EP2245102A1 - Biologisch abbaubare schmelzkleberzusammensetzung - Google Patents

Biologisch abbaubare schmelzkleberzusammensetzung

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Publication number
EP2245102A1
EP2245102A1 EP09721207A EP09721207A EP2245102A1 EP 2245102 A1 EP2245102 A1 EP 2245102A1 EP 09721207 A EP09721207 A EP 09721207A EP 09721207 A EP09721207 A EP 09721207A EP 2245102 A1 EP2245102 A1 EP 2245102A1
Authority
EP
European Patent Office
Prior art keywords
composition according
formula
weight
hot melt
melt adhesive
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Withdrawn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
EP09721207A
Other languages
English (en)
French (fr)
Inventor
Christophe Robert
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.)
Bostik SA
Original Assignee
Bostik SA
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 Bostik SA filed Critical Bostik SA
Publication of EP2245102A1 publication Critical patent/EP2245102A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C09J123/0884—Epoxide containing esters
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0884—Epoxide containing esters
    • 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
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to biodegradable hot melt adhesive compositions and their use in many fields of application and in particular in the field of packaging.
  • Technological Background of the Invention In the context of the evolution of markets towards so-called "organic" products, the major players of the large retailers are turning to their suppliers to demand products meeting these expectations.
  • ENl 3432 specifies that the biodegradability of a product measured according to EN ISO 14855 method by analysis of released carbon dioxide must be greater than 90%.
  • the provision of generally compostable or biodegradable packaging objects therefore also involves the provision of compostable and / or biodegradable hot melt (or hot melt) adhesive compositions.
  • a hot melt glue to also comply with this EN ISO 14855 biodegradability standard while retaining all the other properties of a standard hot melt glue, including the properties necessary for labeling application. any type of food container or not.
  • No. 5,312,850 describes the production of hot melt adhesive compositions using certain ingredients known to be biodegradable. These compositions comprise 20 to 98% by weight of polylactide polymer (PLA) containing at least 20 mol% of lactide monomer, 2 to 80% of a tackifying resin having a softening point according to ASTM E 26 of about 60 0 C, 0 to 50% of a plasticizer and 0 to 30 % of a wax as a diluting agent and 0 to 3% of a stabilizing agent. No indication is provided as to the biodegradability of the final composition according to EN ISO 14855.
  • PLA polylactide polymer
  • HMPSA hot-melt pressure-sensitive adhesive compositions
  • compositions which contain PLA are not suited to the fields of food packaging because they have the drawbacks of being rather rigid and of having a heat reactivation temperature that is too high for applications in the desired fields.
  • EP553394 discloses the production of hot melt adhesive compositions comprising a specific polyester obtained from 3-hydroxy-butyric acid and 3-hydroxy-valeric acid. No indication is provided as to the biodegradability of the final composition according to EN ISO 14855.
  • EP 741178 also describes obtaining hot-melt adhesive biodegradable compositions comprising a specific polyester obtained by reaction between a dicarboxylic acid and an ether or diglycidyl ester. No indication is provided as to the biodegradability of the final composition according to EN ISO 14855.
  • the object of the present invention is therefore to provide hot-melt adhesive compositions, preferably without residual tack at room temperature (in other words without tack or even immediate tack at room temperature) and whose biodegradability, measured according to the method by carbon dioxide released according to EN ISO 14855, is greater than 55%, preferably greater than 60%, preferably greater than 90%. This percentage is given by reference to the biodegradability measure of the cellulose which represents under the same conditions 100%.
