unsaturated C 3 -Cιo ether residues, such as vinyl, allyl, 1-butenyl, 1-hexenyl and / or - CH 2 -CH 2 CH 2 OCH 2 CH = CH 2 etc., preferably vinyl or allyl, particularly preferably vinyl;
R1 = einwertige, gesättigte gegebenenfalls substituierte Kohlenwasserstoffreste mit bis zu 10 Kohlenstoffatomen aus der Gruppe der substituierten und unsubstituierten Alkyl-, Aryl-, und Arylalkylreste, wobei a und b ganze Zahlen in folgenden Grenzen sind: 0 < a < 3 bzw. 0 <b<3 und 0 <a + b<4 und jedes einzelne R bzw. R1 innerhalb der Moleküls gleich oder ungleich sein kann.R 1 = monovalent, saturated, optionally substituted hydrocarbon radicals having up to 10 carbon atoms from the group of substituted and unsubstituted alkyl, aryl and arylalkyl radicals, where a and b are integers within the following limits: 0 <a <3 and 0 < b <3 and 0 <a + b <4 and each individual R or R 1 within the molecule can be the same or different.
Beispiele für R1 sind Methyl, Ethyl, Propyl, Isopropyl, Butyl, Octyl, u.s.w., Cyclo- butyl, Cyclopentyl, Cyclohexyl, u.s.w., Phenyl, Tolyl, Xylyl, Naphtyl, u.s.w. Benzyl, Phenylethyl, Phenylpropyl. In einer Ausfuhrungsform der Erfindung sind einige oder alle der Wasserstoffatome Alkyl-, Aryl-, und Arylalkylradikale R1 durch Fluor- und/oder Chlor-, Brom-, bzw. Iodatome und/oder Cyanoradikale substituiert. In diesem Fall entspricht R1 beispielsweise Chlormethyl-, Trifiuoropropyl-, Chlorophenyl-, Dibromophenyl-, ß-Cyanoethyl, ß-Cyanopropyl oder γ-Cyanopropylresten. Bevorzugt sind jedoch mindestens 90 % der Reste R1 Methyl.Examples of R 1 are methyl, ethyl, propyl, isopropyl, butyl, octyl, etc., cyclobutyl, cyclopentyl, cyclohexyl, etc., phenyl, tolyl, xylyl, naphthyl, etc. benzyl, phenylethyl, phenylpropyl. In one embodiment of the invention, some or all of the hydrogen atoms alkyl, aryl and arylalkyl radicals R 1 are substituted by fluorine and / or chlorine, bromine or iodine atoms and / or cyano radicals. In this case, R 1 corresponds, for example, to chloromethyl, trifiuoropropyl, chlorophenyl, dibromophenyl, β-cyanoethyl, β-cyanopropyl or γ-cyanopropyl radicals. However, at least 90% of the radicals R 1 are preferably methyl.
In einer bevorzugten Ausführungsform der Erfindung ist a gleich 0 oder 1.In a preferred embodiment of the invention, a is 0 or 1.
Mit der dem Fachmann geläufigen Nomenklatur mitWith the nomenclature familiar to the expert with
M= (CH3)3Si 01/2,M = (CH 3 ) 3 Si 0 1/2 ,
D= (CH3)2SiO2/2,D = (CH 3 ) 2 SiO 2/2 ,
T= (CH3)SiO3/2,T = (CH 3 ) SiO 3/2 ,
Mvi= (CH2=CH)(CH3)2SiO, 2 undM vi = (CH 2 = CH) (CH 3 ) 2 SiO, 2 and
Dvi= (CH2=CH)(CH3)SiO2 2 lassen sich folgende Beispiele für die Komponente A) angeben: M2Dι00Dv'3, MV, 2D180, MviMD100Dvi 3, T5D550Mvi 7, T3D500Mvi 2M3 und/oder T6D300Dvi M4 Mvi 4.D vi = (CH 2 = CH) (CH 3 ) SiO 2 2 the following examples can be given for component A): M 2 Dι 00 D v ' 3 , M V, 2 D 180 , M vi MD 100 D vi 3 , T 5 D 550 M vi 7 , T 3 D 500 M vi 2 M 3 and / or T 6 D 300 D vi M 4 M vi 4 .
Der molare Anteil an ungesättigten Resten des Typs R kann beliebig gewählt werden.The molar proportion of unsaturated radicals of type R can be chosen as desired.
