EP0855146A1 - Method for making a fusible interlining and interlining obtained thereby - Google Patents
Method for making a fusible interlining and interlining obtained thereby Download PDFInfo
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- EP0855146A1 EP0855146A1 EP98490005A EP98490005A EP0855146A1 EP 0855146 A1 EP0855146 A1 EP 0855146A1 EP 98490005 A EP98490005 A EP 98490005A EP 98490005 A EP98490005 A EP 98490005A EP 0855146 A1 EP0855146 A1 EP 0855146A1
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- Prior art keywords
- hot
- polymer
- support
- melt polymer
- melt
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06H—MARKING, INSPECTING, SEAMING OR SEVERING TEXTILE MATERIALS
- D06H5/00—Seaming textile materials
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D27/00—Details of garments or of their making
- A41D27/02—Linings
- A41D27/06—Stiffening-pieces
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/008—Treatment with radioactive elements or with neutrons, alpha, beta or gamma rays
Definitions
- the present invention relates to the field of fusible linings which are supports, textile or non-woven, on one side of which are applied points of hot-melt polymer, likely to adhere later on the piece of clothing to be reinforced under the effect of the application of a certain hot pressure. It concerns more particularly a process for manufacturing such a covering, is carrying out an electronic bombardment in order to locally modify the melting point and / or viscosity of the hot-melt polymer; she also relates to a fusible interlining obtained by said process whose hot melt polymer dots have a melting temperature or their viscosity differentiated in their thickness.
- this piercing has for effect of locally increasing the stiffness of the interlining and therefore of the part of clothing, which may be contrary to the desired effect. cause bonding on lining fabrics such as lining and lapels of drapery, which causes degradation of the quality of the garment.
- the applicant has already proposed, in the document FR 2 606 603 to implement means of a nature chemical, acting on the hot-melt polymer in order to modify its chemical structure, at least partially, at least at the interface with the interlining support, so as to prevent the hot-melt polymer from stick through the interlining under the effect of heat and / or pressure and / or steam.
- the means, chemical in nature, suitable for modify the chemical structure of the hot-melt polymer at least one reactive material and at least one reactive means capable of initiating, ensure, promote the reaction between the reactive material and the polymer hot melt.
- the reactive means the heat inputs, the ultraviolet radiation, electronic bombardment. It is stipulated that this reactive means can be used in the presence of catalysts. More precisely when the reactive means of the crosslinking reaction of the hot melt polymer and modified vinyl reactive polymer is UV radiation, it is expected that this will occur with contact of photo-initiator products.
- the goal set by the applicant is to propose a method of manufacture of a fusible interlining using a electron bombardment to modify the chemical structure of the polymer hot-melt which overcomes the aforementioned difficulties.
- a stabilizer support chosen from textile supports and non-woven, dots of hot melt polymers of medium thickness E and one of the faces of said support is subjected to bombardment electronic.
- the points of hot-melt polymers containing a radical activator and being free of photo-inhibitor, the depth of penetration of the electrons in the points of the hot-melt polymer is adjusted to obtain a modification of the physico-chemical properties of the hot-melt polymer, chosen from the melting temperature and the viscosity, over a thickness e with respect to the average thickness E.
- the function of the radical activator is to create free radicals allowing to initiate the polymerization reaction on itself of the polymer hot melt. It is akin to the photo-initiating agent provided for in the document FR 2 606 603 during the implementation of UV irradiation as a reactive medium. The radical activator is therefore not properly speak of a reactive substance in the sense provided for in document FR 2 606 603.
- this radical activator is of the acrylic type, in particular trimethylol propane trimethacrylate or trimethylol propane triacrylate.
- acrylic-functional monomers are acrylic-functional monomers and are not part of the explicitly provided list, for the subject reactive, in document FR 2 606 603.
- the reverse side of the interlining support is subjected to electronic bombardment and the penetration depth of the electrons is adjusted to obtain the modification of the physicochemical properties over a thickness e of between 10 and 50% of l 'average thickness E , the modification consisting in an increase in the melting temperature or in an increase in the viscosity of the hot-melt polymer.
- the face side of the interlining support is subjected to electronic bombardment and the depth of penetration of the electrons is adjusted to obtain a modification of physicochemical properties over a limited thickness of between 50 and 90% of l 'average thickness E , the modification consisting in a decrease in the melting temperature or a decrease in the viscosity of the hot-melt polymer.
- each point of polymer happens to be made by a single deposit, monolayer, and after the bombardment action electronic, said layer has a melting temperature and / or a differentiated viscosity between a first lower zone which is in contact with the textile support and which has a melting temperature and / or a given viscosity and a second upper zone which has a temperature of melt or a viscosity lower than that of the hot-melt polymer of the first zone.