  • a biodegradable hot melt adhesive composition comprising (A) from 30% to 90%, preferably 40% to 60%; or else from 45% to 55% by weight relative to the total weight of the adhesive composition of a (co) polymer chosen from (Al) the polycaprolactones, (A2) the polyesters resulting from the condensation between a dicarboxylic acid of formula Rl - [COOH] 2 in which R1 represents a linear or slightly branched or cyclic, saturated or unsaturated, mono or polyhydroxylated C2 to C30 hydrocarbon group and a diol of formula R2 [OH] 2 in which R2 represents a C2-C2 hydrocarbon group; C32 linear, weakly branched, cyclic or polycyclic, saturated, unsaturated or polyunsaturated, mono- or polyhydroxylated or (A3) copolymers of polycaprolactones (Al) and of polyesters (A2); (B) from 10% to 50%, preferably from 20% to 40%, or from 25% to 35% by weight relative to the
  • a stiffening agent represented by a wax having a melting point in the range of 40 ° C at 150 ° C, preferably selected from optionally hydroxylated amide waxes, hydrogenated castor oils, or oxidized or unoxidized synthetic waxes, functionalized or otherwise, polyethylene oxides whose weight average molecular weight is greater than 1000;
  • the (co) polymer (A) has a number-average molecular weight (Mn) ranging from 500 to 100 000 g / mol, preferably from 2000 to 60000 g / mol.
  • the dicarboxylic acid of formula R [COOH] 2 is selected from sebacic acid, succinic acid, adipic acid, aldaric, alpha-ketoglutarique, aspartic acid, azelaic acid, camphoric acid, fumaric acid, glutaconic acid, glutaric itaconic, maleic, malic, malonic, meglutol, mesaconic, mesoxalic, 3-methylglutaconic.
  • R2 [OH] 2 is chosen from diols of linear structure, weakly branched, saturated or unsaturated, of formula R2 [OH] 2 in which R2 represents a C2-C22 hydrocarbon group, the diols of formula HO - (- CH2- CH2-O-) n -H such that n is an integer of 1 to 6.
  • composition according to the invention (B) is chosen from glycerol or pentaerythritol rosin esters, terpenes or terpenes phenol, in particular phenol terpenes with a softening point of between 100 ° C. and 150 ° C.
  • composition according to the invention (C) is chosen from amide type oleamide, stearamide, ethylene bis-oleamide and ethylene bis-stearamide amides, preferably those having a melting point of between 60 ° C. and 120 ° C.
  • (A) represents a polyester obtained by reaction between monoethylene glycol and sebacic acid
  • (B) represents a phenolic terpene resin
  • (C) represents an amide wax selected from oleamide or cis 1,3 docosenamide erucamide
  • (D) represents a blocking enhancement additive selected from polyethylene glycol, precipitated silica or a mixture thereof.
  • hot-melt adhesives according to the invention also have the following properties:
  • viscosity in a wide range from 500 to 200,000 mPa.s, which makes them adaptable to applications on flexible support or non-flexible support;
  • reactivation temperature ranging from about 40 ° C. to 150 ° C., which makes them suitable for any type of flexible or non-flexible application; for more specific applications on flexible support, one will choose formulations whose reactivation temperature is in the range 60-1 10 0 C.
  • a hot-melt adhesive having an open time of almost zero or less than 1 second or preferably less than 0.5 seconds will be chosen; for rigid support applications, a hot melt adhesive having an open time greater than or equal to 2 seconds, preferably from 3 to 30 seconds or from 5 to 15 seconds will be chosen.
  • the composition according to the invention has an open time measured on OLINGER apparatus less than 1 second, preferably less than 0.5 seconds).
  • the composition according to the invention has an open time measured on OLINGER apparatus greater than or equal to 2 seconds, preferably ranging from 5 to 30 seconds).
  • the invention relates to the use of a composition according to the invention that can be reactivated to create a seal between two non-flexible supports, for example two cartons.
  • a composition according to the invention that can be reactivated to create a seal between two non-flexible supports, for example two cartons.
  • the use is carried out with a composition whose viscosity is between 500 and 20000 mPa.s for applications by melter and roll coating.
  • the use is carried out with a composition whose viscosity is between 2000 and 50000 mPa.s for applications by melter or barrel and nozzle coating.
  • the use is carried out with a composition whose viscosity is between 70000 and 200000 mPa.s for applications by extruder and coating by nozzle.
  • the invention relates to the use of a composition according to the invention for the preparation of non-flexible to rigid biodegradable packaging intended for food or non-food use.
  • the invention relates to the use of a composition according to the invention for textile applications such as automotive or aeronautical lining, cosmetics, tobacco, pharmaceutical, medical.
