EP0000867B1 - Adhesives for methacrylic ester plastics - Google Patents
Adhesives for methacrylic ester plastics Download PDFInfo
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- EP0000867B1 EP0000867B1 EP78100311A EP78100311A EP0000867B1 EP 0000867 B1 EP0000867 B1 EP 0000867B1 EP 78100311 A EP78100311 A EP 78100311A EP 78100311 A EP78100311 A EP 78100311A EP 0000867 B1 EP0000867 B1 EP 0000867B1
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- Prior art keywords
- adhesive
- nitromethane
- nitroethane
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- plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/122—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using low molecular chemically inert solvents, swelling or softening agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/125—Adhesives in organic diluents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
- C08L2666/36—Nitrogen-containing compounds
Definitions
- Volatile organic solvents that can dissolve these plastics are used to bond methacrylic ester plastics to one another or to other plastics.
- the solvents swell or dissolve the boundary layers of the plastic parts to be glued and, under favorable conditions, result in an optically almost homogeneous bond after evaporation.
- organic solvents for polymethacrylates, but only a few of them can be used as adhesives.
- the solvent should quickly dissolve the plastic surfaces to be bonded, quickly achieve sufficient stability to prevent unintentional movement of the bonded parts, and cure to form a visually clear, bubble-free and tensile bond.
- the majority of organic solvents only meet part of these requirements.
- the tensile strength of the bonded seam is lower than that of the bonded plastics themselves, so that the bonded seam tears off under load.
- methylene chloride (dichloromethane) has proven to be the most suitable adhesive for acrylic ester plastics to date. It dissolves the plastic quickly and results in a stable bond within 10 seconds, so that often even desired corrections of the mutual position of the plastic parts are no longer possible. The final strength of the bond is reached after two days, but the edge of the bond surface is slightly cloudy, which can only be avoided if work is carried out in an atmosphere of low absolute humidity.
- the object of the invention is to provide adhesives for methacrylic ester plastics which do not have the disadvantages of the known solvents and which result in haze-free and bubble-free bonds with increased tensile strength.
- nitromethane and / or nitroethane are used as an adhesive or as an adhesive additive for methacrylic ester plastics.
- These include polymethyl methacrylate and copolymers of predominant proportions, in particular more than 80% by weight, methyl methacrylate and smaller proportions, in particular less than 20% by weight, of unsaturated comonomers which can be copolymerized therewith, such as other methacrylic acid esters, esters of acrylic acid, styrene, acrylic or methacrylonitrile, vinyl chloride, vinylidene chloride or vinyl esters.
- the plastics to be bonded should be soluble or at least strongly swellable in suitable organic solvents, i.e.
- Nitroethane acts a little more slowly on methacrylic ester plastics than nitromethane. This extends the period of time in which the mutual position of the plastic parts to be glued can be corrected after assembly. As a result of its higher boiling point, nitroethane evaporates more slowly than nitromethane, therefore generates less evaporative cooling and further reduces the risk of the adhesive seam becoming cloudy due to condensation water in high air humidity. This is especially true in the event that nitroethane is mixed with other solvents, e.g. Methylene chloride, is used as an adhesive or additive. Nitroethane can be used in any mixing ratio with nitromethane for all types of application described. The differences mentioned with regard to the rate of action and the rate of evaporation then occur in accordance with the mixing ratio.
- nitromethane or nitroethane can each be used alone as an adhesive, it is preferred to use mixtures of nitromethane and / or nitroethane with other volatile organic liquids with boiling points not above 200 °, preferably below 150 °.
- These liquids can themselves be solvents for the plastics to be bonded and belong to the classes of ketones, esters, ethers or aliphatic chlorinated hydrocarbons, e.g. acetone, cyclohexanone, methyl acetate, butyl acetate, tetrahydrofuran, chloroform, carbon tetrachloride, dichloromethane, dichloroethane, etc.
- These solvents are of their own alone as an adhesive the disadvantages described above.
- Nitromethane alone allows an adhesive tensile strength of 36.6 N / mm 2 to be achieved under the same conditions.
- the aliphatic chlorinated hydrocarbons which alone give similarly high strengths, allow higher strength values when mixed with nitromethane or ethane than with any of the components alone.