- the electron beam generated by the cannons at industrial electrons does not have a uniform action in the thickness of a given material.
- the quantity of electrons or dose decreases as and thickness measurement, until it becomes zero at a given thickness, which is a function of the acceleration voltage of the electron beam.
- the electron dose is canceled for a thickness of 200 ⁇ m, through a material of density 1. This dose is still around 50%, in this case, for a thickness of around 130 ⁇ m.
- the applicant has found that in order to obtain a modification of the physicochemical properties of the hot-melt polymer which is such that the lower layer of the point can play the desired barrier effect, avoiding the piercing of the fusible interlining, it was necessary for it there is a certain dose of electrons which has reached the radical activator.
- the adjustment of the depth of penetration of the electrons therefore aims to ensure that there is this sufficient dose of electrons which could have penetrated into the limited thickness e of the hot-melt polymer, that is to say the thickness for which the modification of physicochemical properties is sought.
- the depth of penetration of the electron beam into the polymer points hot melt by interposing a filter between the electron beam and the stabilizer support.
- This filter has the effect of artificially reducing the thickness of penetration of the electron beam into the hot-melt polymer and therefore to precisely adjust the really effective penetration depth.
- filter which can in particular be a sheet of paper and, in particular its thickness, depends on the material constituting the stabilizing support and on the thickness e for which a modification of the physicochemical properties is desired.
- the operating conditions of the bombardment electronics as well as the choice and quantity of radical activator are determined so that the melting point of the polymer hot-melt has a variation, more or less of the order of 1O to 20 ° C in the area subject to electronic bombardment.
- a fusible interlining 1 consists of a support 2 and points 3 of thermofusible and fusible polymer.
- the support can be either a textile support proper, of the woven, knitted or knitted type weft insertion, a nonwoven.
- 3 points of polymer hot-melt are arranged on all or part of the surface of one of the two faces of the support 2, called the face side. It is this face that is intended to be applied against the reverse side of the piece of clothing to protect or strengthen.
- the hot-melt polymer is a known type, among polyamides, polyethylenes, polyurethanes, polyesters, aminoplasts ... This can also be a copolymer. The important thing is that the polymer in question can, at the temperature of application of the piece of clothing under hot pressure, react by locally melting to adhere to the fibers or filaments on the reverse side of the piece of clothing.
- the polymer dots are deposited in the form of an aqueous dispersion which is then subjected to a heat treatment so as to evaporate the solvent and agglomerate new hot melt polymer particles to achieve their hanging on the support.
- the polymer points are deposited by any conventional technique, in particular printing with a rotary frame or other.
- the polymer points on the surface of the interlining support represent of the order of 5 to 20 g / m 2 , depending on the type of support.
- the aqueous dispersion of hot-melt polymer comprises also a radical activator, i.e. a compound which is capable of form free radicals under the effect of electronic bombardment, and is free of photo-inhibiting agent.
- a radical activator i.e. a compound which is capable of form free radicals under the effect of electronic bombardment, and is free of photo-inhibiting agent.
- an activator of the acrylic type such as trimethylol propane trimethacrylate or else trimethylol propane triacrylate.
- the proportion of radical activator can be between 5 and 20% by weight relative to the hot-melt polymer.
- aqueous dispersion of hot-melt polymer after having carried out the deposition of the aqueous dispersion of hot-melt polymer and then the heat treatment of the latter in order to evaporate the water contained in the dispersion and to agglomerate the mixture of hot-melt polymer and activator, electron bombardment is carried out on the reverse side 2 b of the interlining support 2, that is to say the face which does not include the points 3 of polymer.
- the electrons pass through the filaments or fibers 4 of the support 2 and penetrate into the point of polymer 3 where they meet the radical activator. Under the effect of these electrons, the radical activator generates free radicals which develop crosslinking reactions in zone 3 a of the hot-melt polymer.
- the penetration depth of the electrons, the quantity and the choice of the radical activator are determined so that only zone 3 a of the hot-melt polymer which is in contact or in the immediate vicinity of the fibers or filaments 4 of the support and subjected to the action of the electrons undergoes the desired modification of the physicochemical properties, namely an increase in the melting temperature or in the viscosity of the hot-melt polymer.
- FIG. 2 is shown schematically the separation of this first zone 3 a , with modified structure, from the second zone 3 b with unmodified structure by a broken line 5.
- the action is gradual in thickness point.
