EP1237987A1 - Adhesif thermofusible se presentant sous la forme d'un granule - Google Patents

Adhesif thermofusible se presentant sous la forme d'un granule

Info

Publication number
EP1237987A1
EP1237987A1 EP00969399A EP00969399A EP1237987A1 EP 1237987 A1 EP1237987 A1 EP 1237987A1 EP 00969399 A EP00969399 A EP 00969399A EP 00969399 A EP00969399 A EP 00969399A EP 1237987 A1 EP1237987 A1 EP 1237987A1
Authority
EP
European Patent Office
Prior art keywords
sensitive adhesive
weight
hot
melt pressure
hot melt
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Withdrawn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
EP00969399A
Other languages
German (de)
English (en)
Inventor
Steve Hatfield
Gerald Petry
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1237987A1 publication Critical patent/EP1237987A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/124—Treatment for improving the free-flowing characteristics

Definitions

  • the invention relates to a hotmelt pressure-sensitive adhesive in the form of granules with at least one outer layer (shell) made of a non-pressure-sensitive adhesive composition and with a core of the hotmelt pressure-sensitive adhesive surrounded by it.
  • Coated granules of this type from pressure sensitive adhesives to be applied to the melt are known.
  • EP 294 141 describes coated pellets made of synthetic polymers, e.g. EVA, coated with PE. They are produced by a) extruding a first synthetic polymer into a strand or into pellets, b) cutting the strand into pellets while still molten, c) powdering the pellets with powder of a second polymer, the powder due to the high temperature the pellet melts and forms a layer, d) cools the coated pellet.
  • synthetic polymers e.g. EVA, coated with PE.
  • the powder can be heated to 30 to 40 ° C before application.
  • the coated pellets do not stick together.
  • a disadvantage of the coated pellets described is that the enveloping layer is not closed and parts can escape from the melt ("bleeding").
  • WO 96/00747 describes a process for coating hot melt adhesives which essentially comprises the following steps: a) extrusion of the hot melt adhesive through a suitable nozzle, b) spraying the surface of the extruded hot melt adhesive with a melted film-forming polymeric material with a lower molecular weight or with a polymer formulation, the coating material not significantly impairing the properties of the adhesive composition after it has been remelted, c) heating the surface of the coated adhesive so that the film-forming polymer is remelted and forms a continuous coating; and d) cooling the adhesive coated in this way to temperatures that are suitable for handling.
  • the extruded hot melt adhesive can be cooled after extrusion and prior to spray coating. However, direct coating after extrusion is preferred. The coated extrudate is finally cut. A disadvantage of this process and the products that result is that the interfaces are not coated. The portions are therefore not pourable.
  • EP 14 467 describes a process for underwater pelletizing ethylene copolymers, e.g. of ethylene-vinyl acetate copolymers, 1 to 1000 ppm of a surface-active agent being added to the water to reduce the agglomeration. This increases the agglomeration temperature by at least 10 ° C.
  • WO 97/19582 describes a thermoplastic polymer composition with a non-tacky surface in pellet form which consists of 97 to 99.9% by weight of a pressure sensitive adhesive and 0.1 to 3% by weight of a pelletizing agent. There is agent that surrounds the thermoplastic composition. Substances from the group of PE wax, modified PE wax, PA wax and stearamide wax and their mixtures are specifically mentioned as pelleting agents. They are powdery. Underwater granulation is also mentioned as a manufacturing process for the sticky hot melt adhesive pellets, from which pellets with the non-sticky surfaces that do not block are produced using the pelletizing agents. The production comprises the following steps:
  • the pelleting agent should be used with each extruder run. It is added to the cooling medium. Its concentration in the water is in the range of 0.1 to 3% by weight.
  • Granules stick to each other and to the packaging.
  • EP 156 274 describes an aqueous release agent for the superficial temporary anti-adhesive treatment of sticky pastilles, granules, etc., which consists of a 0.5 to 25% by weight solution or dispersion of an at least difunctional aliphatic alcohol having 3 to 7 carbon atoms and / or an at least trifunctional aliphatic hydroxycarboxylic acid or its water-soluble salts. If necessary, 0.2 to 15% by weight of water-insoluble salts of a C 2 -C 36 -aliphatic or alicyclic mono- or dicarboxylic acid can also be used.
  • the release agent is primarily used to make granules made of pressure-sensitive hot-melt adhesives anti-adhesive.
  • the granules are treated with the solution or the suspension at 18 to 22 ° C. and then, after the solution or the suspension has been suctioned off, dried with air at 30 ° C. in 15 minutes.
  • the granules then contain 0.3 to 0.5% by weight of active substance. It is protectable. The release effect remains at 25 ° C for at least 3 months. However, it is not sufficient to increase the bearing temperature and pressure. In addition, the finishing process is difficult because of the agglomeration of the unrefined granules.
  • the sticky materials are first extruded and crushed into particles while in contact with the fluid that contains a compatible non-sticky material that coats the sticky particles as they form. This is preferred Underwater granulation.