In der Komponente A) sollte bevorzugt der molare Anteil an ungesättigten Resten des Typs R 0,01 bis 10 mmol/g, besonders bevorzugt 0,05 bis 1 mmol/g und ganz besonders bevorzugt 0,1 bis 0,7 mmol/g der Komponente A) betragen. Die Viskosität der Komponente A) beträgt bei 25°C vorzugsweise 10 bis 100 000 mPas, besonders bevorzugt 50 bis 10 000 mPas.In component A) the molar proportion of unsaturated radicals of the type R should preferably be 0.01 to 10 mmol / g, particularly preferably 0.05 to 1 mmol / g and very particularly preferably 0.1 to 0.7 mmol / g Component A). The viscosity of component A) at 25 ° C. is preferably 10 to 100,000 mPas, particularly preferably 50 to 10,000 mPas.
In einer bevorzugten Ausfuhrungsform der Erfindung werden als Komponente A) die in DE-A 43 28 657 beschriebenen Organopolysiloxane eingesetzt, da diese verzweigt sind, das Verhältnis der Anzahl der Diorganosiloxyeinheiten (D-Einheiten) zur Anzahl der Verzweigungsstellen durchschnittlich 15 und 40 beträgt, mindestens eine Triorganosiloxyeinheit (M-Einheit) und maximal die Hälfte aller M-Einheiten von ungesättigten Resten frei sind, die restlichen M-Einheiten nur je einen ungesättigten Rest tragen, und der Gehalt an ungesättigten Resten 0,1 bis 1 mmol/g beträgt.In a preferred embodiment of the invention, the organopolysiloxanes described in DE-A 43 28 657 are used as component A), since these are branched, the ratio of the number of diorganosiloxy units (D units) to the number of branching points is on average 15 and 40, at least a triorganosiloxy unit (M unit) and a maximum of half of all M units are free of unsaturated residues, the remaining M units each carry only one unsaturated residue, and the content of unsaturated residues is 0.1 to 1 mmol / g.
Die Verzweigungsstellen der Komponente A) sind vorzugsweise Monoorganosiloxy- einheiten, d. h., trifunktionelle Siloxyeinheiten (T-Einheiten), die jedoch teilweise auch durch tetrafunktionelle Siloxyeinheiten (SiO4/2-Einheiten, Q-Einheiten) ersetzt sein können.The branching points of component A) are preferably monoorganosiloxy units, ie, trifunctional siloxy units (T units), but some of these can also be replaced by tetrafunctional siloxy units (SiO 4/2 units, Q units).
Die von ungesättigten Resten freien Endgruppen des verzweigten Organopoly- siloxans erfüllen die Funktion eines internen Weichmachers. Über die Anzahl der von ungesättigten Resten freien Endgruppen (M-Einheiten) kann die Flexibilität des vernetzten Films gesteuert werden.The end groups of the branched organopolysiloxane that are free of unsaturated residues perform the function of an internal plasticizer. The flexibility of the crosslinked film can be controlled via the number of end groups (M units) free of unsaturated residues.
Beispiele für die bevorzugte Komponente A) sind Verbindungen der Formeln T5D200Mvi 5M2, T7D28oMVi 5M4, T6D180Dvi 2Mvi 4M4 und oder T8D250Mvi 7M3. Nerzweigte, mindestens 2 ungesättigte Kohlenwasserstoffgruppen aufweisende Orga- nopolysiloxane A) können nach üblichen Verfahren hergestellt werden, wie z. B. durch Hydrolyse von Chlorsilanen und anschließender Polymerisation mit niedermolekularen cyclischen Diorganopolysiloxanen.Examples of the preferred component A) are compounds of the formulas T 5 D 200 M vi 5 M 2 , T 7 D 28 oM Vi 5 M 4 , T 6 D 180 D vi 2 M vi 4 M 4 and or T 8 D 250 M vi 7 M 3 . Branched, at least 2 unsaturated hydrocarbon groups containing organopolysiloxanes A) can be prepared by conventional methods, such as. B. by hydrolysis of chlorosilanes and subsequent polymerization with low molecular weight cyclic diorganopolysiloxanes.
Das Methylhydrogenpolysiloxan B) enthält vorzugsweise Einheiten der allgemeinen FormelThe methylhydrogenpolysiloxane B) preferably contains units of the general formula
Hc(R2)dSiO(4 ^y2 (II)H c (R 2 ) d SiO (4 ^ y 2 (II)
mit R2 = einwertige, gesättigte gegebenenfalls substituierte Kohlenwasserstoffreste mit bis zu 10 Kohlenstoffatomen aus der Gruppe der substituierten und unsubstitu- ierten Alkyl-, Aryl-, Arylalkyl- und / oder C2-C8-Alkenylreste, wobeiwith R 2 = monovalent, saturated, optionally substituted hydrocarbon radicals having up to 10 carbon atoms from the group of substituted and unsubstituted alkyl, aryl, arylalkyl and / or C 2 -C 8 alkenyl radicals, where
c und d ganze Zahlen sind mit 0 < d < 3 und 0 < c < 2 sowie 0 < c + d < 4, bevorzugt 0 < c < 1.c and d are integers with 0 <d <3 and 0 <c <2 and 0 <c + d <4, preferably 0 <c <1.