- Mixtures of nitromethane or ethane and dichloromethane in a weight ratio between 30:70 to 80:20 are preferably used in the sense of the invention.
- nitromethane or nitroethane in a mixture with organic liquids that are not solvents for the plastics to be bonded and do not develop their own adhesive effect. They can be chosen so that they increase the swelling time or the time until the stability is reached, which is sometimes desirable in the case of difficult bonds. These additives can be less volatile than nitromethane or ethanol. The lower evaporation rate prevents the formation of bubbles in the adhesive seam and the cloudiness due to condensation of air humidity.
- nitromethane or nitroethane or its mixture with volatile organic liquids is used as an adhesive
- the adhesive connection is produced by the material of the plastics to be bonded themselves.
- So-called adhesive varnishes can also be used which contain a polymer dissolved in the solvent.
- the adhesives used according to the invention can be used as such polymer additives e.g. Contain polymethyl methacrylate, polyvinyl acetate, polyvinyl ether or cellulose acetobutyrate.
- the viscosity of the solution places an upper limit on the polymer content.
- the solution viscosity at 20 ° should generally not exceed 10,000 mPa.s. It is advantageous to use about 3 to 30% by weight of such a polymer which gives the solution a viscosity in the range from 500 to 2,000 mPa.s.
- the adhesives to be used according to the invention primarily serve to bond parts made of methacrylic ester plastics to one another.
- materials such as wood, paper, cardboard, leather, metal, ceramic material, glass, porcelain or other types of plastics, for example phenol resin or aminoplast resin moldings, polycarbonate, PVC, urethane foams and the like. If nitromethane or nitroethane alone or their mixtures with volatile organic liquids do not allow the desired adhesive strength to be achieved, adhesive lacquers are advantageously used.
- Acrylic glass is understood to mean cast or extruded polymethyl methacrylate or copolymers of methyl methacrylate with at most 10% by weight of other unsaturated monomers.
- nitromethane or ethane in a mixture with dichloromethane is preferred for this purpose.
- the second table already indicates the use of a solution mixture consisting of 40 parts by weight of nitromethane and 55 parts by weight of dichloromethane, to which 5 parts by weight of phenoxyethanol have been added.
- a solution mixture consisting of 40 parts by weight of nitromethane and 55 parts by weight of dichloromethane, to which 5 parts by weight of phenoxyethanol have been added.
- Phenoxyethanol can be replaced by other glycol ethers such as methyl glycol or alkyl diglycol ether to achieve the same effect.
- these additives should be used in amounts of up to 10% by weight, based on the total solvent mixture.
- test specimens (10 mm x 270 mm x 60 mm) made of polymethyl methacrylate are immersed in nitromethane or nitroethane for approx. 60 seconds and joined together.
- the bond is stable within 120 seconds, ie it no longer slips.
- the adhesive surfaces are brought into intimate contact by loading a joining part with a weight of 150 g / cm 2 .
- the load was maintained for 24 hours.
- 10 test specimens (8 mm x 20 mm x 120 mm) are worked out from the bond and the tensile strength is determined in accordance with DIN 53455. Result 36.6 N / mm 2 or 34.8 N / mm 2 .
- the bonding is carried out as in Example 1.
- a mixture of methylene chloride and nitromethane or nitroethane (60/40) is used as the solvent adhesive.
- the sample is stable in 20 seconds.
- the tensile strength after storage for 14 days is 43.7 N / mm 2 or 36.4 N / mm 2 .
- Example 2 Carried out as described in Example 1. A solution of 30 parts of polymethyl methacrylate in 70 parts of a solvent mixture consisting of methylene chloride / nitromethane or -ethane / phenoxyethanol (57/40/3) is used.
- the bond is stable after 3 minutes. After 14 days of storage, a strength of 37 N / mm 2 or 31.8 N / mm 2 is achieved.