  • the coated sticky particles are then separated from the cooling fluid and coated a second time with a non-sticky material.
  • the coating material should consist of silicones, surface-active compounds or powders, the powders preferably being polyolefins and polyolefin waxes with a particle size of about 1 to 600 ⁇ m. Among the polyolefins, polypropylene waxes and Fischer-Tropsch waxes are preferred.
  • the powder should have a proportion of about 0.5 to 8% by weight, based on the polymer particles.
  • a hotmelt pressure-sensitive adhesive in the form of granules with at least one compact outer layer (shell) composed of at least one to 45 ° C. non-tacky component of the hotmelt pressure-sensitive adhesive and with a core surrounding it from the remaining components of the hotmelt pressure-sensitive adhesive ,
  • the weight fraction of the outer layers is preferably in the range from 0.5 to 10% by weight.
  • the granulate is produced from the melt of the hotmelt PSA by the underwater pelletizing process. After the granulate has cooled to below 15 ° C., it is sprayed with the finely divided liquid coating component until a sufficiently dense layer is formed on the core.
  • the coating material can consist of a thermoplastic elastomer, the melting point of which can be reduced by mixing with other adhesive components, e.g. with waxes or plasticizers.
  • the coating component is liquid when applied, preferably an anhydrous melt, e.g. a PE wax. But it can also be an aqueous dispersion, e.g. an emulsion of Fischer-Tropsch wax with PES film formers.
  • the wax is finely divided and has an average diameter of 0.5 to 12 ⁇ m.
  • a separating agent in particular a fatty acid derivative, e.g. a stearate.
  • EP 575 900 B1 describes the use of micronized polyethylene wax as a release agent for sticky granules.
  • the polyethylene wax has an average particle size of 1 to 30 ⁇ m and an average Molecular weight Mn from 50 to 10,000. An amount of 0.1 to 2% by weight, based on the granules, is applied.
  • the PE wax is expediently applied by powdering and spraying on the melt.
  • Polyethylene waxes have the disadvantage that they usually lead to problems with the treated hotmelt PSAs after heating over a long period of time, e.g. Gel formation, charring, skin formation and deteriorated adhesive properties.
  • Powders generally have the disadvantage that they are difficult to disperse and require a large amount of dispersant.
  • problems associated with this during manufacture e.g. Foaming during shredding. Bigger problems arise later. For example, their non-stick effect is insufficient due to the lack of a continuous film, and the adhesive properties are ultimately deteriorated.
  • the invention is based on this prior art. It is based on the object of providing a hotmelt pressure-sensitive adhesive which, even after long storage at changing temperatures and a high intrinsic pressure, is still easy to handle, in particular easy to dose. This also includes avoiding sticking to one another or to packaging. Rapid melting should also be made possible. Of course, the adhesive properties must not be adversely affected by the anti-adhesive finish.
  • the solution can be found in the patent claims. It essentially consists in producing a coating of a granulate core with a special film former and a special release agent. In order to improve the application of the coating composition, it is expedient to add a wetting agent or a defoamer.
  • the subject of the application is primarily a hot melt pressure sensitive adhesive in the form of granules with at least one outer layer (shell) made of a non-pressure sensitive adhesive composition and with a core of the hot melt pressure sensitive adhesive surrounded by it, characterized in that at least one of the outer layers consists of a composition that contains the following components:
  • polyolefin wax in particular PE wax and
  • Fischer-Tropsch wax as a release agent
  • the outer layers surround the core so completely, preferably more than 90%, in particular more than 99%, of the core surface that one can speak of a continuous coating. This degree of coverage is determined by area evaluation of microscopic images.
  • the granulate is free-flowing. This means that due to its own weight, it still flows through an opening of 5 cm in diameter after storage for 4 or at least 2 months at temperatures from -10 to +40 ° C on a weekly basis and with an internal pressure of 30 cm filling height.
  • the granules have a grain diameter of 1 to 30, preferably 4 to 10 mm.
  • the grain size is determined by sieve analysis.
  • the grain preferably has a spherical shape. But it can also be disc-shaped, cube-shaped, Egyptian or cylindrical.
  • the percentage by weight of the outer layers in the hot melt adhesive is approximately 0.1 to approximately 0.7, preferably 0.2 to 0.5% by weight.
  • the proportion by weight is determined by carrying out statistical weighing.
  • the granules can also be made up of several layers, the tackifier generally making up the core, which is surrounded by a first layer of a mixture of plasticizers and fillers and a second layer of polymers and antioxidants.
  • the outer layer can also consist of a mixture of polymers and plasticizers in order to lower the melting temperature or softening temperature in this way. However, the plasticizer must be carefully selected here in order to avoid undesired migration into the outer layer.