- This differentiation due to a certain crosslinking results in this first example by an increase of the melting temperature of the hot melt polymer constituting the first zone 3 a , this melting temperature remaining unchanged with regard to the second zone 3 b not significantly modified by the action of the electrons.
- each point of hot-melt polymer, in which penetrate the electrons, constitutes a solid medium. Therefore, the cross-linking reactions, generated by free radicals, do not propagate only very weakly, unlike what might happen if it was a liquid medium.
- the hot-pressing interlining 1 When the hot-pressing interlining 1 is applied under hot pressure to the item of clothing, at the temperature usually used for the hot-melt polymer in question, only the second zone 3b of each point 3 is brought to react, that is to say to exercise its adhesive power by melting the hot-melt polymer.
- the application temperature is insufficient, due to the increase in its melting temperature, to react the polymer contained in the first zone 3 a .
- the polymer of the second zone 3 b cannot creep through the wires or filaments 4 of the support 2, this creep being prevented by the first zone 3 a at point 3, which does not react and acts as a barrier.
- the operating conditions, and in particular the penetration depth of the electrons are determined so that the relative thickness of the first zone 3 has to be between 1O and 5O% of the total thickness from the point of polymer 3, preferably between 10 and 20%.
- Polyamides or high density polyethylenes or polyurethanes have been used as hot melt polymers and as radical activators trimethylol propane trimethacrylate or trimethylol propane triacrylate in an amount of 5 to 20% by weight of polymer.
- the hot melt polymer deposition was carried out at a rate of 9 to 16 g / m 2 on the interlining support.
- An electron gun was used, with doses between 10 and 75 KGy and acceleration voltages from 100 to 200 kV.
- the electron penetration depth is adjusted by interposing paper filters weighing between 50 and 100 g / m 2 .
- this effect of increasing the temperature of the hot-melt polymer can also be obtained by adding a curable filler to the polymer dispersion, i.e. a charge which under the action of electronic bombardment will polymerize and harden irreversibly, thus no longer being reactivated thermally as is the case with the hot-melt polymer.
- a curable filler i.e. a charge which under the action of electronic bombardment will polymerize and harden irreversibly, thus no longer being reactivated thermally as is the case with the hot-melt polymer.
- the acrylic monomers are part of the curable fillers. So if he is itself of the acrylic type, the radical activator can also constitute partly a curable filler.
- the electron bombardment takes place on the two facing support 2.
- the operating conditions of the electron bombardment, the thermofusible polymers, and the activators are selected so to have the opposite effect to that of the first example, namely a decrease in the melting temperature and / or the viscosity of the polymers under the action of electron bombardment. With this difference, the considerations given above remain valid.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Details Of Garments (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Manufacturing Of Multi-Layer Textile Fabrics (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
Abstract
Selon le procédé de fabrication , on dépose sur la face endroit d'un support d'entoilage des points de polymère thermofusible contenant un activateur radicalaire, puis on soumet l'une ou l'autre des faces du support à un bombardement électronique en sorte de modifier localement la température de fusion et/ou la viscosité du polymère thermofusible. Avantageusement, on soumet la face (2a) envers du support (2) à un bombardement électronique ; le polymère thermofusible et les conditions opératoires sont déterminés en sorte que la température de fusion du polymère et/ou la viscosité soit augmentée , dans la zone soumise au bombardement électronique , sur une épaisseur limitée e de chaque point (3). L'entoilage thermocollant de l'invention est composé d'un support d'entoilage et de points de polymère déposés sur la face endroit dudit support, chaque point étant monocouche et ayant une température de fusion différenciée selon l'épaisseur du point, étant plus élevée dans la zone proche du support. <IMAGE>According to the manufacturing process, hot-melt polymer dots containing a radical activator are deposited on the right side of a stabilizer support, then one or other of the faces of the support is subjected to electronic bombardment so as to locally modify the melting temperature and / or the viscosity of the hot-melt polymer. Advantageously, the face (2a) is subjected to the backing of the support (2) to an electronic bombardment; the hot-melt polymer and the operating conditions are determined so that the melting temperature of the polymer and / or the viscosity is increased, in the zone subjected to electron bombardment, over a limited thickness e of each point (3). The fusible interlining of the invention is composed of a covering support and of polymer points deposited on the right side of said support, each point being monolayer and having a melting temperature differentiated according to the thickness of the point, being more high in the area near the support. <IMAGE>
Description
La présente invention concerne le domaine des entoilages thermocollants qui sont des supports, textiles ou non-tissés, sur une face desquels sont appliqués des points de polymère thermofusible, susceptibles d'adhérer ultérieurement sur la pièce d'habillement à renforcer sous l'effet de l'application d'une certaine pression à chaud. Elle concerne plus particulièrement un procédé de fabrication d'un tel entoilage mettant en oeuvre un bombardement électronique en vue de modifier localement la température de fusion et/ou la viscosité du polymère thermofusible ; elle concerne également un entoilage thermocollant obtenu par ledit procédé dont les points de polymère thermofusible ont une température de fusion ou leur viscosité différenciée dans leur épaisseur.The present invention relates to the field of fusible linings which are supports, textile or non-woven, on one side of which are applied points of hot-melt polymer, likely to adhere later on the piece of clothing to be reinforced under the effect of the application of a certain hot pressure. It concerns more particularly a process for manufacturing such a covering, is carrying out an electronic bombardment in order to locally modify the melting point and / or viscosity of the hot-melt polymer; she also relates to a fusible interlining obtained by said process whose hot melt polymer dots have a melting temperature or their viscosity differentiated in their thickness.