Die Methylhydrogenpolysiloxane B) sind vorzugsweise linear. Mindestens die Hälfte der D-Einheiten weisen vorzugsweise direkt an Silicium gebundene Wasserstoffatome (H(CH3)SiO-Gruppen) auf. Vorzugsweise beträgt die Anzahl der direkt an Silicium gebundenen Wasserstoffatome aufweisenden Gruppen zwischen 70 und 85 % der difunktionellen Einheiten.The methylhydrogenpolysiloxanes B) are preferably linear. At least half of the D units preferably have hydrogen atoms (H (CH 3 ) SiO groups) bonded directly to silicon. The number of groups having hydrogen atoms bonded directly to silicon is preferably between 70 and 85% of the difunctional units.
Der molare Anteil von direkt an ein Siliciumatom gebundenen Wasserstoffatomen in der Komponente B) kann - im Rahmen der o. g. strukturellen Einschränkungen - beliebig gewählt werden.The molar proportion of hydrogen atoms directly bonded to a silicon atom in component B) can - in the context of the abovementioned. structural restrictions - can be chosen arbitrarily.
In der Komponente B) beträgt vorzugsweise der molare Anteil von direkt an ein Siliciumatom gebundenen Wasserstoffatomen 0,01 bis 17 mmol, besonders bevorzugt 0,1 bis 17 mmol und ganz besonders bevorzugt 1 bis 17 mmol pro Gramm der Komponente B).In component B) the molar proportion of hydrogen atoms bonded directly to a silicon atom is preferably 0.01 to 17 mmol, particularly preferably 0.1 to 17 mmol and very particularly preferably 1 to 17 mmol per gram of component B).
Beispiele für die Komponente B) sind Verbindungen der Formeln MH 2Dι0, M2D10DH,0, MH 2DH 20Dι0, Mvi 2DH π und /oder M2Dvi 3DH 8 , mit MH = H(CH3)2SiOι/2 und DH = H(CH3)SiO2/2.Examples of component B) are compounds of the formulas M H 2 Dι 0 , M 2 D 10 D H , 0 , M H 2 D H 20 Dι 0 , M vi 2 D H π and / or M 2 D vi 3 D H 8 , with M H = H (CH 3 ) 2 SiOι / 2 and D H = H (CH 3 ) SiO 2/2 .
Vorzugsweise liegen die Komponenten A) und B) in einem solchen Mengenverhältnis vor, dass das molare Verhältnis von direkt an ein Siliciumatom gebundenen Wasserstoffatomen (SiH) in der Komponente B) zu den ungesättigten Resten (Si- Vinyl) in der Komponente A) 0,05 bis 20, besonders bevorzugt 0,5 bis 10 und ganz besonders bevorzugt 1 bis 3, beträgt.Components A) and B) are preferably present in a quantity ratio such that the molar ratio of hydrogen atoms (SiH) in component B) bonded directly to a silicon atom to the unsaturated radicals (Si-vinyl) in component A) is 0, 05 to 20, particularly preferably 0.5 to 10 and very particularly preferably 1 to 3.
Das Organopolysiloxan C) im Sinne der vorliegenden Erfindung ist vorzugsweise ein Polysiloxan, das Einheiten der allgemeinen FormelThe organopolysiloxane C) in the sense of the present invention is preferably a polysiloxane, the units of the general formula
(R'jeS (HI)(R'jeS (HI)
enthält,contains
wobei R1 einwertige, gesättigte gegebenenfalls Kohlenwasserstoffreste substituierte mit bis zu 10 Kohlenstoffatomen aus der Gruppe der substituierten und unsubstitu- ierten Alkyl-, Aryl-, und Arylalkylreste sind, die innerhalb des Moleküls gleich oder verschieden sein können und e ganze Zahlen zwischen 0 und 3 annehmen kann.where R 1 are monovalent, saturated, optionally hydrocarbon radicals substituted with up to 10 carbon atoms from the group of substituted and unsubstituted alkyl, aryl and arylalkyl radicals which can be the same or different within the molecule and e are integers between 0 and 3 can accept.
