EP0022455B1 - A process for the preparation of striking surfaces for matches - Google Patents

A process for the preparation of striking surfaces for matches Download PDF

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Publication number
EP0022455B1
EP0022455B1 EP80102454A EP80102454A EP0022455B1 EP 0022455 B1 EP0022455 B1 EP 0022455B1 EP 80102454 A EP80102454 A EP 80102454A EP 80102454 A EP80102454 A EP 80102454A EP 0022455 B1 EP0022455 B1 EP 0022455B1
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EP
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Prior art keywords
weight
polyester
copolymer
added
acid
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EP80102454A
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German (de)
French (fr)
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EP0022455A1 (en
Inventor
Wilhelm Dr. Adam
Hannsjörg Dr. Ulrich
Franz-Josef Dr. Dany
Gerd Kalteyer
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Hoechst AG
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Hoechst AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • B24D3/28—Resins or natural or synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06F—MATCHES; MANUFACTURE OF MATCHES
    • C06F3/00—Chemical features in the manufacture of matches
    • C06F3/08—Strike-surface compositions
    • 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]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31859—Next to an aldehyde or ketone condensation product
    • Y10T428/31862—Melamine-aldehyde
    • Y10T428/31866—Impregnated or coated cellulosic material

Definitions

  • the present invention relates to a method for the production of matchstick surfaces by first of red phosphorus, abrasives, such as.
  • abrasives such as.
  • binders in the form of aqueous urea-formaldehyde or melamine-formaldehyde condensates and optionally hardeners, such as. B. ammonium chloride, fillers such. B. Fe 2 0 3 , Mn0 2 , Sb 2 S 3 or additional water to regulate the viscosity of the mixture prepares an aqueous mash.
  • This mash is then used to coat the respective friction surface underlay, which can consist of paper, wood, cardboard, etc., and if necessary, the surface obtained is subsequently treated with heat, the coated surfaces being dried and the binders contained therein being condensed and hardened.
  • the mashes can be applied to the friction surface supports, for example, with brushes or with printing machines.
  • the mashes should be thin and spreadable so that an evenly thin distribution of the mash on the surface is guaranteed. Pads that are too thick tend to crumble and tear after drying.
  • a serious disadvantage of the friction surfaces produced with them is their resistance to moisture, in particular under tropical conditions, and at the same time bacterial attack can additionally destroy the friction surfaces.
  • the urea or melamine resins were largely resistant to bacterial attack, but tended to form brittle, brittle paint surfaces. In addition, the penetration of the friction surfaces by moisture or water is not eliminated in these cases, but at most is only inhibited.
  • the polyester is expediently added in the form of an aqueous solution, the copolymer in the form of an aqueous dispersion or an aqueous-alcoholic solution, the weight percentages given for the addition being based on the solids content of the urea or melamine-formaldehyde condensates and on the solids content of the crosslinker.
  • the pH of the mixture obtained is then adjusted to between 6.5 and 8.0, preferably from 7 to 7, by adding an aqueous solution of ammonia, organic amines or a mineral acid, in particular phosphoric acid, if the copolymer is used , 5, and in the case of using the polyester to values of 7 to 11, preferably 9.2 to 9.6, before coating the friction surface underlay with the mixture.
  • organic amines are used for pH adjustment, low-boiling organic amines such as. B. trimethylamine, triethylamine, but preferably dimethylethanolamine used.
  • the surfaces can be annealed at about 90 to 130 ° C for about 5 minutes.
  • the friction surfaces obtained are elastically flexible even in a thick layer and adhere well to substrates made of wood, paper, cardboard, etc. Additional adhesives can optionally be incorporated for use on plastic surfaces.
  • the ignitability can be described as "very good” and is only slightly reduced by moisture and water.
  • a mash produced according to the invention has the following composition, for example:
  • Suitable melamine-formaldehyde condensates are mononuclear or polynuclear methylolated melamines with a molar ratio of 1: 1.3 to 1: 6, the methylol groups of which are not etherified or with at least one mono- or polyhydric aliphatic alcohol with 1 to 6, preferably 1 to 4, Atoms are partially or completely etherified, with limited, preferably unlimited water dilutability, or mixtures thereof.
  • the mono- or polyhydric aliphatic alcohol can be saturated or unsaturated, and its carbon chain can also be interrupted by one or more ether bridges.
  • Suitable alcohols are, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, n-pentanol, iso-pentanol, n-hexanol, iso-hexanol, allyl alcohol, ethylene glycol, propylene glycol, butanediols, such as butane diol -1,4, hexanediols, such as 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin.
  • Methanol is preferred as the aliphatic alcohol.
  • Preferred melamine-formaldehyde condensates are trimethylol melamine trimethyl ether, hexamethylol melamine hexamethyl ether or peniamethyl oil melamine trimethyl ether.
  • the mono- and multinuclear methylolmelamines can also contain the modifiers customary in aminoplast chemistry in amounts of about 2 to 20% by weight, based on mononuclear or multinuclear methylolmelamine.
  • Such modifiers are, for example, sorbitol, sugar, lactam, such as. B. B -aminocaprolactam, methylene bisformamide, toluenesulfonamides, such as. B. p-toluenesulfonamide.
  • sorbitol sugar, lactam, such as. B. B -aminocaprolactam
  • methylene bisformamide toluenesulfonamides
  • B. p-toluenesulfonamide such as.