Description
Zum Verkleben von Methacrylesterkunststoffen untereinander oder mit anderen Kunststoffen werden flüchtige organische Lösungsmittel verwendet, die diese Kunststoffe zu lösen vermögen. Die Lösungsmittel quellen oder lösen die Grenzschichten der zu verklebenden Kunststoffteile und ergeben unter günstigen Bedingungen nach dem Verdunsten einen optisch nahezu homogenen Verbund.Volatile organic solvents that can dissolve these plastics are used to bond methacrylic ester plastics to one another or to other plastics. The solvents swell or dissolve the boundary layers of the plastic parts to be glued and, under favorable conditions, result in an optically almost homogeneous bond after evaporation.
Es gibt zahllose organische Lösungsmittel für Polymethacrylate, jedoch sind nur wenige davon als Klebmittel verwendbar. Das Lösungsmittel soll die zu verklebenden Kunststoffflächen schnell anlösen, rasch eine ausreichende Standfestigkeit erreichen lassen, um unbeabsichtigtes Verrücken der verklebten Teile auszuschließen, und zu einer optisch klaren, blasenfreien und zugfesten Verklebung aushärten. Die Mehrzahl der organischen Lösungsmittel erfüllt nur einen Teil dieser Forderungen.There are numerous organic solvents for polymethacrylates, but only a few of them can be used as adhesives. The solvent should quickly dissolve the plastic surfaces to be bonded, quickly achieve sufficient stability to prevent unintentional movement of the bonded parts, and cure to form a visually clear, bubble-free and tensile bond. The majority of organic solvents only meet part of these requirements.
Die meisten Lösungsmittel erzeugen im oberflächennahen Bereich rasch einen hohen Quellungsdruck. Er verursacht besonders bei spannungsreichen, beispielsweise gebogenen, Teilen sogenannte Spannungsrisse, die senkrecht von der Klebfläche ausgehen. Nur wenige Lösungsmittel, z.B. einige aliphatische Chlorkohlenwasserstoffe, erzeugen keine Spannungsrisse. Die meisten davon verdunsten jedoch an der Luft so schnell, daß sich infolge der Verdunstungskälte die Luftfeuchtigkeit in der Klebnaht niederschlägt und eine bleibende Trübung hervorruft. Oft entstehen Luftblasen infolge der Schrumpfung der angequollenen Kunststoffoberfläche beim allmählichen Verdunsten des Lösungsmittels.Most solvents quickly generate a high swelling pressure in the area near the surface. It causes so-called stress cracks, particularly in the case of high-tension, for example curved, parts, which start perpendicularly from the adhesive surface. Few solvents, e.g. some aliphatic chlorinated hydrocarbons do not generate stress cracks. Most of them evaporate so quickly in the air, however, that due to the evaporative cold, the humidity condenses in the bonded seam and causes permanent cloudiness. Air bubbles often arise due to the shrinkage of the swollen plastic surface as the solvent gradually evaporates.
In allen Fällen ist die Zugfestigkeit der Klebnaht geringer als die der verklebten Kunststoffe selbst, so daß bei Belastung die Klebnaht abreißt.In all cases, the tensile strength of the bonded seam is lower than that of the bonded plastics themselves, so that the bonded seam tears off under load.
Unter Berücksichtigung dieser zahlreichen Gesichtspunkte hat sich Methylenchlorid (Dichlormethan) als das bisher bestgeeignete Klebmittel für Acrylesterkunststoffe erwiesen. Es löst den Kunststoff schnell an und ergibt innerhalb von 10 sec eine standfeste Verklebung, so daß oft sogar erwünschte Korrekturen der gegenseitigen Stellung der Kunststoffteile nicht mehr möglich sind. Nach zwei Tagen ist die Endfestigkeit der Verklebung erreicht, jedoch ist der Rand der Klebfläche leicht trüb, was sich nur vermeiden läßt, wenn in einer Atmosphäre von niedriger absoluter Luftfeuchtigkeit gearbeitet wird.Taking these numerous aspects into account, methylene chloride (dichloromethane) has proven to be the most suitable adhesive for acrylic ester plastics to date. It dissolves the plastic quickly and results in a stable bond within 10 seconds, so that often even desired corrections of the mutual position of the plastic parts are no longer possible. The final strength of the bond is reached after two days, but the edge of the bond surface is slightly cloudy, which can only be avoided if work is carried out in an atmosphere of low absolute humidity.