Bevorzugt ist Komponente C) ein lineares, mit Trimethylsiloxygruppen-endgestopp- tes Polydimethylsiloxan, wie es beispielsweise von der Bayer AG unter der Bezeichnung Baysilone -Öle M vertrieben wird. Besonders bevorzugt ist der Einsatz von solchen Baysilone®-Ölen M mit einer Viskosität zwischen 50 mmV1 und 5000 mmV. Der Begriff Inhibitor D) im Sinne der Erfindung umfasst alle nach dem Stand der Technik bekannten Inhibitoren, wie z. B. Maleinsäure und ihre Derivate, Amine, Alkylisocyanurate und acetylenisch ungesättigte Alkohole, in denen die OH-Gruppe an ein der C-C-Dreifachbindung benachbartes Kohlenstoffatom gebunden ist, wie sie z. B. in US-A 3 445 420 näher beschrieben sind. Vorzugsweise ist Komponente D) 2-Methyl-3-butin-2-ol, 1-Ethinylcyclohexanol und/oder (±) 3-Phenyl-l-butin-3-ol. Die Menge an Komponente D) in der Mischung beträgt vorzugsweise 0,0001 bisComponent C) is preferably a linear polydimethylsiloxane end-terminated with trimethylsiloxy groups, as is sold, for example, by Bayer AG under the name Baysilone oils M. The use of such Baysilone ® oils M with a viscosity between 50 mmV 1 and 5000 mmV is particularly preferred. The term inhibitor D) in the sense of the invention includes all inhibitors known according to the prior art, such as. B. maleic acid and its derivatives, amines, alkyl isocyanurates and acetylenically unsaturated alcohols, in which the OH group is bound to a carbon atom adjacent to the CC triple bond, as z. B. are described in more detail in US-A 3,445,420. Component D) is preferably 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol and / or (±) 3-phenyl-1-butyn-3-ol. The amount of component D) in the mixture is preferably 0.0001 to
5 Gew.-%, besonders bevorzugt 0,01 bis 2 Gew.-% und ganz besonders bevorzugt 0,1 bis 1 Gew.-%, bezogen auf das Gesamtgewicht der Mischung.5% by weight, particularly preferably 0.01 to 2% by weight and very particularly preferably 0.1 to 1% by weight, based on the total weight of the mixture.
Komponente E) umfasst prinzipiell alle zur Bildung und Stabilisierung von Emulsionen geeigneten Emulgatoren und/oder Verdicker (vgl. z.B. Mc Cutcheon's DetergentsComponent E) basically includes all emulsifiers and / or thickeners suitable for the formation and stabilization of emulsions (see e.g. Mc Cutcheon's Detergents
6 Emulsiliers, International Edition). Für den Fall, dass die Emulsionen zur Herstellung von Trennbeschichtungen für die Produktion von im Lebensmittelbereich eingesetzten Holzwerkstoffen verwendet werden, sind solche Emulgatoren bevorzugt, die in den FDA Regulations 176.170 „Components of Paper and Paperboard" genannt sind. Besonders bevorzugt sind Emulgatoren und Verdicker, die in der Empfehlung XV des Bundesgesundheitsamtes (BGA) Erwähnung finden, falls die Holzwerkstoffe für einen Einsatz in Transportkisten für Lebensmittel oder in Lkw-Auf- bauten vorgesehen sind.6 Emulsiliers, International Edition). In the event that the emulsions are used to produce release coatings for the production of wood-based materials used in the food sector, preference is given to those emulsifiers which are mentioned in FDA Regulations 176,170 "Components of Paper and Paperboard". Emulsifiers and thickeners are particularly preferred, which are mentioned in recommendation XV of the Federal Health Office (BGA) if the wood-based materials are intended for use in transport boxes for food or in truck bodies.