  • the invention relates to the use of a composition according to the invention for the preparation of rigid packaging, box closure and cases, the formation of cardboard tray, the labeling of bottles, the binding , cardboard paper coating.
  • This part comprises a (co) polymer preferably having a molecular weight of 500 to 100000 g / mol, chosen from (Al) polycaprolactones, (A2) the polyesters resulting from the condensation between a dicarboxylic acid of formula R1- [COOH] 2 in which R1 represents a linear or slightly branched or cyclic, saturated or unsaturated, mono or polyhydroxylated C2 to C30 hydrocarbon group and a diol of formula R2 [ OH] 2 in which R2 represents a linear, slightly branched, cyclic or polycyclic, saturated, unsaturated or polyunsaturated, mono- or polyhydroxylated C 2 to C 32 hydrocarbon group, or (A3) copolymers obtained from polycaprolactones (Al) and polyesters; (A2) or one of their mixture.
  • R1- [COOH] 2 in which R1 represents a linear or slightly branched or cyclic, saturated or unsaturated, mono or polyhydroxylated C2 to C
  • (A) is from 30% to 90%, preferably 40% to 60%; more preferably 45% to 55% by weight relative to the total weight of the adhesive composition.
  • Polycaprolactones are formed by ring-opening reaction of an epsilon-caprolactone monomer with a mono-, di-, or multi-functional initiator in which the functional groups, generally hydroxy groups, are capable of perform a ring opening reaction with epsilon-caprolactone momoners.
  • the initiator will be a minor component and the weight ratio of initiator to monomer will determine the molecular weight of the resulting polymer.
  • the polycaprolactone polymers preferably have a molecular weight of 5000 to 100000 g / mol.
  • the polyesters of the invention are formed by reaction between a dicarboxylic acid of formula R1- [COOH] 2 in which R1 represents a linear or slightly branched or cyclic, saturated or unsaturated, mono or polyhydroxylated C2 to C30 hydrocarbon group and a diol of formula R2 [OH] 2 in which R2 represents a linear, weakly branched, cyclic or polycyclic, saturated, unsaturated or polyunsaturated, mono or polyhydroxylated hydrocarbon group,
  • the diacid is chosen alone or as a mixture from:
  • R1- [COOH] 2 a linear diacid, saturated or unsaturated, of natural or synthetic origin of formula R1- [COOH] 2 in which R1 represents a C2-C30 hydrocarbon group such as, for example, succinic acid, glutaric acid, pimelic acid, acid azelaic acid, sebacic acid, traumatic acid, suberin ( ⁇ , ⁇ -diacids C 6 to C 26);
  • a mono- or polyhydroxy diacid such as, for example, tartaric acid, tartaronic acid, aldaric acids
  • the dicarboxylic acids are preferably chosen from the acids, adipic, aldaric, alpha-ketoglutaric, aspartic, azelaic, camphoric, fumaric, glutaconic, glutaric, itaconic, maleic, malic, malonic, meglutol, mesaconic, mesoxalic, 3-methylglutaconic, alone. or one of their mix.
  • the diols are chosen alone or in mixture from:
  • DAG 3,6-dianhydro-D-glucitol
  • DAM 3,6-dianhydro-D-Mannitol
  • DAI 6-Dianhydro-L-Iditol
  • R2 represents a monoethylene glycol or polyethylene glycol of formula HO - (- CH2-CH2-O-) n -H such that n is between 1 and 6.
  • the diols are preferably chosen from diols of linear structure, saturated or unsaturated, of structure of formula R2 [OH] 2 in which R2 represents a C2-C22 hydrocarbon group, diols of formula HO - (- CH2-CH2- O-) n -H where n is an integer from 1 to 6.
  • the polyesters of the invention preferably have a number average molecular weight (Mn) of between 500 and 100,000 g / mol.
  • the polyesters of the invention preferably have an MFI at 160 ° C. under 2.16 kg of between 0.2 and 1000.
  • the polyester will have a number-average molecular weight (Mn) of between 2000 and 60000 g / m 2. mol and an MFI of between 1 and 500 g / mol.
  • the polyesters of the invention are obtained by reaction of monoethylene glycol with sebacic acid.