Der Erfindung liegt die Aufgabe zugrunde, Klebmittel für Methacrylesterkunststoffe bereitzustellen, die die Nachteile der bekannten Lösungsmittel nicht aufweisen und trübungs- und blasenfreie Verklebungen von erhöhter Zugfestigkeit ergeben.The object of the invention is to provide adhesives for methacrylic ester plastics which do not have the disadvantages of the known solvents and which result in haze-free and bubble-free bonds with increased tensile strength.
Erfindungsgemäß werden Nitromethan und/oder Nitroäthan als Klebmittel oder als Klebmittelzusatz für Methacrylesterkunststoffe verwendet. Darunter werden Polymethylmethacrylat und Mischpolymerisate aus überwiegenden Anteilen, insbesondere mehr als 80 Gew.-%, Methylmethacrylat und geringeren Anteilen, insbesondere weniger als 20 Gew.-%, an damit mischpolymerisierbaren ungesättigten Comonomeren, wie anderen Methacrylsäureestern, Estern der Acrylsäure, Styrol, Acryl- oder Methacrylnitril, Vinylchlorid, Vinylidenchlorid oder Vinylestern, verstanden. Die zu verklebenden Kunststoffe sollen in geeigneten organischen Lösungsmitteln löslich oder zumindest stark quellbar sein, d.h. sie dürfen nicht oder nur wenig vernetzt sein. Das Molekulargewicht der Kunststoffe spielt für die Verklebbarkeit eine nur untergeordnete Rolle. Daher können unschmelzbare Substanzpolymerisate ebenso verklebt werden wie extrudierte oder spritzgegossene Kunststoffteile. Die Verklebbarkeit von Spritzgußteilen gehört zu den besonderen Vorzügen der Klebmittel der Erfindung.According to the invention, nitromethane and / or nitroethane are used as an adhesive or as an adhesive additive for methacrylic ester plastics. These include polymethyl methacrylate and copolymers of predominant proportions, in particular more than 80% by weight, methyl methacrylate and smaller proportions, in particular less than 20% by weight, of unsaturated comonomers which can be copolymerized therewith, such as other methacrylic acid esters, esters of acrylic acid, styrene, acrylic or methacrylonitrile, vinyl chloride, vinylidene chloride or vinyl esters. The plastics to be bonded should be soluble or at least strongly swellable in suitable organic solvents, i.e. they may not be networked or only slightly. The molecular weight of the plastics only plays a subordinate role for the bondability. Therefore, non-meltable bulk polymers can be glued as well as extruded or injection molded plastic parts. The bondability of injection molded parts is one of the particular advantages of the adhesives of the invention.
Nitroäthan wirkt auf Methacrylesterkunststoffe etwas langsamer ein als Nitromethan. Dadurch wird die Zeitspanne verlängert, in der sich die gegenseitige Stellung der zu verklebenden Kunststoffteile nach dem Zusammenfügen korrigieren läßt. Infolge seines höheren Siedepunktes verdunstet Nitroäthan langsamer als Nitromethan, erzeugt daher weniger Verdunstungskälte und setzt die Gefahr, daß sich die Klebnaht bei hoher Luftfeuchtigkeit durch Kondenswasser trübt, noch weiter herab. Das gilt besonders in dem Fall, daß Nitroäthan im Gemisch mit anderen Lösungsmitteln, wie z.B. Methylenchlorid, als Klebmittel oder Klebmittelzusatz verwendet wird. Nitroäthan kann in jedem beliebigen Mischungsverhältnis mit Nitromethan für alle beschriebenen Anwendungsarten eingesetzt werden. Die erwähnten Unterschiede hinsichtlich der Einwirkungs- und der Verdunstungsgeschwindigkeit treten dann nach Maßgabe des Mischungsverhältnisses ein.Nitroethane acts a little more slowly on methacrylic ester plastics than nitromethane. This extends the period of time in which the mutual position of the plastic parts to be glued can be corrected after assembly. As a result of its higher boiling point, nitroethane evaporates more slowly than nitromethane, therefore generates less evaporative cooling and further reduces the risk of the adhesive seam becoming cloudy due to condensation water in high air humidity. This is especially true in the event that nitroethane is mixed with other solvents, e.g. Methylene chloride, is used as an adhesive or additive. Nitroethane can be used in any mixing ratio with nitromethane for all types of application described. The differences mentioned with regard to the rate of action and the rate of evaporation then occur in accordance with the mixing ratio.