Beispiele für geeignete Emulgatoren und Verdicker E) sind.C8-C22-Alkyldimethyl- benzylammoniumchlorid, vorzugsweise in einer Menge von höchstens 1 ,5 Gew.-%, Natriumlaurylsulfat, vorzugsweise in einer Menge von höchstens 0,5 Gew.-%, Poly- ethylenglykolether von einwertigen aliphatischen Alkoholen Cι2-C20- und C2-C9A1- kylphenolen, Polyethylenglykolester natürlicher Fettsäuren C8-C22 und pflanzlicher Öle, und/oder teilacetylierter Polyvinylalkohol mit weniger als 20 % Acetylgruppen und einem K-Wert von über 40. Die Menge an Emulgatoren und Verdicker E) sollte vorzugsweise 10 Gew.-%, bezogen auf die Komponenten A), B) und C), nicht überschreiten. Unter die BGA-Emp fehlung XV fallende Emulgatoren sind zudem Carboxymethyl- cellulose, aufgeschlossene Stärke, Alginate, Kasein, Hartparaffin- und Wachsdispersionen, Dispersionen auf Basis von Mischpolymerisaten aus Acrylsäure- und Methacrylsäureestern, Butadien und Styrol, soweit sie der Empfehlung XIV entsprechen und/oder Polyvmylalkohol (Viskosität der 4 %igen wässrigen Lösung bei 20°C mindestens 4 cP), gemäß Empfehlung XIV).Examples of suitable emulsifiers and thickeners E) are: C 8 -C 22 -alkyldimethyl-benzylammonium chloride, preferably in an amount of at most 1.5% by weight, sodium lauryl sulfate, preferably in an amount of at most 0.5% by weight, Polyethylene glycol ethers of monohydric aliphatic alcohols C 2 -C 20 and C 2 -C 9 A1 alkyl phenols, polyethylene glycol esters of natural fatty acids C 8 -C 22 and vegetable oils, and / or partially acetylated polyvinyl alcohol with less than 20% acetyl groups and a K Value of over 40. The amount of emulsifiers and thickeners E) should preferably not exceed 10% by weight, based on components A), B) and C). Emulsifiers falling under BGA recommendation XV are also carboxymethyl cellulose, digested starch, alginates, casein, hard paraffin and wax dispersions, dispersions based on copolymers of acrylic and methacrylic acid esters, butadiene and styrene, insofar as they comply with recommendation XIV and / or polyalcohol (viscosity of the 4% aqueous solution at 20 ° C at least 4 cP), according to recommendation XIV).
Bevorzugt ist insbesondere Polyvmylalkohol in Kombination mit Natriumlaurylsulfat oder Alkyldimethylbenzylammoniumchlorid.Polyvinyl alcohol in combination with sodium lauryl sulfate or alkyldimethylbenzylammonium chloride is particularly preferred.
Zusatz- und Hilfsstoffe F) im Sinne der Erfindung sind z. B. Polysiloxanharze, die aus Bausteinen der allgemeinen Formeln (I) und (II) aufgebaut sind, Füllstoffe, wie z.B. Diatomeenerden, feinteilige Quarzmehle, amorphe Kieselsäuren, pyrogene und oder gefällte Kieselsäuren mit einer BET- Oberfläche von 50 bis 500 m2/g. Derartige Füllstoffe können oberflächenmodifiziert sein, z.B. durch Umsetzung mit siliziumorganischen Verbindungen wie Hexamethyldisilazan oder l,3-Divinyl-l,l,3,3-tetra- methyldisilazan. Der Einsatz von Füllstoffen ist insbesondere dann vorteilhaft, wenn das Trennmittel nicht durch Aufsprühen, sondern durch Aufwalzen aufgebracht wird.Additives and auxiliary substances F) in the sense of the invention are e.g. B. polysiloxane resins, which are composed of building blocks of the general formulas (I) and (II), fillers, such as diatomaceous earths, finely divided quartz flours, amorphous silicas, pyrogenic and or precipitated silicas with a BET surface area of 50 to 500 m 2 / g , Such fillers can be surface-modified, for example by reaction with organosilicon compounds such as hexamethyldisilazane or 1,3-divinyl-1,3,1-tetramethyldisilazane. The use of fillers is particularly advantageous when the release agent is applied by rolling rather than spraying.
Zusatz- und Hilfsstoffe F) im Sinne der Erfindung sind ebenfalls Verlaufsmittel, die die Benetzung des Substrates mit der Emulsion verbessern helfen. Hierfür eignen sich zum Beispiel Polyethersiloxane ("Silicontenside und/oder Fluortenside"). Ebenfalls sind keimhemmende Mittel (z. B. Formaldehyd-abspaltende Produkte) zu den Zusatz- und Hilfsmittel F) zu rechnen.Additives and auxiliaries F) in the sense of the invention are also leveling agents which help improve the wetting of the substrate with the emulsion. For example, polyether siloxanes (“silicone surfactants and / or fluorosurfactants”) are suitable for this. Germ inhibitors (e.g. formaldehyde-releasing products) are also to be included in the additives and auxiliaries F).
Die Menge an Komponente F) bzw. der Summe der Komponenten F) beträgt vorzugsweise weniger als 5 Gew. - %, bezogen auf die Gesamtmischung.The amount of component F) or the sum of components F) is preferably less than 5% by weight, based on the total mixture.