  • the chosen diacid is an aromatic diacid
  • the content of aromatic diacid (terephthalic or isophthalic type) in the polyester will be less than 53 mol%, preferably less than 25%, especially less than 25% isophthalic aromatic.
  • the tackifying resin or resins have average molar masses by weight M w generally between 300 and 5000 and are chosen in particular from:
  • Rosin of natural origin or modified such as for example rosin extracted from pine gum, wood rosin extracted from tree roots and their hydrogenated derivatives, partially hydrogenated, dimerized, polymerized or esterified by monoalcohols or polyols such as glycerol;
  • terpene resins generally resulting from the polymerization of terpenic hydrocarbons such as for example mono-terpene (or pinene) in the presence of Friedel-Crafts catalysts, optionally modified by the action of phenols;
  • copolymers based on natural terpenes for example styrene / terpene, alpha-methyl styrene / terpene and vinyl toluene / terpene.
  • (B) is from 10% to 50%, preferably from 20% to 40%, more preferably from 25% to 35% by weight, based on the total weight of the adhesive composition.
  • (B) is preferably chosen from rosin esters containing glycerol or pentaerythritol, terpenes or terpenes phenol, in particular phenol terpenes having a softening point of between 100 ° C. and 150 ° C.
  • the softening temperature (or point) of these resins is determined according to the ASTM E 28 standard test, the principle of which is as follows.
  • a brass ring about 2 cm in diameter is filled with the resin to be tested in the molten state.
  • the ring and the solid resin are placed horizontally in a thermostated bath of glycerine whose temperature can vary from 5 ° C per minute.
  • a steel ball with a diameter of about 9.5 mm is centered on the solid resin disc.
  • the softening temperature is - during the temperature rise phase of the bath at a rate of 5 ° C per minute - the temperature at which the resin disc flows 25.4 mm under the weight of the ball.
  • C Rigidifying agent part.
  • These agents are waxes characterized by a melting point measured by differential scanning calorimetry DSC, between 40 0 C and 150 ° C, preferably between 50 ° C and 100 ° C in the case of a coating on flexible support delayed bonding and between 100 ° C and 140 ° C in the case of an immediate bonding application on a flexible or non-flexible support.
  • waxes are chosen from optionally hydroxylated amide waxes, hydrogenated castor oils, or oxidized or unoxidized synthetic waxes, functionalized or otherwise, polyethylene oxides whose weight average molecular weight is greater than 1000.
  • the waxes chosen are preferably chosen from ethylene bis stearamide, ethylene bis oleamide, stearamide, paraffins, fischer tropsch waxes, oleamides, cis-1,3-docosenamide, erucamide and the like. ethylene glycol monostearate, cetyl palmitate, saturated linear alcohols, carboxylic acids, and the waxes chosen from amide-type amide, stearamide, ethylene bis-oleamide and ethylene bis-stearamide waxes, preferably amide type oleamide, stearamide, ethylene bis-oleamide waxes having a melting point between 60 ° C and 120 ° C.
  • (C) is from 10% to 30%, preferably 10% to 25% by weight based on the total weight of the adhesive composition.
  • (C) is preferably an amide wax selected from oleamide or cis 1,3 docosenamide erucamide.
  • an amount of from 0% to 20%, preferably 3% to 7% by weight, based on the total weight of the adhesive composition of one or more additives, may optionally be used.
  • additives are chosen from stabilizers, antioxidants, blocking agents, pigments, dyes or fillers.
  • Stabilizers or antioxidants are introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat, light or catalysts residuals on certain raw materials such as tackifying resins.
  • the compounds selected from pentaerythritol Tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2- (1- (2-hydroxy-3,5-ditertiopenthylphenyl) ethyl acrylate are used.
  • aromatic polycarbodiimide substituted diarylcarbodiimide, aromatic polycarbodiimide.
  • Any primary antioxidants are used which trap free radicals and are generally substituted phenols like Irganox ® 1010 from the CIBA (tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate pentaerythritol).
  • the primary antioxidants can be used alone or in combination with other antioxidants such as phosphites such as Irgafos ® 168 also CIBA, or with UV stabilizers such as amines.