Obwohl Nitromethan oder Nitroäthan jeweils allein als Klebmittel verwendet werden können, wird es bevorzugt, Gemische des Nitromethans und/oder Nitroäthans mit anderen flüchtigen organischen Flüssigkeiten mit Siedepunkten nicht über 200°, vorzugsweise unter 150°, zu verwenden. Diese Flüssigkeiten können selbst Lösungsmittel für die zu verklebenden Kunststoffe sein und den Klassen der Ketone, Ester, Äther oder aliphatischen Chlorkohlenwasserstoffe angehören, z.B. Aceton, Cyclohexanon, Methylacetat, Butylacetat, Tetrahydrofuran, Chloroform, Tetrachlorkohlenstoff, Dichlormethan, Dichloräthan usw. Diese Lösungsmittel haben für sich allein als Klebmittel die oben geschilderten Nachteile. Im Gemisch mit wenigstens 30 Gew.-% Nitromethan oder -äthan (berechnet auf das Gewicht des Gemisches) werden diese Nachteile erheblich unterdrückt. So nimmt die Spannungsrißbildung deutlich ab und die Klebfestigkeit wird erhöht. In der nachfolgenden Tabelle ist die Klebzugfestigkeit von verklebten Teilen aus extrudiertem Acrylglas 14 Tage nach der Verklebung angegeben.
Nitromethan allein läßt unter den gleichen Bedingungen eine Klebzugfestigkeit von 36,6 N/mm2 erreichen. Die aliphatischen Chlorkohlenwasserstoffe, die allein ähnlich hohe Festigkeiten ergeben, lassen im Gemisch mit Nitromethan oder -äthan höhere Festigkeitswerte erreichen als mit jeder der Komponenten allein. Gemische aus Nitromethan oder -äthan und Dichlormethan in einem Gewichtsverhältnis zwischen 30 : 70 bis 80 : 20 werden bevorzugt im Sinne der Erfindung verwendet.Nitromethane alone allows an adhesive tensile strength of 36.6 N / mm 2 to be achieved under the same conditions. The aliphatic chlorinated hydrocarbons, which alone give similarly high strengths, allow higher strength values when mixed with nitromethane or ethane than with any of the components alone. Mixtures of nitromethane or ethane and dichloromethane in a weight ratio between 30:70 to 80:20 are preferably used in the sense of the invention.
Man kann Nitromethan oder Nitroäthan auch im Gemisch mit solchen organischen Flüssigkeiten anwenden, die keine Lösungsmittel für die zu verklebenden Kunststoffe sind und keine eigene Klebwirkung entwickeln. Sie können so gewählt werden, daß sie die Quellzeit oder die Zeit bis zum Erreichen der Standfestigkeit verlängern, was bei schwierigen Verklebungen zuweilen erwünscht ist. Diese Zusätze können weniger flüchtig als Nitromethan oder -äthan sein. Die geringere Verdunstungsgeschwindigkeit verhindert die Blasenbildung in der Klebnaht und die Trübung durch Kondensation von Luftfeuchtigkeit.You can also use nitromethane or nitroethane in a mixture with organic liquids that are not solvents for the plastics to be bonded and do not develop their own adhesive effect. They can be chosen so that they increase the swelling time or the time until the stability is reached, which is sometimes desirable in the case of difficult bonds. These additives can be less volatile than nitromethane or ethanol. The lower evaporation rate prevents the formation of bubbles in the adhesive seam and the cloudiness due to condensation of air humidity.