  • At least one of these layers preferably consists of the following parts by weight: 10 to 25 parts by weight of Fischer-Tropsch wax, 1 to 5 parts by weight of mannitol and 0.05 to 0.25 parts by weight of a wetting agent or defoamer.
  • the Fischer-Tropsch wax should preferably be micronized, i.e. its average particle size should be in the range of about 1 to 30 microns.
  • the Fischer-Tropfsch wax can contain up to 100% by weight, in particular up to
  • Polyethylene wax are replaced, preferably if it is not modified, especially not oxidized.
  • Sugar alcohols are polyhydroxy compounds which can be obtained by reducing the carbonyl function from low-molecular saccharides, in particular from the monosaccharides. Examples are: tetrite, pentite, hexite and heptite. The following may be mentioned in particular: styracitol, mannitol, ribitol, heptitol and sorbitol.
  • the anhydrides of the sugar alcohols may also be useful, e.g. Polygalitol.
  • Mannitol is preferred. Mannitol is a low molecular film former. Up to 50% by weight can be replaced by other polyhydric low molecular weight alcohols, in particular by other sugar alcohols.
  • the wetting agent or defoamer should preferably be a nonionic surface-active substance and be based essentially on epoxidation products. For example, ethoxylated acetylenediols or acetylenediol-EO-acetylenediol mixtures (90:10) from Air Products, in particular Surfynol DF 37, can be used.
  • Resins may be included.
  • the material of the granulate core corresponds to the type and amount of the individual components of a conventional hot melt adhesive composition, in particular a hot melt pressure sensitive adhesive composition, provided that it is compatible with the selected material of the coating, so that the coating is suitable for the user can be easily dissolved in the melted hot melt adhesive.
  • the hot melt adhesive systems comprise a variety of base polymers which are mixed with other ingredients such as plasticizers, tackifiers, stabilizers, waxes and extenders to form the adhesive.
  • the basic polymers essentially determine the properties of the adhesive layer with regard to adhesion, strength and temperature behavior.
  • the most important basic polymers are polyolefins, polyacrylates, polychloroprene, polyesters, polyvinyl ethers, polyamides and polyurethanes. Above all, they are rubbers, especially synthetic rubbers such as EVA, SBR and EPDM.
  • Outer layer olefinic materials such as polyethylene and poly (ethylene-co-vinyl acetate) are compatible with aliphatic and aromatic hydrocarbon hot melt adhesives.
  • Commercial hot melt adhesive compositions of this type contain hot melt adhesives based on ethylene vinyl acetate copolymer and on amorphous propylene-alpha-olefm (APAO).
  • APAO amorphous propylene-alpha-olefm
  • hot melt adhesives based on styrene-butadiene-styrene (SBS) copolymer-ABABA-Multiblock construction hot-melt adhesives based on radial styrene-butadiene-styrene, (SB) n copolymers and construction hot melt adhesives based on styrene-isoprene-styrene (SIS) and ABA- Block copolymers.
  • SBS styrene-butadiene-styrene
  • SB n copolymers
  • construction hot melt adhesives based on styrene-isoprene-styrene (SIS) and ABA- Block copolymers construction hot melt adhesives based on styrene-isoprene-styrene (SIS) and ABA- Block copolymers.
  • Other polymers are: polybutene, ethylene / acrylate, ethylene / CO and
  • Hot melt adhesives based on polyamides can also be packaged using the method according to the invention.
  • Possible polyamides are PA6,6, PA6,10, PA6 and especially polyamides made from diamines and dimerized fatty acids, especially from ethylenediamine and dimerized linoleic acid.
  • copolymers are also possible, e.g. B. polyamide / EVA copolymers, polyamide / siloxane copolymers, polyester amides, polyether amides,
  • Polyester amide imides and polyether ester amides are examples of polyester amide imides and polyether ester amides.
  • the present invention can also be applied to hot melt adhesives made from polymers and copolymers of synthetic resins, rubbers, polyethylene, polypropylene, polyurethane, polyacrylic, polyvinyl acetate, ethylene vinyl acetate copolymer and polyvinyl alcohol.
  • the present invention is particularly advantageous for hot melt adhesives with serious handling problems, e.g. B. for the above-mentioned, even at room temperature still tacky hot melt adhesives.
  • hot melt adhesives made from the following components:
  • Elastic polymers such as block copolymers, e.g. B. styrene-butadiene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene;
  • ethylene vinyl acetate polymers other ethylene esters and copolymers, e.g. B. ethylene methacrylate, ethylene n-butyl acrylate and ethylene acrylic acid;
  • polyolefins such as polyethylene and polypropylene
  • polyester polyvinyl alcohols and copolymers therewith;
  • Aldehydes containing resins such as phenol aldehyde, urea aldehyde, melamine aldehyde and the like.
  • Components for strengthening the adhesion may also be present.
  • diluents are liquid polybutene or polypropylene, petroleum waxes such as paraffin and microcrystalline waxes, semi-liquid polyethylene, hydrogenated animal, fish and vegetable fats, mineral oil and synthetic waxes and hydrocarbon oils.
  • the invention also relates to the process for producing the hotmelt pressure-sensitive adhesive in the form of granules.