  • the blocking improvers are introduced in particular to prevent the adhesion of the coated surface of hot melt adhesive on the printed face during the production and storage of the coils. For example for yogurt wrapping applications.
  • These compounds are selected from ethylene bis-stearamide, ethylene bis-amide, stearamide, oleamide, cis-1,3-docosenamide, erucamide, ethylene glycol monostearate, cetyl palmitate, saturated linear alcohol, carboxylic acid.
  • Polyethylene glycol or precipitated silica may also be used.
  • (D4) fillers are introduced to reinforce the cohesion of the adhesive, reduce the cost, or modify the adhesive performance by varying the amount and nature of the feed introduced.
  • These compounds are chosen from talc, carbonates, silica, kaolin, sulphates and clays. Process for the preparation of the compositions
  • the hot melt composition according to the invention is prepared by simply mixing its components at a temperature of between 100 and 200 ° C., until a homogeneous mixture is obtained. Required * mixing techniques are well known in the art. Properties of the compositions according to the invention.
  • compositions have all the properties necessary to be biodegradable hot melt adhesive compositions. Biodegradability.
  • the adhesive compositions are preferably non-pressure sensitive, with no residual tack at room temperature. Insofar as the compositions of the invention do not exhibit residual tack at room temperature, no plasticizer is introduced because they are generally liquid at room temperature and their melting point is low, less than 25 ° C.
  • the selected formulations also have the following properties: Viscosity.
  • the final viscosity of the hot melt adhesive according to the invention is dependent on the nature of the components used, their respective amount and their molar mass.
  • hot melt adhesives have a viscosity in a wide range of 500 to 200,000 mPa.s at the application temperature, making them adaptable to applications according to different types of processes or tools.
  • flexible support or non-flexible support are examples of flexible support or non-flexible support.
  • the applications can be targeted by melter and roller coating.
  • the viscosity is between 2000 and 50000 mPa.s at the application temperature we can target the applications by melter or barrel and nozzle coating. When the viscosity is between 70000 and 200000 mPa.s at the application temperature can be targeted applications by extruder and coating by nozzle. Reactivation temperature.
  • the hot melt adhesives have a reactivation temperature ranging from about 40 ° C to 150 ° C which makes them suitable for any type of flexible or non-flexible application.
  • a reactivation temperature ranging from about 40 ° C to 150 ° C which makes them suitable for any type of flexible or non-flexible application.
  • the formulations whose reactivation temperature is in the range 60-1 10 ° C.
  • polymer A has an impact on the reactivation temperature of the final composition.
  • certain polymers of the prior art do not make it possible to obtain hot melt adhesives with the targeted reactivation temperatures. Indeed, it has been possible to record reactivation temperatures greater than 150 ° C. in formulations J and K, comparative examples when component A is PLA (poly lactic acid) or an aromatic copolyester.
  • a reactivation temperature between 60 0 C and 90 ° C will allow the hot melt adhesive to be sealed on yogurt pots during the formation thereof.
  • the yoghurt pot streamer is a printed paper coated with hot-melt glue on widths (coil width) of the order of 1300 mm thanks to the coating process described above.
  • hot melt adhesive a hot melt adhesive
  • the compositions according to the invention have an open time of less than 1 second or preferably less than 0.5 seconds, for example for flexible bonded delayed bonding applications.
  • This feature allows the hot melt adhesive to freeze instantly when placed on the paper rolls.
  • the rewinding of the coil coated with adhesive on itself can be carried out without delay after gluing.
  • a hot melt adhesive having an open time greater than or equal to 2 seconds, preferably from 3 to 30 seconds, will be chosen.
  • formulations also have the following necessary properties of hot melt adhesives. Thermal stability.
  • compositions according to the invention are suitable for any type of packaging for food or non-food applications.
  • Non-flexible packaging include box closures and cases, cardboard tray formations, bottle labeling, bookbinding, cardboard paper coating that can be reactivated to create a seal.
  • the hot melt composition according to the invention is prepared by simply mixing its components at a temperature of between 100 and 200 ° C., until a homogeneous mixture is obtained.
  • the mixing techniques required are well known to those skilled in the art.