Beispiele für derartige Mischungen und die bei der Verklebung von extrudiertem Acrylglas erzielten Festigkeiten sind in der nachfolgenden Tabelle angegeben :
Wenn Nitromethan oder Nitroäthan oder dessen Gemisch mit flüchtigen organischen Flüssigkeiten als Klebmittel eingesetzt werden, wird die Klebverbindung durch das Material der zu verklebenden Kunststoffe selbst hergestellt. Man kann auch sogenannte Kleblacke verwenden, die in dem Lösungsmittel ein gelöstes Polymerisat enthalten.If nitromethane or nitroethane or its mixture with volatile organic liquids is used as an adhesive, the adhesive connection is produced by the material of the plastics to be bonded themselves. So-called adhesive varnishes can also be used which contain a polymer dissolved in the solvent.
Nach dem Verdunsten des Lösungsmittels bildet das Polymerisat die Klebverbindung. Die erfindungsgemäß verwendeten Klebmittel können als derartige Polymerisatzusätze z.B. Polymethyl methacrylat, Polyvinylacetat, Polyvinyläther oder Celluloseacetobutyrat enthalten. Dem Polymerisatanteil ist durch die Viskosität der Lösung eine obere Grenze gesetzt. Die Lösungsviskosität bei 20° soll im allgemeinen nich über 10 000 mPa.s liegen. Mit Vorteil werden etwa 3 bis 30 Gew.-% eines solchen Polymeren verwendet, das eine Viskosität der Lösung im Bereich von 500 bis 2 000 mPa.s ergibt.After the solvent has evaporated, the polymer forms the adhesive bond. The adhesives used according to the invention can be used as such polymer additives e.g. Contain polymethyl methacrylate, polyvinyl acetate, polyvinyl ether or cellulose acetobutyrate. The viscosity of the solution places an upper limit on the polymer content. The solution viscosity at 20 ° should generally not exceed 10,000 mPa.s. It is advantageous to use about 3 to 30% by weight of such a polymer which gives the solution a viscosity in the range from 500 to 2,000 mPa.s.
Die erfindungsgemäß zu verwendenden Klebmittel dienen in erster Linie dazu, Teile aus Methacrylesterkunststoffen untereinander zu verkleben. Um diese mit anderen Werkstoffen, wie Holz, Papier, Karton, Leder, Metall, keramischem Material, Glas, Porzellan oder andersartigen Kunststoffen, z.B. Phenolharz-oder Aminoplastharz-Formkörpern, Polycarbonat, PVC, Urethanschaumstoffen und dergl., zu verkleben, werden, wenn Nitromethan oder Nitroäthan allein oder deren Gemische mit flüchtigen organischen Flüssigkeiten nicht die erwünschte Klebfestigkeit erreichen lassen, mit Vorteil Kleblacke verwendet.The adhesives to be used according to the invention primarily serve to bond parts made of methacrylic ester plastics to one another. In order to glue them to other materials, such as wood, paper, cardboard, leather, metal, ceramic material, glass, porcelain or other types of plastics, for example phenol resin or aminoplast resin moldings, polycarbonate, PVC, urethane foams and the like, If nitromethane or nitroethane alone or their mixtures with volatile organic liquids do not allow the desired adhesive strength to be achieved, adhesive lacquers are advantageously used.
Die Verklebung von Teilen aus Acrylglas, insbesondere extrudiertem Acrylglas, untereinander stellt ein bevorzugtes Anwendungsgebiet der Erfindung dar. Dabei werden unter Acrylglas gegossenes oder extrudiertes Polymethyl-methacrylat oder Mischpolymerisate des Methyl-methacrylats mit höchstens 10 Gew.-% an anderen ungesättigten Monomeren verstanden. Die Verwendung von Nitromethan oder - äthan im Gemisch mit Dichlormethan wird für diesen Zweck bevorzugt.The bonding of parts made of acrylic glass, in particular extruded acrylic glass, to one another represents a preferred field of application of the invention. Acrylic glass is understood to mean cast or extruded polymethyl methacrylate or copolymers of methyl methacrylate with at most 10% by weight of other unsaturated monomers. The use of nitromethane or ethane in a mixture with dichloromethane is preferred for this purpose.