  • the essence of this process invention is that the core of the hotmelt PSA is treated with an aqueous dispersion of the shell components until the desired amount has been applied.
  • the solids content of the dispersion is preferably in the range from about 15 to 28, in particular up to 25% by weight.
  • the coating is expediently carried out directly in connection with underwater pelletizing.
  • the cooling medium is expediently the release agent dispersion. In particular, it has a temperature of below 25, preferably below 15 and especially below 10 ° C.
  • the manufacturing process according to the underwater pelletizing process is therefore preferably characterized by the following process steps: It is essential that a) the core components are melted, b) the melt is pelletized under water, c) the underwater pellet is cooled, d) the cooled one Separates underwater granules from the water and e) dries with air at from 5 to 60, in particular from 25 to 50 ° C., until it is expedient to still contain less than 0.25, preferably less than 0.10,% by weight of moisture.
  • the temperature of the melted adhesive is preferably chosen such that its viscosity during the extrusion is at least 2000 to a maximum of 100,000 mPas, measured according to Brookfield (ASTM D 3236).
  • the preferred adhesive temperature during extrusion depends on the composition of the hot melt pressure sensitive adhesive. It has been found to be advantageous in the case of conventional hotmelt adhesives that the temperature of the adhesive during the extrusion is 80 to 150 ° C. and in particular 110 to 130 ° C.
  • the production process can be described more precisely by the following steps:
  • the pressure sensitive hot melt adhesive is now allowed to flow to the nozzle plate when the cooled coating suspension has reached a constant flow rate of approximately 20 m 3 / hour in the transfer tube.
  • the solids concentration of the coating suspension or the cooling medium is maintained by adding a 50% basic mixture, so as to maintain uniform conditions.
  • the granules are protected from further sticking because of the coating and can be packed directly in boxes, sacks etc., for example in conventional 20 kg boxes with a sack made of a polymer. When it is used, the free-flowing granules are melted and applied as a melt.
  • the solution according to the invention offers e.g.
  • the powder coating has the following advantages: Completely closed surface, clean process (dust), better control of the coating, easier or better handling by the customer.
  • the granules according to the invention are free-flowing and therefore easy to handle, even if they have been stored under pressure at a higher temperature.
  • the granules according to the invention do not dust when compared to powder-coated granules.
  • Hot melt pressure sensitive adhesive Technomelt-Q-8701 from Henkel based on SBS, melt viscosity at 150 ° C. 100 Pa s; Softening temperature: 105 ° C (ring and ball).
  • Fischer-Tropsch wax Type HS28W from Kromachem GmbH, Leverkusen; Solids content: 53% by weight,
  • the granules were processed with an underwater pelletizer
  • the cooling liquid being the coating
  • the coated granules were tested for free-flowing properties after storage at 40 ° C. for 7 days at a pressure of 30 g / cm 2 . This corresponds to a storage of 3 months under the usual environmental conditions in a warehouse.
  • the thermal stability of the coated granules was examined by heating them in air at 180 ° C. for 72 hours. Attention was paid to color changes and charring. In both cases it was coated granules better than a corresponding melt of the uncoated hot melt pressure sensitive adhesive. 3. With regard to the use of hot-melt pressure sensitive adhesives in the production of disposable diapers, the adhesive properties were examined using films and nonwovens. This includes a) the peel strength and b) the creep resistance. When applying the same amount of adhesive (approx.
  • the creep resistance according to the Du Pont test was practically the same, both at room temperature after 24 hours and at 40 ° C after 1 to 4 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention vise à faciliter la manipulation d'adhésifs thermofusibles, même après un stockage à température élevée et sous pression. A cet effet, l'adhésif thermofusible selon l'invention se présente sous la forme d'un granulé comportant au moins une couche extérieure (enveloppe) constituée d'une composition non adhésive et un noyau entouré par cette dernière et constitué de l'adhésif thermofusible. La couche extérieure renferme les constituants suivants : 1) 10 à 35 % en poids de cire de polyoléfine, notamment de cire de polyéthylène et de cire de Fischer-Tropsch comme agent de séparation ; 2) 1 à 5 % en poids d'alcool de sucre, notamment de sorbitol et de mannitol comme agent filmogène ; 3) 0,05 à 0,25 % en poids d'un agent mouillant ou d'un antimousse ainsi qu'éventuellement 4) un additif, par ex. une résine. Le noyau constitué de l'adhésif thermofusible est produit de préférence selon le procédé connu de granulation par immersion. La couche extérieure est obtenue par traitement avec un réfrigérant qui contient au moins les constituants 1 et 2 de la couche extérieure.
EP00969399A 1999-10-11 2000-10-04 Adhesif thermofusible se presentant sous la forme d'un granule Withdrawn EP1237987A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19949027 1999-10-11
DE19949027 1999-10-11
PCT/EP2000/009685 WO2001027188A1 (fr) 1999-10-11 2000-10-04 Adhesif thermofusible se presentant sous la forme d'un granule