  • Formulations 1 to 6 of compositions according to the invention are described in Table 1.
  • Formulations I to M of the comparison compositions are described in Table 1.
  • Example 2 Use of the Compositions in Paper Banner Coating Processes
  • the coating process is carried out according to the following scheme:
  • Adhesive hot melt 10 g / m 2
  • This method is particularly used in the preparation of a pot of yoghurt, typically consisting of a polystyrene container, a lid and a banner coated with hot melt adhesive (hot melt).
  • a pot of yoghurt typically consisting of a polystyrene container, a lid and a banner coated with hot melt adhesive (hot melt).
  • the yoghurt pot streamer is a printed paper coated with hot-melt glue on widths (coil width) of the order of 1300 mm thanks to the coating process described above.
  • This streamer is then cut, positioned around the yoghurt pots and reactivated, that is to say warmed to slightly remelt the hot melt adhesive (hot melt) and cause adhesion between the paper streamer and the polystyrene pot.
  • the temperature at which the streamer is heated is greater than the reactivation temperature of the corresponding hot melt adhesive.
  • Example 3 Properties of the compositions obtained. The formulations obtained are then evaluated in the characteristic tests of the hot-melt adhesives described below:
  • the viscosity is measured on each composition at 170 ° C. using a Brookfield viscometer. 2 / Blocking
  • the support surface (pieces of coated paper 4cm x 8cm) coated with hot melt adhesive is brought into contact with the printed face and varnished and pressurized to 0.7 bars at a temperature of 40 ° C for 7 days.
  • a backing sheet coated with hot melt adhesive is positioned horizontally on a flat surface.
  • a steel pad surrounded by a second coated support sheet, externally coated face and having a mass of 200 g is positioned on the coated support, in contact with the coated side of said support.
  • the force required to move the pad at a given speed is measured as follows: On a dynamometer is positioned the pad surrounded by the coated support on the coated face of the streamer. Then the pad is moved horizontally to 150 mm / min and the average of the force during displacement is measured, which after division by the weight of the pad is expressed in the form of the dynamic coefficient of friction (or dynamic COF). 4 / Reactivation temperature
  • the hot melt adhesive coated paper backing tape is positioned on a PLA strip at a reference temperature of between 50 and 150 ° C so that the coated side is in contact with the PLA.
  • a pressure of 3 bar is applied to the assembly for a time of 1 s. After returning to ambient temperature of the assembly, ie after about 5 minutes, the two strips are separated and the% defibering, that is to say, cohesive rupture within the paper support, is visually estimated.
  • the open times are measured according to the following measurement method: A bead of hot melt adhesive is applied to a support, then a second support is displayed after X seconds. The open time is the maximum value of X for the hot melt adhesive to adhere to the second support. The measurements are done at room temperature.
  • the open time measurement is carried out on OLINGER type equipment which makes it possible to precisely manage the time between the removal of the hot melt adhesive and the contacting of the support.
  • the hot melt adhesive is melted at its application temperature and then applied in a bead of 1 to 2 mm in diameter on a reference cardboard support.
  • a duration of X seconds is timed then a second reference card is positioned on the bead of hot melt adhesive thus creating the bond between the two boxes.
  • the 2 boxes are then separated manually.
  • the open time is the maximum value of the time X for which a defibration of the second cardboard during the separation is observed.
  • the test method determines the ultimate biodegradability and disintegration of a test material under conditions simulating an intensive aerobic composting process.
  • the inoculum is a stabilized and mature compost, obtained if possible from the composting of the organic fraction of municipal solid waste.
  • test material is mixed with the inoculum and introduced into a static composting vessel where it is composted under optimum conditions for oxygen present, moisture and temperature, during a period of time. duration not exceeding 6 months.
  • products of ultimate biodegradation are carbon dioxide, water, mineral salts, and new microbial cell constituents (biomass).
  • the carbon dioxide produced is continuously monitored or measured at regular intervals in the test vessels and blank, and then integrated to determine cumulative CO2 production.