Parmi tous les problèmes rencontrés dans le domaine de l'entoilage thermocollant, l'un des plus délicats à résoudre consiste dans le risque de transpercement du support d'entoilage lors de l'application par pression à chaud de l'entoilage thermocollant contre la pièce d'habillement à renforcer. En effet la température qui est choisie pour effectuer cette application à chaud doit permettre de réaliser la fusion du point de polymère de manière à ce que le polymère ainsi fondu puisse se répartir et adhérer sur les fibres ou filaments en surface de la pièce d'habillement. Il arrive cependant fréquemment que cette répartition ne se fasse pas uniquement en surface mais que le polymère flue à travers les fibres ou filaments et apparaisse sur la surface opposée du support d'entoilage. Ceci n'a pas d'incidence sur le plan esthétique, sauf si l'entoilage est destiné à être apparent et à former la face arrière du vêtement. En tout état de cause ce transpercement a pour effet d'augmenter localement la rigidité de l'entoilage et donc de la pièce d'habillement, ce qui peut être contraire à l'effet souhaité.Il peut également provoquer des collages sur les tissus de doublage tels que doublure et parties de draperies en revers, ce qui provoque une dégradation de la qualité du vêtement. Among all the problems encountered in the field of interlining one of the most difficult to solve is the risk of piercing of the interlining support during application by pressure to hot of the fusible interfacing against the piece of clothing to be reinforced. Indeed the temperature which is chosen to carry out this application at hot must allow the polymer point to be melted so that so that the polymer thus melted can distribute and adhere to the fibers or filaments on the surface of the piece of clothing. It happens however frequently this distribution is not only made on the surface but that the polymer flows through the fibers or filaments and appears on the opposite surface of the interlining support. This does not affect the aesthetically, unless the interlining is intended to be visible and to form the back side of the garment. In any event, this piercing has for effect of locally increasing the stiffness of the interlining and therefore of the part of clothing, which may be contrary to the desired effect. cause bonding on lining fabrics such as lining and lapels of drapery, which causes degradation of the quality of the garment.
Pour résoudre cette difficulté, on a déjà proposé de réaliser un entoilage thermocollant dont les points de polymère thermofusible comporteraient deux couches superposées, à savoir une première couche en contact avec la face endroit du support d'entoilage et une deuxième couche disposée précisément au-dessus de la première. Bien sûr les constituants des deux couches sont déterminés en sorte que lors de l'application avec pression à chaud de la pièce d'habillement, seul le polymère thermofusible de la seconde couche réagisse à l'action de la température. La diffusion du polymère thermofusible peut dans ce cas ne se faire que vers la pièce d'habillement, étant empêchée vers le support d'entoilage, la première couche faisant office en quelque sorte de barrière.To resolve this difficulty, it has already been proposed to carry out a fusible interlining with hot melt polymer points have two superimposed layers, namely a first layer in contact with the right side of the stabilizer support and a second layer arranged precisely above the first. Course constituents of the two layers are determined so that when hot press application of the piece of clothing, only the second layer hot melt polymer reacts to the action of temperature. The diffusion of the hot-melt polymer may in this case not to be done only towards the piece of clothing, being prevented towards the support interlining, the first layer acting as a kind of barrier.
En pratique cette technique double couche présente des inconvénients, notamment difficulté de réalisation de la superposition des deux couches et risque de délamination des deux couches.In practice this double layer technique presents disadvantages, in particular difficulty in achieving the superposition of two layers and risk of delamination of the two layers.