  • the urea with a molar ratio urea to Formaldei l yd of 1 as urea-formaldehyde condensates include monomeric or polycondensed methylol: to 1: 3 into consideration, the aliphatic also with the abovementioned monohydric or polyhydric alcohols may be etherified completely or partially. Mixtures of etherified or unetherified monomeric and / or polycondensed methylolated ureas can also be used, as can mixtures of the melamine-formaldehyde condensates mentioned with the urea-formaldehyde condensates mentioned.
  • the water-soluble amino resin-crosslinking polyester to be used as crosslinking agent has in particular an OH number of 30 to 450, preferably 80 to 200, an acid number of 20 to 300, preferably 60 to 100, and, measured in 50% strength by weight solution in butyl glycol, a dynamic viscosity of 100 to 750mPa ⁇ s.
  • Such polyesters are known and are produced by polycondensation of dihydric dicarboxylic acids and dihydric alcohols, it also being possible for small amounts of trihydric and polyhydric carboxylic acids and / or alcohols to be present. Derivatives of carboxylic acids and alcohols, in particular esters with lower alcohols, acid chlorides, anhydrides or lactones, can also be used in the polycondensation.
  • Suitable dibasic carboxylic acids or their derivatives are for example phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic anhydride, Hexachloroendomethylen-tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid.
  • Suitable unsaturated dibasic carboxylic acids or their derivatives are, for example: maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid.
  • trihydric or polyvalent carboxylic acids and / or alcohols branching or crosslinking of the polyester can be achieved.
  • trihydric or polyvalent carboxylic acids and / or alcohols branching or crosslinking of the polyester can be achieved.
  • trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, glycerol, pentaerythritol are suitable for this.
  • polyesters in which the polycarboxylic acid component consists wholly or partly of aliphatic dicarboxylic acids, in particular adipic, succinic, sebacic or azelaic acid, are particularly suitable.
  • the polyester can optionally also be modified by a content of monocarboxylic acids.
  • the polyesters used are not air-drying systems.
  • the condition "water-soluble" in connection with the polyester means that the polyester can be dissolved in water at pH values above 7.
  • a suitable polyester was e.g. B. made as follows: were condensed for 41 ⁇ 2 hours, the temperature rising from 125 ° C to 185 ° C and 65 kg of distillate was obtained, which consisted of 60 kg of water and 5 kg of ethylene glycol. The yield of polyester was 574 kg.
  • the solids content of the polyester was practically 100% by weight (determined by heating a 1 g sample at 140 ° C. for one hour), the OH number was found to be 181 and the acid number was 96 mg KOH / g.
  • the viscosity of a 50% by weight solution in butyl glycol was 132 mPa ⁇ s.
  • aqueous urea-formaldehyde resin condensate which is commercially available under the name “Madurit VMW 69 / 1®” (manufacturer Cassella Aktiengesellschaft, Frankfurt / Main), has proven particularly useful as a binder, while one is used as a crosslinker Also commercially available, about 50% by weight aqueous dispersion of a copolymer, which is available under the name "Mowilith DM 56®” (manufacturer Hoechst Aktiengesellschaft, Frankfurt / Main), in which the copolymer contains more than 50% by weight. % consists of an acrylic acid ester and less than 50% by weight of vinyl acetate and the dispersion has a glass transition temperature of -18 ° C.
  • a mixture with a pH of 9.7 consisting of was applied to a cardboard base with a bristle brush and dried and cured at 100 ° C for 5 minutes.
  • a mixture according to Example 8 was adjusted to a pH of 7.8 with ammonia water.
  • the friction surface produced from this as above was uniform, elastic and only weakly brittle after sharp kinking movements and thus rated "good".
  • a binder based on a melamine-formaldehyde resin was mixed with a polyester which was produced in the manner described above. (This mixture is commercially available under the name ®Madurit VMW 82; manufacturer Cassella AG, Frankfurt.)
  • the pH of the mash obtained fluctuated widely depending on the provenance of the phosphorus. In order to delimit the optimal condensation conditions, the pH was adjusted to higher values in NaOH (40%) in Examples 13-16.
  • the mash was then applied to a cardboard in a covering layer with a brush and dried at 120 ° C. for 3 minutes.
  • the evaluation of the friction surfaces obtained is shown in the table below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Zündholzreibflächen, indem man zunächst aus rotem Phosphor, Reibmitteln, wie z. B. Glasmehl oder Sand, Bindemitteln in Form von wäßrigen Harnstoff-Formaldehyd- oder Melamin-Formaldehyd-Kondensaten sowie gegebenenfalls Härtern, wie z. B. Ammoniumchlorid, Füllstoffen, wie z. B. Fe203, Mn02, Sb2S3 oder zusätzlichem Wasser zur Regulierung der Viskosität der Mischung eine wäßrige Maische bereitet. Mit dieser Maische beschichtet man dann die jeweilige Reibflächenunterlage, welche aus Papier, Holz, Karton usw. bestehen kann und behandelt gegebenenfalls die erhaltene Fläche anschließend mit Wärme, wobei die beschichteten Flächen getrocknet und die darin enthaltenen Bindemittel kondensiert und gehärtet werden.The present invention relates to a method for the production of matchstick surfaces by first of red phosphorus, abrasives, such as. As glass powder or sand, binders in the form of aqueous urea-formaldehyde or melamine-formaldehyde condensates and optionally hardeners, such as. B. ammonium chloride, fillers such. B. Fe 2 0 3 , Mn0 2 , Sb 2 S 3 or additional water to regulate the viscosity of the mixture prepares an aqueous mash. This mash is then used to coat the respective friction surface underlay, which can consist of paper, wood, cardboard, etc., and if necessary, the surface obtained is subsequently treated with heat, the coated surfaces being dried and the binders contained therein being condensed and hardened.