Publications (1)

Publication Number Publication Date
EP1237987A1 true EP1237987A1 (fr) 2002-09-11

Family

ID=7925285

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00969399A Withdrawn EP1237987A1 (fr) 1999-10-11 2000-10-04 Adhesif thermofusible se presentant sous la forme d'un granule

Country Status (5)

Country Link
EP (1) EP1237987A1 (fr)
AU (1) AU7913000A (fr)
BR (1) BR0014659A (fr)
DE (1) DE10048923A1 (fr)
WO (1) WO2001027188A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10122437A1 (de) 2001-05-09 2002-11-28 Henkel Kgaa Schmelzklebstoff in Form eines Granulates
US7442739B1 (en) 2003-11-12 2008-10-28 Henkel Corporation Hot melt pressure sensitive adhesives
CN102216373B (zh) * 2008-11-19 2013-10-30 埃克森美孚化学专利公司 粘合剂组合物和其制备方法
EP2686398A1 (fr) * 2011-03-17 2014-01-22 Henkel AG&Co. KGAA Granulés de psa enrobés
WO2015129903A1 (fr) 2014-02-25 2015-09-03 住友化学株式会社 Adhésif particulaire
US9758626B2 (en) 2014-09-19 2017-09-12 Honeywell International Inc. High performance anti-block treatments for viscoelastic solids
EP3243622B1 (fr) * 2016-05-13 2020-09-09 Borealis AG Procédé de transport hydraulique de granulés de polyoléfine
US20250154392A1 (en) 2022-02-23 2025-05-15 Sasol South Africa Limited Hot melt adhesive composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3410957A1 (de) * 1984-03-24 1985-09-26 Henkel KGaA, 4000 Düsseldorf Waessrige trennmittel
US5041251A (en) * 1989-07-27 1991-08-20 Eastman Kodak Company Pourable particles of normally tacky plastic materials and process for their preparation
JPH03181465A (ja) * 1989-12-11 1991-08-07 Takeda Chem Ind Ltd キノリン誘導体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0127188A1 *

Also Published As

Publication number Publication date
AU7913000A (en) 2001-04-23
WO2001027188A1 (fr) 2001-04-19
DE10048923A1 (de) 2001-04-12
BR0014659A (pt) 2002-06-11

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