Pour pallier ces inconvénients, le demandeur a déjà proposé, dans
le document FR 2 606 603 de mettre en oeuvre des moyens de nature
chimique, agissant sur le polymère thermofusible en vue de modifier sa
structure chimique, au moins partiellement, au moins à l'interface avec le
support d'entoilage, de manière à empêcher le polymère thermofusible de
coller à travers le support d'entoilage sous l'effet de la chaleur et/ou de la
pression et/ou de la vapeur. Les moyens, de nature chimique, propres à
modifier la structure chimique du polymère thermofusible comportent au
moins une matière réactive et au moins un moyen réactif apte à amorcer,
assurer, favoriser la réaction entre la matière réactive et le polymère
thermofusible.To overcome these drawbacks, the applicant has already proposed, in
the
Sont explicitement citées différentes catégories de matières réactives à savoir produits thermodurcissables aminoplaste, notamment urée-formol et mélamine formol, molécules simples ou polymères portant au moins une fonction isocyanate bloquée ou non, molécules simples ou polymères portant au moins une fonction aziridine, polymères modifiés portant au moins une fonction chimique réactive, notamment fonction époxy ou fonction vinylique.Are explicitly mentioned different categories of materials reagents, namely aminoplast thermosetting products, in particular urea formaldehyde and melamine formaldehyde, single molecules or polymers bearing at least one isocyanate function blocked or not, simple molecules or polymers carrying at least one aziridine function, modified polymers carrying at least one reactive chemical function, in particular epoxy function or vinyl function.
Parmi les moyens réactifs, sont cités les apports de chaleur, les radiations ultraviolettes, le bombardement électronique. Il est précisé que ce moyen réactif peut être utilisé en présence de catalyseurs. Plus précisément lorsque le moyen réactif de la réaction de réticulation du polymère thermofusible et du polymère modifié à fonction réactive vinylique est une radiation UV, il est prévu que celle-ci intervienne avec mise en contact de produits photo-initiateurs.Among the reactive means, the heat inputs, the ultraviolet radiation, electronic bombardment. It is stipulated that this reactive means can be used in the presence of catalysts. More precisely when the reactive means of the crosslinking reaction of the hot melt polymer and modified vinyl reactive polymer is UV radiation, it is expected that this will occur with contact of photo-initiator products.
S'agissant plus particulièrement du bombardement électronique comme moyen réactif, il est prévu d'ajouter au mélange de polymère thermofusible et de matière réactive un agent photo-inhibiteur pour imiter la propagation de la réaction chimique de modification. On fait passer le support d'entoilage enduit du mélange devant une source photonique ou électronique située du côté de la face non enduite du support de manière à ce que les particules bombardent préférentiellement les trous ou perforations du support, en regard du polymère thermofusible.With particular regard to electronic bombardment as a reactive medium, provision is made to add to the polymer mixture hot melt and reactive material a photo-inhibitor to mimic propagation of the chemical modification reaction. We pass the interlining support coated with the mixture in front of a photonic source or electronic located on the side of the uncoated side of the support so that the particles preferentially bombard the holes or perforations of the support, opposite the hot-melt polymer.
En pratique, il s'est avéré impossible d'obtenir, dans les conditions
décrites dans le document FR 2 606 603, des résultats satisfaisants en
utilisant comme moyen réactif un bombardement électronique, malgré tout
l'intérêt que présentait cette technique. La difficulté de contrôle, à l'aide
d'agents photo-inhibiteurs, de la propagation de la réaction chimique et la
difficulté d'agir préférentiellement au niveau des trous ou perforations du
support d'entoilage, en regard du polymère thermofusible, font partie des
raisons de ce constat d'échec.In practice, it has proved impossible to obtain, under the conditions
described in
Le but que s'est fixé le demandeur est de proposer un procédé de fabrication d'un entoilage thermocollant mettant en oeuvre un bombardement électronique pour modifier la structure chimique du polymère thermofusible qui pallie les difficultés précitées.The goal set by the applicant is to propose a method of manufacture of a fusible interlining using a electron bombardment to modify the chemical structure of the polymer hot-melt which overcomes the aforementioned difficulties.
De manière connue, selon ce procédé, on dépose sur la face endroit d'un support d'entoilage, choisi parmi les supports textiles et les non-tissés, des points de polymères thermofusibles d'épaisseur moyenne E et on soumet l'une des faces dudit support à un bombardement électronique.In a known manner, according to this method, is deposited on the face location of a stabilizer support, chosen from textile supports and non-woven, dots of hot melt polymers of medium thickness E and one of the faces of said support is subjected to bombardment electronic.