In der zweiten Tabelle ist bereits auf die Verwendung eines Lösungsgemisches, bestehend aus 40 Gew.-Teilen Nitromethan und 55 Gew.-Teilen Dichlormethan, dem 5 Gew.-Teile Phenoxyäthanol zugesetzt wurden, hingewiesen. Eine solche Nitromethan oder-äthan enthaltende Dreierkombination, die hinsichtlich ihrer mengenmäßigen Zusammensetzung variieren kann, verdient hervorgehoben zu werden, da bei ihrer Anwendung auch beim Arbeiten in einer Atmosphäre mit hoher relativer Luftfeuchtigkeit klare Klebnähte erhalten werden. Phenoxyäthanol kann unter Erzielung des gleichen Effekts durch andere Glykoläther, wie Methylglykol oder Alkyldiglykoläther, ersetzt werden. Zur Erhaltung einer hohen Klebfestigkeit sollen diese Zusätze in Mengen bis 10 Gew.-%, bezogen auf das gesamte Lösungsmittelgemisch, zur Anwendung kommen.The second table already indicates the use of a solution mixture consisting of 40 parts by weight of nitromethane and 55 parts by weight of dichloromethane, to which 5 parts by weight of phenoxyethanol have been added. Such a combination of three containing nitromethane or ethane, which can vary in terms of its quantitative composition, deserves to be emphasized, since when it is used, clear adhesive seams are obtained even when working in an atmosphere with high relative atmospheric humidity. Phenoxyethanol can be replaced by other glycol ethers such as methyl glycol or alkyl diglycol ether to achieve the same effect. To maintain a high adhesive strength, these additives should be used in amounts of up to 10% by weight, based on the total solvent mixture.
In den nachfolgenden Beispielen werden jeweils eine Verklebung unter Verwendung von Nitromethan und eine zweite Verklebung unter Verwendung von Nitroäthan unter sonst gleichen Bedingungen durch-geführt. Bei den Festigkeitsergebnissen wird jeweils zuerst der mit Nitromethan und danach der mit Nitroäthan erhaltene Wert angegeben.In the examples below, one bond using nitromethane and a second bond using nitroethane are carried out under otherwise identical conditions. In the strength results, the value obtained with nitromethane and then with nitroethane is given first.
Die Längsseiten zweier Probekörper (10 mm x 270 mm x 60 mm) aus Polymethylmethacrylat werden ca. 60 sec. in Nitromethan bzw. Nitroäthan getaucht und zusammengefügt. Der Verbund ist innerhalb von 120 sec. standfest, d.h. er verrutscht nicht mehr. Durch Belastung eines Fügeteils mit einem Gewicht von 150 g/cm2 werden die Klebflächen in innigen Kontakt gebracht. Die Belastung wurde 24 Std. aufrechterhalten. Nach 13 Tagen Lagerung ohne Belastung bei Raumtemperatur werden 10 Probekörper (8 mm x 20 mm x 120 mm) aus der Verklebung herausgearbeitet und die Zugfestigkeit in Anlehnung an DIN 53455 ermittelt. Ergebnis 36,6 N/mm2 bzw. 34,8 N/mm2.The long sides of two test specimens (10 mm x 270 mm x 60 mm) made of polymethyl methacrylate are immersed in nitromethane or nitroethane for approx. 60 seconds and joined together. The bond is stable within 120 seconds, ie it no longer slips. The adhesive surfaces are brought into intimate contact by loading a joining part with a weight of 150 g / cm 2 . The load was maintained for 24 hours. After 13 days of storage without load at room temperature, 10 test specimens (8 mm x 20 mm x 120 mm) are worked out from the bond and the tensile strength is determined in accordance with DIN 53455. Result 36.6 N / mm 2 or 34.8 N / mm 2 .
Durchführung der Verklebung wie in Beispiel 1. Als Lösungsmittelkleber wird eine Mischung aus Methylenchlorid und Nitromethan bzw. Nitroäthan (60/40) angewendet. Die Probe ist in 20 sec. standfest. Die Zugfestigkeit nach 14 Tagen Lagerung beträgt 43,7 N/mm2 bzw. 36,4 N/mm2.The bonding is carried out as in Example 1. A mixture of methylene chloride and nitromethane or nitroethane (60/40) is used as the solvent adhesive. The sample is stable in 20 seconds. The tensile strength after storage for 14 days is 43.7 N / mm 2 or 36.4 N / mm 2 .