Das Auftragen der Maischen auf die Reibflächenunterlagen kann beispielsweise mit Pinseln oder mit Druckmaschinen erfolgen.The mashes can be applied to the friction surface supports, for example, with brushes or with printing machines.

Die Maischen sollen dünn und streichfähig sein, damit eine gleichmäßig dünne Verteilung der Maische auf der Unterlage gewährleistet ist. Zu dicke Auflagen neigen nach dem Austrocknen zum Abbröckeln und Reißen.The mashes should be thin and spreadable so that an evenly thin distribution of the mash on the surface is guaranteed. Pads that are too thick tend to crumble and tear after drying.

Früher, und z. T. auch noch heute, verwandte man als Bindemittel Haut- oder Knochenleim oder Gummi arabicum, gegebenenfalls in Verbindung mit Gummi traganth.Earlier, and e.g. T. still today, skin or bone glue or gum arabic were used as binders, possibly in combination with gum tragacanth.

Ein gravierender Nachteil der damit hergestellten Reibflächen ist ihre Unbeständigkeit gegen Feuchtigkeit, insbesondere unter tropischen Bedingungen, wobei gleichzeitig ein Bakterienbefall zusätzlich zur Zerstörung der Reibflächen beitragen kann.A serious disadvantage of the friction surfaces produced with them is their resistance to moisture, in particular under tropical conditions, and at the same time bacterial attack can additionally destroy the friction surfaces.

Aus diesem Grunde sind schon häufig Versuche unternommen worden, Bindemittel auf Basis von Harnstoff- bzw. Melamin-Formaldehydharzen oder Polyvinylchloriddispersionen zu verwenden. Dabei erwiesen sich Formulierungen auf PVC-Basis zwar als gut aber auch als sehr teuer.For this reason, attempts have often been made to use binders based on urea or melamine-formaldehyde resins or polyvinyl chloride dispersions. Formulations based on PVC proved to be good but also very expensive.

Die Harnstoff- oder Melaminharze zeigten sich zwar weitgehend resistent gegen bakteriellen Befall, neigten aber zur Ausbildung spröder, brüchiger Anstrichflächen. Außerdem ist in diesen Fällen die Durchdringung der Reibflächen durch Feuchtigkeit oder Wasser nicht aufgehoben, sondern äußerstenfalls nur gehemmt.The urea or melamine resins were largely resistant to bacterial attack, but tended to form brittle, brittle paint surfaces. In addition, the penetration of the friction surfaces by moisture or water is not eliminated in these cases, but at most is only inhibited.

Hinzu kam, daß die Aushärtung dieser Harze nicht in jedem Falle in der gleichen-Weise erfolgte, und daß, in Abhängigkeit vom jeweils eingesetzten roten Phosphor, sehr häufig klebrige oder brüchige Reibflächen entstanden.In addition, these resins were not cured in the same way in every case, and, depending on the red phosphorus used, very often sticky or brittle friction surfaces were formed.