De manière caractéristique selon l'invention, les points de polymères thermofusibles, contenant un activateur radicalaire et étant exempts de photo-inhibiteur, on règle la profondeur de pénétration des électrons dans les points du polymère thermofusible pour obtenir une modification des propriétés physico-chimiques du polymère thermofusible, choisies parmi la température de fusion et la viscosité, sur une épaisseur e par rapport à l'épaisseur moyenne E.Characteristically according to the invention, the points of hot-melt polymers, containing a radical activator and being free of photo-inhibitor, the depth of penetration of the electrons in the points of the hot-melt polymer is adjusted to obtain a modification of the physico-chemical properties of the hot-melt polymer, chosen from the melting temperature and the viscosity, over a thickness e with respect to the average thickness E.
L'activateur radicalaire a pour fonction de créer des radicaux libres
permettant d'initier la réaction de polymérisation sur lui-même du polymère
thermofusible. Il s'apparente à l'agent photo-initiateur prévu dans le
document FR 2 606 603 lors de la mise en oeuvre de l'irradiation UV
comme moyen réactif. L'activateur radicalaire n'est donc pas à proprement
parler une matière réactive au sens où le prévoyait le document FR 2 606
603.The function of the radical activator is to create free radicals
allowing to initiate the polymerization reaction on itself of the polymer
hot melt. It is akin to the photo-initiating agent provided for in the
De préférence, cet activateur radicalaire est du type acrylique,
notamment le triméthylol propane triméthacrylate ou le triméthylol propane
triacrylate. Ces deux composés sont des monomères à fonction acrylique
et ne font pas partie de la liste explicitement prévue, pour la matière
réactive, dans le document FR 2 606 603.Preferably, this radical activator is of the acrylic type,
in particular trimethylol propane trimethacrylate or trimethylol propane
triacrylate. These two compounds are acrylic-functional monomers
and are not part of the explicitly provided list, for the subject
reactive, in
Grâce à l'activateur radicalaire et à l'absence de photo-inhibiteur, il est possible d'obtenir une modification structurelle du polymère thermofusible sur une épaisseur limitée e de chaque point de l'entoilage thermocollant.Thanks to the radical activator and the absence of photo-inhibitor, it is possible to obtain a structural modification of the hot-melt polymer over a limited thickness e of each point of the fusible interlining.
Dans une première variante de réalisation, on soumet la face envers du support d'entoilage au bombardement électronique et on règle la profondeur de pénétration des électrons pour obtenir la modification des propriétés physico-chimiques sur une épaisseur e comprise entre 10 et 50% de l'épaisseur moyenne E, la modification consistant dans une augmentation de la température de fusion ou dans une augmentation de la viscosité du polymère thermofusible.In a first alternative embodiment, the reverse side of the interlining support is subjected to electronic bombardment and the penetration depth of the electrons is adjusted to obtain the modification of the physicochemical properties over a thickness e of between 10 and 50% of l 'average thickness E , the modification consisting in an increase in the melting temperature or in an increase in the viscosity of the hot-melt polymer.
Dans une seconde variante de réalisation, on soumet la face endroit du support d'entoilage au bombardement électronique et on règle la profondeur de pénétration des électrons pour obtenir une modification de propriétés physico-chimiques sur une épaisseur limitée comprise entre 50 et 90% de l'épaisseur moyenne E, la modification consistant dans une diminution de la température de fusion ou une diminution de la viscosité du polymère thermofusible.In a second alternative embodiment, the face side of the interlining support is subjected to electronic bombardment and the depth of penetration of the electrons is adjusted to obtain a modification of physicochemical properties over a limited thickness of between 50 and 90% of l 'average thickness E , the modification consisting in a decrease in the melting temperature or a decrease in the viscosity of the hot-melt polymer.
Dans tous les cas, chaque point de polymère se trouve être réalisé par un dépôt unique, monocouche, et après l'action du bombardement électronique, ladite couche présente une température de fusion et/ou une viscosité différenciée entre une première zone inférieure qui est en contact avec le support textile et qui a une température de fusion et/ou une viscosité donnée et une seconde zone supérieure qui a une température de fusion ou une viscosité inférieure à celle du polymère thermofusible de la première zone.In any case, each point of polymer happens to be made by a single deposit, monolayer, and after the bombardment action electronic, said layer has a melting temperature and / or a differentiated viscosity between a first lower zone which is in contact with the textile support and which has a melting temperature and / or a given viscosity and a second upper zone which has a temperature of melt or a viscosity lower than that of the hot-melt polymer of the first zone.