Vorzugsweise werden erfindungsgemäß wässrige Emulsionen mit folgenden Bestandteilen eingesetzt: als Komponente A): T8D250Mvi 7M3 als Methylhydrogenpolysiloxan B): M2DH 30Dι0 als Organopolysiloxan C): Polydimethylsiloxan der Viskosität 1000 mm2/s als Inhibitor D): Ethinylcyclohexanol als Emulgator und/oder Verdicker E): Polyvmylalkohol gegebenenfalls in Kombination mit Natriumlaurylsulfat als Zusatz- und/oder Hilfsstoffe F): keimhemmende Mittel und oder Polyether- siloxanAqueous emulsions with the following constituents are preferably used according to the invention: as component A): T 8 D 250 M vi 7 M 3 as methylhydrogenpolysiloxane B): M 2 D H 30 Dι 0 as organopolysiloxane C): polydimethylsiloxane with a viscosity of 1000 mm 2 / s as inhibitor D): ethinylcyclohexanol as emulsifier and / or Thickener E): Polyvinyl alcohol, optionally in combination with sodium lauryl sulfate as additives and / or auxiliaries F): germ-inhibiting agents and or polyether siloxane
Erfindungsgemäß werden die Holzwerkstoffe durch Heißverpressen von mit Poly- isocyanat enthaltendem Bindemittel beleimten lignocellulosehaltigen Werkstoffen hergestellt. Dabei wird auf die Pressbleche oder Pressbänder auf der dem Pressgut zugewendeten Oberfläche ein erfindungsgemäßes Trennmittel aufgebracht, beispielsweise mit Hilfe einer Sprühvorrichtung oder eines Walzenauftragsgeräts. Dabei kann das erfindungsgemäße Trennmittel unverdünnt, das heißt in der Regel als Emulsion mit einem Wassergehalt von bevorzugt 50 bis 60 Gew.-%, besonders bevorzugt 55 bis 60 Gew.-%, aufgetragen werden, bevorzugt wird es jedoch im Verhältnis von 1:50 bis 1:100 mit Wasser verdünnt. Bei geeigneter Vorkonditionierung der Pressbänder sind auch höhere Verdünnungen möglich, beispielsweise 1:150 bis 1:250. Insgesamt beträgt in der Praxis der Wassergehalt in den erfindungsgemäßen Trennmitteln bevorzugt 50 bis 99,85 Gew.-%, besonders bevorzugt 55 bis 99,85 Gew.-%.According to the invention, the wood-based materials are produced by hot pressing of lignocellulose-containing materials glued with binder containing polyisocyanate. A release agent according to the invention is applied to the press plates or press belts on the surface facing the material to be pressed, for example with the aid of a spraying device or a roller application device. The release agent according to the invention can be applied undiluted, ie generally as an emulsion with a water content of preferably 50 to 60% by weight, particularly preferably 55 to 60% by weight, but is preferred in a ratio of 1:50 diluted to 1: 100 with water. With suitable preconditioning of the press belts, higher dilutions are also possible, for example 1: 150 to 1: 250. Overall, in practice the water content in the release agents according to the invention is preferably 50 to 99.85% by weight, particularly preferably 55 to 99.85% by weight.
Das Trennmittel wird dann bei einer Temperatur von 150°C bis 240°C, bevorzugt 180 bis 240°C ausgehärtet. Zu Beginn eines Produktionslaufs wird mit einer höheren Konzentration an Trennmittel (unverdünnt bis im Verhältnis 1:50 mit Wasser verdünnt) angefahren. Eine besondere Vorbehandlung der Presswerkzeuge ist nicht notwendig. Bevorzugt wird im Produktionsprozess das Trennmittel kontinuierlich auf die heißen Pressbleche oder Pressbänder aufgesprüht. BeispieleThe release agent is then cured at a temperature of 150 ° C to 240 ° C, preferably 180 to 240 ° C. At the start of a production run, a higher concentration of release agent (undiluted to 1:50 in water) is used. A special pretreatment of the pressing tools is not necessary. In the production process, the release agent is preferably sprayed continuously onto the hot press plates or press belts. Examples
Als Komponenten wurden eingesetzt:The following components were used:
Trennemulsion IRelease emulsion I
Eine Emulsion der Komponenten:An emulsion of the components:
Trennemulsion II (Vergleich) Eine Emulsion der Komponenten:Release emulsion II (comparison) An emulsion of the components:
Trennemulsion III (Vergleich) entspricht EP-A 819 735 Release emulsion III (comparison) corresponds to EP-A 819 735
Es wurde eine Abmischung aus 50 Gew.-Teilen Trennemulsion I und 50 Gew.-TeilenThere was a mixture of 50 parts by weight of release emulsion I and 50 parts by weight
Trennemulsion II hergestellt.Release emulsion II prepared.