Überraschenderweise wurde nun gefunden, daß sich bei Verwendung von rotem Phosphor in Verbindung mit Harnstoff-Formaldehyd- oder Melamin-Formaldehyd-Kondensaten als Bindemittel, unabhängig von der Herkunft des Phosphors gleichgleibend gute Reibflächen herstellen lassen, wenn man der wäßrigen Maische der Ausgangsprodukte, bezogen auf den Feststoffgehalt der Harnstoff- bzw. Melamin-Formaldehyd-Kondensate, als Vernetzer 5 bis 20 Gew.-%, vorzugsweise 10 bis 15 Gew.-%, eines aminharzvernetzenden Polyesters oder eines durch Copolymerisation von Acryl-und/oder Methacrylester mit Vinylacetat im Gewichtsverhältnis 9:1 1 bis 1:9 hergestelltes Copolymerisat, das, bezogen auf den monomeren Esteranteil, auch bis zu 20 Gew.-% Acryl- und/oder Methacrylsäure einpolymerisiert enthalten kann, zusetzt. Zweckmäßigerweise wird der Polyester in Form einer wäßrigen Lösung, das Copolymerisat in Form einer wäßrigen Dispersion oder einer wäßrig-alkoholischen Lösung zugesetzt, wobei die angegebenen Gewichtsprozente für den Zusatz sich auf den Feststoffgehalt der Harnstoff- bzw. Melamin-Formaldehyd-Kondensate und auf den Feststoffgehalt des Vernetzers beziehen. Dann stellt man den pH-Wert der erhaltenen Mischung durch Zugabe einer wäßrigen Lösung von Ammoniak, organischen Aminen oder einer Mineralsäure, insbesondere von Phosphorsäure, im Falle der Verwendung des Copolymerisats auf Werte zwischen 6,5 und 8,0, vorzugsweise von 7 bis 7,5, und im Falle der Verwendung des Polyesters auf Werte von 7 bis 11, vorzugsweise 9,2 bis 9,6, ein, bevor man mit der Mischung die Reibflächenunterlage beschichtet.Surprisingly, it has now been found that when using red phosphorus in conjunction with urea-formaldehyde or melamine-formaldehyde condensates as binders, irrespective of the origin of the phosphorus, uniformly good friction surfaces can be produced if the aqueous mash of the starting products is based on the solids content of the urea or melamine-formaldehyde condensates, as a crosslinking agent 5 to 20% by weight, preferably 10 to 15% by weight, of an amine resin-crosslinking polyester or by copolymerization of acrylic and / or methacrylic ester with vinyl acetate in a weight ratio 9: 1 1 to 1: 9 copolymer which, based on the monomeric ester fraction, can also contain up to 20% by weight of acrylic and / or methacrylic acid in copolymerized form. The polyester is expediently added in the form of an aqueous solution, the copolymer in the form of an aqueous dispersion or an aqueous-alcoholic solution, the weight percentages given for the addition being based on the solids content of the urea or melamine-formaldehyde condensates and on the solids content of the crosslinker. The pH of the mixture obtained is then adjusted to between 6.5 and 8.0, preferably from 7 to 7, by adding an aqueous solution of ammonia, organic amines or a mineral acid, in particular phosphoric acid, if the copolymer is used , 5, and in the case of using the polyester to values of 7 to 11, preferably 9.2 to 9.6, before coating the friction surface underlay with the mixture.

Falls für die pH-Wert-Einstellung organische Amine verwendet werden, werden niedrigsiedende organische Amine wie z. B. Trimethylamin, Triäthylamin, vorzugsweise jedoch Dimethyläthanolamin, verwendet.If organic amines are used for pH adjustment, low-boiling organic amines such as. B. trimethylamine, triethylamine, but preferably dimethylethanolamine used.

Zur Trocknung und/oder Aushärtung können die Flächen bei etwa 90 bis 130°C ca. 5 Minuten lang getempert werden. Die erhaltenen Reibflächen sind selbst in dicker Schicht elastisch biegsam und haften gut auf Unterlagen aus Holz, Papier, Karton usw. Für die Anwendung auf Kunststoffflächen können gegebenenfalls zusätzliche Haftvermittler eingearbeitet werden. Die Zündfähigkeit ist mit »sehr gut« zu bezeichnen und wird durch Feuchtigkeit und Wasser nur wenig reduziert.For drying and / or curing, the surfaces can be annealed at about 90 to 130 ° C for about 5 minutes. The friction surfaces obtained are elastically flexible even in a thick layer and adhere well to substrates made of wood, paper, cardboard, etc. Additional adhesives can optionally be incorporated for use on plastic surfaces. The ignitability can be described as "very good" and is only slightly reduced by moisture and water.

Eine erfindungsgemäß hergestellte Maische weist beispielsweise folgende Zusammensetzung auf:

Figure imgb0001
Figure imgb0002
 A mash produced according to the invention has the following composition, for example:
Figure imgb0001
Figure imgb0002

Geeignete Melamin-Formaldehyd-Kondensate sind ein- oder mehrkernige methylolierfe Melamine mit einem Molverhältnis 1 : 1,3 bis 1 : 6, deren Methylolgruppen unveräthert oder mit mindestens einem ein- oder mehrwertigen aliphatischen Alkohol mit 1 bis 6, vorzugsweise 1 bis 4 C-Atomen teilweise oder vollkommen veräthert sind, mit begrenzter, vorzugsweise unbegrenzter Wasserverdünnbarkeit, oder deren Mischungen. Der ein- oder mehrwertige aliphatische Alkohol kann dabei gesättigt oder ungesättigt sein, und seine Kohlenstoffkette kann auch durch eine oder mehrere Ätherbrücken unterbrochen sein. Geeignete Alkohole sind beispielsweise Methanol, Äthanol, n-Propanol, iso-Propanol, n-Butanol, iso-Butanol, n-Pentanol, iso-Pentanol, n-Hexanol, iso-Hexanol, Allylalkohol, Äthylenglykol, Propylenglykol, Butandiole, wie Butandiot-1,4, Hexandiole, wie Hexandiol-1,6, Diäthylenglykol, Triäthylenglykol, Dipropylenglykol, Glyzerin. Methanol wird als aliphatischer Alkohol bevorzugt. Bevorzugte Melamin-Formaldehyd-Kondensate sind Trimethylolmelamin-trimethyläther, Hexamethylolmelamin-hexamethyläther oder Peniamethylölmelamintrimethyl- äther.Suitable melamine-formaldehyde condensates are mononuclear or polynuclear methylolated melamines with a molar ratio of 1: 1.3 to 1: 6, the methylol groups of which are not etherified or with at least one mono- or polyhydric aliphatic alcohol with 1 to 6, preferably 1 to 4, Atoms are partially or completely etherified, with limited, preferably unlimited water dilutability, or mixtures thereof. The mono- or polyhydric aliphatic alcohol can be saturated or unsaturated, and its carbon chain can also be interrupted by one or more ether bridges. Suitable alcohols are, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, n-pentanol, iso-pentanol, n-hexanol, iso-hexanol, allyl alcohol, ethylene glycol, propylene glycol, butanediols, such as butane diol -1,4, hexanediols, such as 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin. Methanol is preferred as the aliphatic alcohol. Preferred melamine-formaldehyde condensates are trimethylol melamine trimethyl ether, hexamethylol melamine hexamethyl ether or peniamethyl oil melamine trimethyl ether.