  • the biodegradation percentage is obtained by comparing the CO2 produced by the test material with the maximum amount of CO2 that could be obtained from the test material and is calculated from the measured total organic carbon (TOC). This percentage of biodegradation will not include the amount of carbon converted to new cell biomass that has not been metabolized to CO2 during the test.
  • the incubation must take place in the dark or under diffuse light, in an enclosure to be maintained at a constant temperature of 58 ° C +/- 2 ° C and free of vapors capable of inhibiting microorganisms.
  • Any individual fragment of compact test material used must have a maximum area of 2cm x 2cm. If the test material has a larger original size, the size of the fragments is reduced.
  • the ratio of the dry mass of the inoculum to that of the test material should be about 6 to 1.
  • the humidity should be maintained at about 50%.
  • compositions tested according to this method have a biodegradability greater than 55%, preferably greater than 60%, more preferably greater than 90%. This percentage is given by reference to the biodegradability of the cellulose which represents under the same conditions 100%. In particular, compositions 3 and 6 have 64% biodegradability.
  • polymer A has an impact on the reactivation temperature of the final composition.
  • certain polymers used in the prior art do not make it possible to obtain hot melt adhesives with the targeted reactivation temperatures.
  • reactivation temperatures higher than 150 ° C. are noted in the formulations J, K, and M of the comparative examples when component A is PLA or an aromatic copolyester.
  • compositions shown in Table 2 above are representative of hot melt adhesive compositions having open times greater than 2 seconds which makes them suitable for rigid media applications such as standard cartons.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP09721207A 2008-02-14 2009-02-13 Biologisch abbaubare schmelzkleberzusammensetzung Withdrawn EP2245102A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0800809A FR2927629B1 (fr) 2008-02-14 2008-02-14 Composition adhesive thermofusible biodegradable.
PCT/FR2009/000162 WO2009115672A1 (fr) 2008-02-14 2009-02-13 Composition adhesive thermofusible biodegradable

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Publication Number Publication Date
EP2245102A1 true EP2245102A1 (de) 2010-11-03

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US (1) US8067492B2 (de)
EP (1) EP2245102A1 (de)
CN (1) CN102007192B (de)
FR (1) FR2927629B1 (de)
WO (1) WO2009115672A1 (de)

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FR2927629B1 (fr) 2008-02-14 2011-07-29 Bostik Sa Composition adhesive thermofusible biodegradable.
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WO2011156878A1 (pt) * 2010-06-14 2011-12-22 Fatima Aparecida Do Amaral "fralda descartável biodegradável (ecologicamente correta)".
CN102250576B (zh) * 2011-06-09 2013-12-04 苏州瀚海化学有限公司 水性共聚多酯热熔型粘合剂及其制备方法
TWI473716B (zh) * 2011-12-22 2015-02-21 Taiwan Textile Res Inst 防水貼條
JP5921946B2 (ja) 2012-04-26 2016-05-24 ヘンケルジャパン株式会社 ホットメルト接着剤
JP5883344B2 (ja) * 2012-04-26 2016-03-15 ヘンケルジャパン株式会社 ホットメルト接着剤
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JP5925094B2 (ja) 2012-09-27 2016-05-25 ヘンケルジャパン株式会社 ラベル用ホットメルト粘着剤
JP6057837B2 (ja) 2013-05-30 2017-01-11 ヘンケルジャパン株式会社 ホットメルト接着剤
KR20160091879A (ko) * 2013-12-02 2016-08-03 유니띠까 가부시키가이샤 폴리에스테르 수지 조성물 및 그것을 함유하는 접착제
WO2015163582A2 (ko) * 2014-04-24 2015-10-29 씨제이제일제당 (주) 수지용 폴리에스테르계 가소제
WO2018090182A1 (zh) * 2016-11-15 2018-05-24 惠州航程世纪科技有限公司 一种可降解胶粘剂组合物及其制备方法
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Publication number Publication date
US8067492B2 (en) 2011-11-29
FR2927629A1 (fr) 2009-08-21
CN102007192B (zh) 2014-02-19
FR2927629B1 (fr) 2011-07-29
WO2009115672A1 (fr) 2009-09-24
US20100330315A1 (en) 2010-12-30
CN102007192A (zh) 2011-04-06

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