Durchführung wie in Beispiel beschrieben. Zur Verklebung wird das Lösungsmittelgemisch Methylenchlorid/Nitromethan bzw. -äthan/Phenoxyäthanol (55/40/5) verwendet. Die Klebnaht ist völlig klar und blasenfrei. Nach 14 Tagen Lagerung bei Raumtemperatur wird eine Festigkeit von 43 N/mm2 bzw. 33,7 N/mm2 erreicht.Execution as described in the example. The solvent mixture methylene chloride / nitromethane or -ethane / phenoxyethanol (55/40/5) is used for bonding. The adhesive seam is completely clear and bubble-free. After 14 days of storage at room temperature, a strength of 43 N / mm 2 or 33.7 N / mm 2 is achieved.
Durchführung wie in Beispiel 1 beschrieben. Zur Anwendung kommt eine Lösung von 30 Teilen Polymethylmethacrylat in 70 Teile eines Lösungsmittelgemisches, bestehend aus Methylenchlorid/Nitromethan bzw. -äthan/Phenoxyäthanol (57/40/3).Carried out as described in Example 1. A solution of 30 parts of polymethyl methacrylate in 70 parts of a solvent mixture consisting of methylene chloride / nitromethane or -ethane / phenoxyethanol (57/40/3) is used.
Die Verklebung ist nach 3 Minuten standfest. Nach 14 Tagen Lagerung wird eine Festigkeit von 37 N/mm2 bzw. 31,8 N/mm2 erreicht.The bond is stable after 3 minutes. After 14 days of storage, a strength of 37 N / mm 2 or 31.8 N / mm 2 is achieved.
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2737270 | 1977-08-18 | ||
| DE2737270A DE2737270C3 (en) | 1977-08-18 | 1977-08-18 | Adhesives for methacrylic ester plastics |
| DE2745420 | 1977-10-08 | ||
| DE19772745420 DE2745420A1 (en) | 1977-10-08 | 1977-10-08 | Solvent adhesives for methyl methacrylate! (co)polymer articles - contain nitromethane and or nitro-ethane opt. mixed with volatile liquids and dissolved polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000867A1 EP0000867A1 (en) | 1979-03-07 |
| EP0000867B1 true EP0000867B1 (en) | 1981-04-15 |
Family
ID=25772566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100311A Expired EP0000867B1 (en) | 1977-08-18 | 1978-07-06 | Adhesives for methacrylic ester plastics |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0000867B1 (en) |
| JP (1) | JPS6056177B2 (en) |
| CA (1) | CA1117856A (en) |
| DE (1) | DE2860616D1 (en) |
| IT (1) | IT1160596B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4401160A1 (en) * | 1994-01-17 | 1995-07-20 | Roehm Gmbh | Adhesive for methacrylic ester plastics |
| JPH08176517A (en) * | 1994-12-22 | 1996-07-09 | Chugoku Kako Kk | Bonding by melting synthetic resin foam material |
| WO2016026884A1 (en) * | 2014-08-21 | 2016-02-25 | Sabic Global Technologies B.V. | An adhesive composition forming structurally integral bonds with the bonding surfaces of the substrates |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE818205A (en) * | 1973-07-30 | 1974-11-18 | Adhesive for bonding polyurethane rubber to substrates - consists of org. isocyanate and nitroso or nitro cpd as adhesion promoter |
-
1978
- 1978-07-06 EP EP78100311A patent/EP0000867B1/en not_active Expired
- 1978-07-06 DE DE7878100311T patent/DE2860616D1/en not_active Expired
- 1978-08-11 CA CA000309139A patent/CA1117856A/en not_active Expired
- 1978-08-17 IT IT7868920A patent/IT1160596B/en active
- 1978-08-18 JP JP53100849A patent/JPS6056177B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2860616D1 (en) | 1981-05-07 |
| CA1117856A (en) | 1982-02-09 |
| IT1160596B (en) | 1987-03-11 |
| IT7868920A0 (en) | 1978-08-17 |
| JPS5443276A (en) | 1979-04-05 |
| JPS6056177B2 (en) | 1985-12-09 |
| EP0000867A1 (en) | 1979-03-07 |
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