Die ein- und mehrkernigen Methylolmelamine können auch die in der Aminoplastchemie üblichen Modifizierungsmittel in Mengen von etwa 2 bis 20 Gew.-%, bezogen auf einkerniges oder mehrkerniges Methylolmelamin, enthalten. Solche Modifizierungsmittel sind beispielsweise Sorbit, Zucker, Lactam, wie z. B. B-Aminocaprolactam, Methylenbisformamid, Toluolsulfonamide, wie z. B. p-Toluolsulfonamid. Eine derartige Modifizierung ist jedoch nicht unbedingt erforderlich.The mono- and multinuclear methylolmelamines can also contain the modifiers customary in aminoplast chemistry in amounts of about 2 to 20% by weight, based on mononuclear or multinuclear methylolmelamine. Such modifiers are, for example, sorbitol, sugar, lactam, such as. B. B -aminocaprolactam, methylene bisformamide, toluenesulfonamides, such as. B. p-toluenesulfonamide. However, such a modification is not absolutely necessary.

Als Harnstoff-Formaldehyd-Kondensate kommen monomere oder polykondensierte Methylolverbindungen des Harnstoffs mit einem Molverhältnis Harnstoff zu Formaldeilyd von 1 : bis 1 : 3 in Betracht, die auch mit den bereits genannten ein- oder mehrwertigen aliphatischen Alkoholen ganz oder teilweise veräthert sein können. Auch Mischungen verätherter oder unverätherter monomerer und/oder polykondensierter methylolierter Harnstoffe können Verwendung finden, ebenso Mischungen der genannten Melamin-Formaldehyd-Kondensate mit den genannten Harnstoff-Formaldehyd-Kondensaten.The urea with a molar ratio urea to Formaldei l yd of 1 as urea-formaldehyde condensates include monomeric or polycondensed methylol: to 1: 3 into consideration, the aliphatic also with the abovementioned monohydric or polyhydric alcohols may be etherified completely or partially. Mixtures of etherified or unetherified monomeric and / or polycondensed methylolated ureas can also be used, as can mixtures of the melamine-formaldehyde condensates mentioned with the urea-formaldehyde condensates mentioned.

Der als Vernetzer zu verwendende wasserlösliche aminoharzvernetzende Polyester besitzt insbesondere eine OH-Zahl von 30 bis 450, vorzugsweise von 80 bis 200, eine Säurezahl von 20 bis 300, vorzugsweise 60 bis 100, und, gemessen in 50gew.-%iger Lösung in Butylglykol, eine dynamische Viskosität von 100 bis 750mPa · s. Derartige Polyester sind bekannt und werden durch Polykondensation zweiwertiger Dicarbonsäuren und zweiwertiger A!kohole hergestellt, wobei auch geringe Mengen drei- und mehrwertiger Carbonsäuren und/oder Alkohole anwesend sein können. Bei der Polykondensation können auch Derivate der Carbonsäuren und Alkohole, insbesondere Ester mit niederen Alkoholen, Säurechloride, Anhydride oder Lactone eingesetzt werden.The water-soluble amino resin-crosslinking polyester to be used as crosslinking agent has in particular an OH number of 30 to 450, preferably 80 to 200, an acid number of 20 to 300, preferably 60 to 100, and, measured in 50% strength by weight solution in butyl glycol, a dynamic viscosity of 100 to 750mPa · s. Such polyesters are known and are produced by polycondensation of dihydric dicarboxylic acids and dihydric alcohols, it also being possible for small amounts of trihydric and polyhydric carboxylic acids and / or alcohols to be present. Derivatives of carboxylic acids and alcohols, in particular esters with lower alcohols, acid chlorides, anhydrides or lactones, can also be used in the polycondensation.

Geeignete zweibasische Carbonsäuren oder deren Derivate sind beispielsweise Phthalsäure, Phthalsäureanhydrid, Isophthalsäure, Terephthalsäure, Tetrahydrophthalsäure, Hexahydrophthalsäure, Endomethylen-Tetrahydrophthalsäureanhydrid, Hexachloroendomethylen-Tetrahydrophthalsäureanhydrid, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure.Suitable dibasic carboxylic acids or their derivatives are for example phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic anhydride, Hexachloroendomethylen-tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid.