Isocyanat IN: pMDI mit einem ΝCO-Gehalt von ca. 31,5 Gew.-% (Desmodur® 44V20 L, Bayer AG)Isocyanate IN: pMDI with a ΝCO content of approx. 31.5% by weight (Desmodur ® 44V20 L, Bayer AG)
4000 Gew.-Teile Deckschichtspäne, die aus einem Gemisch aus Nadelholz und Laubholz bestanden und einen Feuchtigkeitsgehalt von ca. 15 Gew.-% aufwiesen, wurden mit 320 Gew.-Teilen Isocyanat IV (Desmodur® 44V20 L) beleimt. Es wurde ein Formung der Größe 300 x 300 mm auf einem 2 mm-dicken Stahl-Pressblech erstellt, und mit einem zweiten Stahl-Pressblech abgedeckt.4000 parts by weight of coating layer chips, which consisted of a mixture of coniferous wood and deciduous wood and had a moisture content of about 15 wt .-%, were glued with 320 parts by weight of isocyanate IV (Desmodur ® 44V20 L). A 300 x 300 mm size was created on a 2 mm thick steel press plate and covered with a second steel press plate.
Die beiden Pressbleche wurden vorher mit dem zu prüfenden Trennmittel vorbehandelt. Hierzu wurde die Trennemulsion zu der angegebenen Verdünnung mit Wasser verdünnt, im Kreuzgang auf die Bleche aufgesprüht, und dann zwei Minuten bei 140°C zur Aushärtung abgelüftet. Dieser Vorgang wurde dreimal wiederholt.The two press plates were previously pretreated with the release agent to be tested. For this purpose, the separating emulsion was diluted to the specified dilution with water, sprayed onto the metal sheets in a cloister, and then flashed off at 140 ° C. for two minutes for curing. This process was repeated three times.
Der Formung wurde bei der angegebenen Presstemperatur für 100 Sekunden ver- presst. Das Trennverhalten nach jeder Entformung wurde festgehalten und wie folgt bewertet:The molding was pressed at the specified pressing temperature for 100 seconds. The separation behavior after each demoulding was recorded and evaluated as follows:
Nach jeder Entformung wurden die Pressbleche wieder einmal mit der Trennemulsion besprüht, ohne Ablüftungszeit.After each demoulding, the press plates were sprayed again with the release emulsion, without any venting time.
Tabelle 1 - Trennverhalten bei 190°C, Trennemulsion 1:200 verdünntTable 1 - Separation behavior at 190 ° C, separation emulsion diluted 1: 200
Tabelle 2 - Trennverhalten bei 220°C, Trennemulsion 1:100 verdünnt Table 2 - Separation behavior at 220 ° C, separation emulsion diluted 1: 100
Tabelle 3 - Trennverhalten bei 190°C, Bleche nur vorbehandeltTable 3 - Separation behavior at 190 ° C, sheets only pretreated
Es zeigt sich eine hervorragende Trennwirkung die Trennemulsion I, die auch bei höheren Presstemperaturen erhalten bleibt und keine Ablagerungen auf dem Presswerkzeug bildet. Trennemulsion II zeigt keine ausreichende Trennwirkung, weder bei 190°C noch bei 220°C.The separating emulsion I shows an excellent separating effect, which is retained even at higher pressing temperatures and does not form any deposits on the pressing tool. Release emulsion II shows no sufficient release effect, neither at 190 ° C nor at 220 ° C.