Lors de l'application de l'entoilage thermocollant contre la pièce d'habillement, par pression à chaud, c'est la seconde zone qui est en contact avec la pièce d'habillement et qui présente la température de fusion la plus faible qui va réagir le plus à l'action de la chaleur, tandis que la première zone qui a une température de fusion plus élevée ne réagit pas ou dans une moindre proportion. De ce fait cette première zone sert en quelque sorte de barrière au fluage du polymère thermofusible de la seconde zone.When applying fusible interfacing against the workpiece of clothing, by hot pressing, it is the second zone which is in contact with the piece of clothing and which presents the melting temperature the weaker that will react the most to the action of heat, while the first zone that has a higher melting temperature does not react or to a lesser extent. Therefore this first zone is used in some kind of barrier to creep of the hot melt polymer of the second zone.
Quelle que soit la variante de réalisation, on a une modification de la température de fusion et/ou de la viscosité qui est graduelle dans l'épaisseur du point. De ce fait, il n'y a aucun risque de décohésion ou délaminage entre deux couches de densités différentes, comme c'est le cas lors de la mise en oeuvre de la technique double couche, selon laquelle chaque point est constitué de deux couches de duretés différentes présentant toujours un point de rupture préférentiel entre les couches. Whatever the variant, there is a modification of the melting temperature and / or viscosity which is gradual in the thickness of the point. As a result, there is no risk of cohesion or delamination between two layers of different densities, as is the case during the implementation of the double layer technique, according to which each point consists of two layers of different hardnesses always having a preferential breaking point between the layers.
Il est à noter que le faisceau d'électrons généré par les canons à
électrons industriels n'a pas une action uniforme dans l'épaisseur d'une
matière donnée. Au fur et à mesure que le faisceau d'électrons pénètre à
l'intérieur de la matière, la quantité d'électrons ou dose diminue au fur et à
mesure de l'épaisseur, jusqu'à devenir nulle à une épaisseur donnée, qui
est fonction de la tension d'accélération du faisceau d'électrons. Par
exemple pour un canon à électrons dont la tension d'accélération est de
150 kV, on considère que la dose d'électrons s'annule pour une épaisseur
de 200 µm, à travers un matériau de densité 1. Cette dose est encore de
l'ordre de 50%, dans ce cas, pour une épaisseur de l'ordre de 130 µm.It should be noted that the electron beam generated by the cannons at
industrial electrons does not have a uniform action in the thickness of a
given material. As the electron beam enters
inside the material, the quantity of electrons or dose decreases as and
thickness measurement, until it becomes zero at a given thickness, which
is a function of the acceleration voltage of the electron beam. By
example for an electron gun whose acceleration voltage is
150 kV, we consider that the electron dose is canceled for a thickness
of 200 µm, through a material of
Le demandeur a constaté que pour obtenir une modification des propriétés physico-chimiques du polymère thermofusible qui soit telle que la couche inférieure du point puisse jouer l'effet de barrière recherché, évitant le transpercement de l'entoilage thermocollant, il était nécessaire qu'il y ait une certaine dose d'électrons qui ait atteint l'activateur radicalaire. Le réglage de la profondeur de pénétration des électrons, tel que prévu par le procédé de l'invention, vise donc à ce qu'il y ait cette dose suffisante d'électrons qui ait pu pénétrer dans l'épaisseur limitée e du polymère thermofusible, c'est à dire l'épaisseur pour laquelle la modification de propriétés physico-chimiques est recherchée.The applicant has found that in order to obtain a modification of the physicochemical properties of the hot-melt polymer which is such that the lower layer of the point can play the desired barrier effect, avoiding the piercing of the fusible interlining, it was necessary for it there is a certain dose of electrons which has reached the radical activator. The adjustment of the depth of penetration of the electrons, as provided by the process of the invention, therefore aims to ensure that there is this sufficient dose of electrons which could have penetrated into the limited thickness e of the hot-melt polymer, that is to say the thickness for which the modification of physicochemical properties is sought.
Etant donné que les canons à électrons industriels sont standardisés et qu'il n'est pas possible facilement d'en faire varier la tension d'accélération, selon le procédé de l'invention, on diminue la profondeur de pénétration du faisceau d'électrons dans les points de polymère thermofusible en interposant un filtre entre le faisceau d'électrons et le support d'entoilage.Since industrial electron guns are standardized and it is not easy to vary the voltage acceleration, according to the method of the invention, the depth of penetration of the electron beam into the polymer points hot melt by interposing a filter between the electron beam and the stabilizer support.
Ce filtre a pour effet de diminuer artificiellement l'épaisseur de pénétration du faisceau d'électrons dans le polymère thermofusible et donc de régler précisément la profondeur de pénétration réellement efficace .This filter has the effect of artificially reducing the thickness of penetration of the electron beam into the hot-melt polymer and therefore to precisely adjust the really effective penetration depth.