Geeignete ungesättigte zweibasische Carbonsäuren bzw. deren Derivate sind beispielsweise: Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Mesaconsäure.Suitable unsaturated dibasic carboxylic acids or their derivatives are, for example: maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid.

Geeignete Glykole für die Herstellung der Polyester sind beispielsweise: Äthylenglykol, Propylenglykol-(1,2), Propylenglykol-(1,3), Butylenglykol-(1,2), Butylenglykol-(1,3), Butylenglykol-(1,4), Diäthylenglykol, Dipropylenglykol, Triäthylenglykol, 1,5-Pentandiol, 1,6-Hexandiol, Hexylenglykol (=2-Methyl-2,4-pentandiol), Neopentylglykol (=2,2-Dimethyl-1,3-propandiol).Suitable glycols for the production of the polyesters are, for example: ethylene glycol, propylene glycol (1,2), propylene glycol (1,3), butylene glycol (1,2), butylene glycol (1,3), butylene glycol (1,4 ), diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, hexylene glycol (= 2-methyl-2,4-pentanediol), neopentyl glycol (= 2,2-dimethyl-1, 3-propanediol).

Durch Einbau einer geringen Menge von drei- oder mehrwertigen Carbonsäuren und/oder Alkoholen kann eine Verzweigung bzw. Vernetzung des Polyesters erreicht werden. Hierfür sind beispielsweise Trimethylolpropan, Trimethyloläthan, 1,2,6-Hexantriol, Glyzerin, Pentaerythrit geeignet.By incorporating a small amount of trihydric or polyvalent carboxylic acids and / or alcohols, branching or crosslinking of the polyester can be achieved. For example, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, glycerol, pentaerythritol are suitable for this.

Es sind besonders solche Polyester geeignet, bei denen die Polycarbonsäurekomponente ganz oder zum Teil aus aliphatischen Dicarbonsäuren, insbesondere Adipin-, Bernstein-, Sebacin- oder Azelainsäure besteht.Those polyesters in which the polycarboxylic acid component consists wholly or partly of aliphatic dicarboxylic acids, in particular adipic, succinic, sebacic or azelaic acid, are particularly suitable.

Der Polyester kann gegebenenfalls auch durch einen Gehalt an Monocarbonsäuren modifiziert sein. Bei den zur Anwendung kommenden Polyestern handelt es sich nicht um lufttrocknende Systeme. Die Bedingung »wasserlöslich« im Zusammenhang mit dem Polyester bedeutet, daß der Polyester bei pH-Werten über 7 in Wasser gelöst werden kann.The polyester can optionally also be modified by a content of monocarboxylic acids. The polyesters used are not air-drying systems. The condition "water-soluble" in connection with the polyester means that the polyester can be dissolved in water at pH values above 7.

Ein geeigneter Polyester wurde z. B. wie folgt hergestellt:

Figure imgb0003
wurden 4½ h lang kondensiert, wobei die Temperatur von 125° C auf 185° C anstieg und 65 kg Destillat erhalten wurde, das aus 60 kg Wasser und 5 kg Äthylenglykol bestand. Die Ausbeute an Polyester betrug 574 kg. Der Festkörpergehalt des Polyesters betrug praktisch 100 Gew.-% (bestimmt durch einstündiges Erhitzen einer 1-g-Probe auf 140°C), die OH-Zahl wurde zu 181 und die Säurezahl zu 96 mg KOH/g bestimmt. Die Viskosität einer 50gew.-%igen Lösung in Butylglykol betrug 132 mPa · s. Als Bindemittel hat sich insbesondere ein etwa 45gew.-%iges wäßriges Harnstoff-Formaldehydharz-Kondensat bewährt, das unter der Bezeichnung »Madurit VMW 69/1®« (Hersteller Cassella Aktiengesellschaft, Frankfurt/Main) im Handel ist, während sich als Vernetzer eine ebenfalls im Handel befindliche, etwa 50gew.-%ige wäßrige Dispersion eines Copolymerisates ausgezeichnet hat, die unter dem Namen »Mowilith DM 56®« (Hersteller Hoechst Aktiengesellschaft, Frankfurt/Main) erhältlich ist, worin das Copolymerisat zu mehr als 50 Gew.-% aus einem Acrylsäureester und zu weniger als 50 Gew.-% aus Vinylacetat besteht und wobei die Dispersion eine Einfriertemperatur von -18°C hat.A suitable polyester was e.g. B. made as follows:
Figure imgb0003
 were condensed for 4½ hours, the temperature rising from 125 ° C to 185 ° C and 65 kg of distillate was obtained, which consisted of 60 kg of water and 5 kg of ethylene glycol. The yield of polyester was 574 kg. The solids content of the polyester was practically 100% by weight (determined by heating a 1 g sample at 140 ° C. for one hour), the OH number was found to be 181 and the acid number was 96 mg KOH / g. The viscosity of a 50% by weight solution in butyl glycol was 132 mPa · s. An approximately 45% by weight aqueous urea-formaldehyde resin condensate, which is commercially available under the name “Madurit VMW 69 / 1®” (manufacturer Cassella Aktiengesellschaft, Frankfurt / Main), has proven particularly useful as a binder, while one is used as a crosslinker Also commercially available, about 50% by weight aqueous dispersion of a copolymer, which is available under the name "Mowilith DM 56®" (manufacturer Hoechst Aktiengesellschaft, Frankfurt / Main), in which the copolymer contains more than 50% by weight. % consists of an acrylic acid ester and less than 50% by weight of vinyl acetate and the dispersion has a glass transition temperature of -18 ° C.