Trennemulsion I ist schon nach einmaliger Vorbehandlung der Bleche über mehrere Entformvorgänge wirksam, ohne dass die Bleche nach jeder Entformung wieder besprüht werden müssen. Das bietet den Hersteller eine gewisse Sicherheit bei Ausfall der Trennmittelbesprühung während der Produktion. Release emulsion I is effective after a single pretreatment of the sheets over several demolding processes, without the sheets having to be sprayed again after each removal. This offers the manufacturer a certain level of security in the event that the release agent spraying fails during production.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Holzwerkstoffen durch Heißveφressen von mit Polyisocyanat enthaltendem Bindemittel beleimten lignocellulosehaltigen Werkstoffen, bei dem auf die dem Pressgut zugewandten Oberflächen des Presswerkzeugs vor dem Veφressen des Pressguts ein Gemisch siliciumorga- nischer Verbindungen aufgebracht wird, bestehend aus:1. Process for the production of wood-based materials by hot-pressing materials containing lignocellulose glued with a polyisocyanate-containing binder, in which a mixture of organosilicon compounds is applied to the surfaces of the pressing tool facing the pressing material before pressing the pressing material, consisting of:
a) mindestens einem mindestens 2 ungesättigte Kohlenwasserstoffgruppen aufweisenden Organopolysiloxan A), b) mindestens einem Methylhydrogenpolysiloxan B), c) mindestens einem unreaktiven Organopolysiloxan C), d) gegebenenfalls einem Inhibitor D), e) gegebenenfalls Emulgatoren und/oder Verdickern E), f) gegebenenfalls Zusatz- und/oder Hilfsstoffen F), g) Wasser.a) at least one organopolysiloxane A) containing at least 2 unsaturated hydrocarbon groups, b) at least one methyl hydrogen polysiloxane B), c) at least one unreactive organopolysiloxane C), d) optionally an inhibitor D), e) optionally emulsifiers and / or thickeners E), f ) optionally additives and / or auxiliaries F), g) water.
2. Verfahren gemäß Anspruch 1, bei dem die Presstemperatur 150°C bis 240°C beträgt.2. The method according to claim 1, wherein the pressing temperature is 150 ° C to 240 ° C.
3. Verfahren gemäß Anspruch 1 oder 2, bei dem das Gemisch siliciumorga- nischer Verbindungen vor jedem Pressvorgang aufgebracht wird.3. The method according to claim 1 or 2, wherein the mixture of organosilicon compounds is applied before each pressing operation.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, bei dem vor dem ersten Pressvorgang durch thermisches Aushärten des aufgebrachten Gemischs sili- ciumorganischer Verbindungen eine Trennschicht auf den dem Pressgut zugewandten Oberflächen des Presswerkzeugs erzeugt wird.4. The method according to any one of claims 1 to 3, in which a separating layer is produced on the surfaces of the pressing tool facing the material to be pressed before the first pressing process by thermal curing of the applied mixture of silicon-organic compounds.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass neben dem Polyisocyanat enthaltenden Bindemittel auch Bindemittel auf Basis HarnstoffTFormaldehyd- und/oder Melamin/Formaldehyd- und/oder Phenol/Formaldehyd-Harzen mit eingesetzt und gegebenenfalls weitere Hilfsund Zusatzmittel zugesetzt werden.5. The method according to any one of claims 1 to 4, characterized in that in addition to the binder containing polyisocyanate, binders based on urea, formaldehyde and / or melamine / formaldehyde and / or Phenol / formaldehyde resins are used and, if appropriate, further auxiliaries and additives are added.
6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass als Polyisocyanat polymeres Diphenylmethandusocyanat (pMDI) eingesetzt wird.6. The method according to any one of claims 1 to 5, characterized in that polymeric diphenylmethane diisocyanate (pMDI) is used as the polyisocyanate.
7. Verwendung von Gemischen bestehend aus:7. Use of mixtures consisting of:
a) mindestens einem mindestens 2 ungesättigte Kohlenwasserstoffgruppen aufweisenden Organopolysiloxan A), b) mindestens einem Methylhydrogenpolysiloxan B), c) mindestens einem unreaktiven Organopolysiloxan C), d) gegebenenfalls Inhibitoren D), e) gegebenenfalls Emulgatoren und/oder Verdickern E), f) gegebenenfalls Zusatz- und/oder Hilfsstoffen F), g) Wassera) at least one organopolysiloxane A) containing at least 2 unsaturated hydrocarbon groups, b) at least one methylhydrogenpolysiloxane B), c) at least one unreactive organopolysiloxane C), d) optionally inhibitors D), e) optionally emulsifiers and / or thickeners E), f) optionally additives and / or auxiliaries F), g) water
als Trennmittel bei der Herstellung von Holzwerkstoffen durch Heißveφressen von mit Polyisocyanat enthaltendem Bindemittel beleimten lignocellulosehaltigen Werkstoffen. as a release agent in the manufacture of wood-based materials by hot-compressing lignocellulose-containing materials glued with a binder containing polyisocyanate.
EP02704654A 2001-01-22 2002-01-15 Siloxane separating agent for producing derived timber products Withdrawn EP1356005A1 (en)

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DE10102689 2001-01-22
DE2001102689 DE10102689A1 (en) 2001-01-22 2001-01-22 Siloxane release agent for the manufacture of wood-based materials
PCT/EP2002/000323 WO2002057380A1 (en) 2001-01-22 2002-01-15 Siloxane separating agent for producing derived timber products

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