Die folgenden Beispiele sollen den Erfindungsgegenstand näher erläutern, ohne daß er auf den Inhalt der Beispiele beschränkt sein soll.The following examples are intended to explain the subject of the invention in more detail, without being restricted to the content of the examples.

Beispiel 1example 1 (Vergleichsbeispiel)(Comparative example)

Eine Mischung mit einem pH-Wert von 9,7, bestehend aus

Figure imgb0004
wurde mit einem borstigen Pinsel auf eine Unterlage aus Karton aufgebracht und bei 100°C 5 Minuten lang getrocknet und gehärtet.A mixture with a pH of 9.7 consisting of
Figure imgb0004
 was applied to a cardboard base with a bristle brush and dried and cured at 100 ° C for 5 minutes.

Dabei entstand eine ungleichmäßige, sehr brüchige, spröde Reibfläche.This created an uneven, very brittle, brittle friction surface.

Beispiele 2-5Examples 2-5

Einer gleichen Mischung wie im Beispiel 1 beschrieben, wurden, bezogen auf den Feststoffgehalt der Harnstoff-Formaldehyd-Kondensat-Lösung 5, 10, 15 und 20 Gew.-%, berechnet als Festsubstanz, einer 50gew.-%igen wäßrigen Dispersion eines Copolymerisates zugesetzt, das zu mehr als 50 Gew.-% aus einem Acrylsäureester und zu weniger als 50 Gew.-% aus Vinylacetat bestand. Diese Dispersion wies eine Einfriertemperatur von -18°C auf (Handelsbezeichnung »Mowilith DM 56®« der Hoechst Aktiengesellschaft, Frankfurt/Main).5, 10, 15 and 20% by weight, calculated as the solid substance, of a 50% by weight aqueous dispersion of a copolymer were added to the same mixture as described in Example 1, based on the solids content of the urea-formaldehyde condensate solution , which consisted of more than 50 wt .-% of an acrylic acid ester and less than 50 wt .-% of vinyl acetate. This dispersion had a freezing temperature of -18 ° C (trade name "Mowilith DM 56®" from Hoechst Aktiengesellschaft, Frankfurt / Main).

Die erhaltenen Maischen wurden, nachdem sie auf jeweils verschiedene pH-Werte eingestellt worden waren, mit einem Pinsel auf eine Kartonunterlage aufgetragen und bei 100°C 5 Minuten lang getrocknet und gehärtet.The mashes obtained, after having been adjusted to different pH values in each case, were applied to a cardboard base with a brush and dried and cured at 100 ° C. for 5 minutes.

Die Gebrauchsfähigkeit der erhaltenen Reibflächen ist aus der nachfolgenden Tabelle ersichtlich:

Figure imgb0005
The usability of the friction surfaces obtained can be seen from the table below:
Figure imgb0005

Beispiele 6-9Examples 6-9

In Maischen gemäß den Beispielen 2 bis 5 wurde jeweils roter Phosphor eingesetzt, der einen pH-Wert von 2,1 aufwies, wodurch der pH-Wert der Maischen entsprechend beeinflußt wurde:

Figure imgb0006
Red phosphorus which had a pH of 2.1 was used in each of the mashes according to Examples 2 to 5, as a result of which the pH of the mash was influenced accordingly:
Figure imgb0006

Beispiel 10Example 10

Eine Mischung nach Beispiel 8 wurde mit Ammoniakwasser auf einen pH-Wert von 7,8 eingestellt. Die daraus wie oben hergestellte Reibfläche war gleichmäßig, elastisch und erst bei scharfen Knickbewegungen schwach brüchig und somit mit »gut« zu bewerten.A mixture according to Example 8 was adjusted to a pH of 7.8 with ammonia water. The friction surface produced from this as above was uniform, elastic and only weakly brittle after sharp kinking movements and thus rated "good".

Beispiele 11 -16Examples 11-16

Ein Binder auf Basis eines Melamin-Formaldehyd-Harzes wurde mit einem Polyester, der in vorstehend beschriebener Weise hergestellt wurde, versetzt. (Dieses Gemisch ist im Handel unter der Bezeichnung ®Madurit VMW 82 erhältlich; Hersteller Cassella AG, Frankfurt.)A binder based on a melamine-formaldehyde resin was mixed with a polyester which was produced in the manner described above. (This mixture is commercially available under the name ®Madurit VMW 82; manufacturer Cassella AG, Frankfurt.)

63 Teilen dieses Gemisches wurden dann 2 Teile Glasmehl (84%<90 µm) und 35 Teile roter Phosphor zugesetzt.63 parts of this mixture were then added 2 parts of glass powder (84% <90 microns) and 35 parts of red phosphorus.

Der pH-Wert der erhaltenen Maische schwankte dabei je nach Provenienz des Phosphors in weiten Grenzen. Zur Abgrenzung der optimalen Kondensationsbedingungen wurde in den Beispielen 13-16 der pH-Wert mit NaOH (40%ig) auf höhere Werte eingestellt.The pH of the mash obtained fluctuated widely depending on the provenance of the phosphorus. In order to delimit the optimal condensation conditions, the pH was adjusted to higher values in NaOH (40%) in Examples 13-16.

Die Maische wurde dann mit einem Pinsel in deckender Schicht auf einen Karton aufgebracht und 3 Minuten bei 120°C getrocknet. Die Bewertung der erhaltenen Reibflächen ist der nachfolgenden Tabelle zu entnehmen.

Figure imgb0007
The mash was then applied to a cardboard in a covering layer with a brush and dried at 120 ° C. for 3 minutes. The evaluation of the friction surfaces obtained is shown in the table below.
Figure imgb0007

Claims (10)

1. Process for making striking surfaces for matches, wherein red phosphorus, abrasive agents, binders which are in the form of aqueous urea/formaldehyde or melaminei'formaldehyde-condensates and, if desired, hardeners and fillers are made into an aqueous suspension, the suspension is applied on to a striking surface substrate and the substrate is heat-treated, if desired, which comprises: admixing the suspension, based on the solid matter content of the condensates used as binder, with 5 to 20 weight%, calculated as solid matter, of an agent cross-linking the amine resin, the cross-linking agent being a polyester or copolymer produced by subjecting an acryl and/or methacryl ester to copolymerization with vinyl acetate in a ratio by weight of 1 : 9 to 9 : 1, the copolymer having optionally up to 20 weight%, based on the monomeric ester proportion, of acrylic acid or methacrylic acid polymerized thereinto; and establishing, in the resulting mixture, a pH-value of 6.5 to 8.0, in the event of the copolymer being added thereto, or a pH-value of 7 to 11, in the event of the polyester being added thereto.
2. Process as claimed in claim 1, wherein 10 to 15 weight% of cross-linking agent is added to the aqueous suspension.
3. Process as claimed in claim 1 or 2, wherein the copolymer is added in the form of an aqueous dispersion.
4. Process as claimed in claim 1 or 2, wherein the polyester is added in the form of an aqueous solution.
5. Process as claimed in any of claims 1 to 3, wherein a pH-value of 7 to 7.5 is established in the mixture having the copolymer therein.
6. Process as claimed in any of claims 1 to 3 or 5, wherein the pH-value is established by addition of phosphoric acid.
7. Process as claimed in any of claims 1 to 3, 5 or 6, wherein the cross-linking agent is an about 50 weight% aqueous dispersion of a copolymer consisting to an extent of more than 50 weight% of acrylic acid-2-ethylhexyl ester and to an extent of less than 50 weight% of vinyl acetate, the dispersion having a second order transition temperature of -180 C.
8. Process as claimed in any of claims 1, 2 or 4, wherein the polyester added has an OH-number of 30 to 450, an acid number of 20 to 300 and a dynamic viscosity of 100 to 750 mPa - s, determined in a 50 weight% solution in butyl glycol.
5. Process as claimed in claim 8, wherein the polyester has an OH-number of 80 to 200 and an acid number of 60 to 100.
10. Process as claimed in any of claims 1, 2, 4, 8 or 9, wherein a pH-value of 9.2 to 9.6 is established in the mixture having the polyester therein.
EP80102454A 1979-07-12 1980-05-06 A process for the preparation of striking surfaces for matches Expired EP0022455B1 (en)

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DE19792928140 DE2928140A1 (en) 1979-07-12 1979-07-12 METHOD FOR THE PRODUCTION OF MATCH WOOD SURFACES
DE2928140 1979-07-12

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GB8608488D0 (en) * 1986-04-08 1986-05-14 Foseco Int Agglomeration of coal fines
US5055113A (en) * 1988-11-23 1991-10-08 Minnesota Mining And Manufacturing Company Abrasive product having binder comprising an aminoplast resin
US4903440A (en) * 1988-11-23 1990-02-27 Minnesota Mining And Manufacturing Company Abrasive product having binder comprising an aminoplast resin

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BE516138A (en) * 1951-12-20
US2863751A (en) * 1954-08-18 1958-12-09 Bjorn Tore Ignition compositions for matches, striking surfaces and the like
US3441456A (en) * 1966-10-31 1969-04-29 Gaf Corp Striker compositions
FR2236817A1 (en) 1973-07-12 1975-02-07 Forestiere Allumettes Soc Ind Safety matches for use in high humidity tropical conditions - in which the head contains polymerisable acrylic ester resin
SU595270A1 (en) 1976-07-12 1978-02-28 Белорусский технологический институт им.С.М.Кирова Method of applying phosphoric mass on match box

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