Le choix du filtre, qui peut être notamment une feuille de papier et, en particulier son épaisseur, est fonction du matériau constitutif du support d'entoilage et de l'épaisseur e pour laquelle une modification des propriétés physico-chimiques est souhaitée.The choice of filter, which can in particular be a sheet of paper and, in particular its thickness, depends on the material constituting the stabilizing support and on the thickness e for which a modification of the physicochemical properties is desired.
Par exemple, pour un canon à électrons dont la tension d'accélération est de 150 kV, on a interposé un filtre en papier pesant de l'ordre de 50 à 60 g/m2.For example, for an electron gun with an acceleration voltage of 150 kV, a paper filter weighing on the order of 50 to 60 g / m 2 has been interposed.
De préférence les conditions opératoires du bombardement électronique ainsi que le choix et la quantité d'activateur radicalaire sont déterminées en sorte que la température de fusion du polymère thermofusible ait une variation, en plus ou en moins de l'ordre de 1O à 2O°C dans la zone soumise au bombardement électronique.Preferably the operating conditions of the bombardment electronics as well as the choice and quantity of radical activator are determined so that the melting point of the polymer hot-melt has a variation, more or less of the order of 1O to 20 ° C in the area subject to electronic bombardment.
La présente invention sera mieux comprise à la lecture de la description qui va être faite de deux exemples de réalisation d'un entoilage thermocollant dont les points de polymère thermofusible, monocouche, présentent une température de fusion différenciée, illustrée par le dessin annexé dans lequel :
- La figure 1 est une représentation schématique en plan et fortement grosse d'un entoilage thermocollant,
- et la figure 2 est une représentation schématique en coupe dudit entoilage au droit d'un point de polymère.
- FIG. 1 is a schematic plan view and very large of a fusible interlining,
- and Figure 2 is a schematic sectional representation of said interlining in line with a polymer point.
Un entoilage thermocollant 1 est constitué d'un support 2 et de
points 3 de polymère thermofusible et thermocollant. Le support peut être
soit un support textile proprement dit, du type tissé, tricot maille ou tricot à
insertion de trame, soit un non-tissé. Les points 3 de polymère
thermofusible sont disposés sur tout ou partie de la surface d'une des deux
faces du support 2, dénommée face endroit. C'est cette face endroit qui est
destinée à venir s'appliquer contre la face envers de la pièce d'habillement
à protéger ou renforcer.A fusible interlining 1 consists of a
Le polymère thermofusible est un type connu, parmi les polyamides, polyéthylènes, polyuréthannes, polyesters, aminoplastes... Cela peut également être un copolymère. L'important est que le polymère en question puisse, à la température d'application de la pièce d'habillement sous pression à chaud, réagir en fondant localement pour adhérer sur les fibres ou filaments de la face envers de la pièce d'habillement.The hot-melt polymer is a known type, among polyamides, polyethylenes, polyurethanes, polyesters, aminoplasts ... This can also be a copolymer. The important thing is that the polymer in question can, at the temperature of application of the piece of clothing under hot pressure, react by locally melting to adhere to the fibers or filaments on the reverse side of the piece of clothing.
De manière conventionnelle, les points de polymère sont déposés sous forme d'une dispersion aqueuse qui est ensuite soumise à un traitement thermique de manière à évaporer le solvant et à agglomérer de nouveau les particules de polymère thermofusible pour réaliser leur accrochage sur le support. Le dépôt des points de polymère se fait par toute technique classique, notamment d'impression au cadre rotatif ou autre.Conventionally, the polymer dots are deposited in the form of an aqueous dispersion which is then subjected to a heat treatment so as to evaporate the solvent and agglomerate new hot melt polymer particles to achieve their hanging on the support. The polymer points are deposited by any conventional technique, in particular printing with a rotary frame or other.
En pratique, les points de polymère en surface du support d'entoilage représentent de l'ordre de 5 à 2Og/m2, en fonction du type de support.In practice, the polymer points on the surface of the interlining support represent of the order of 5 to 20 g / m 2 , depending on the type of support.
La dispersion aqueuse de polymère thermofusible comprend également un activateur radicalaire, c'est-à-dire un composé qui est apte à former des radicaux libres sous l'effet d'un bombardement électronique, et est exempte d'agent photo-inhibiteur.The aqueous dispersion of hot-melt polymer comprises also a radical activator, i.e. a compound which is capable of form free radicals under the effect of electronic bombardment, and is free of photo-inhibiting agent.
Il s'agit par exemple mais non exclusivement, d'un activateur du type acrylique, tel que le triméthylol propane triméthacrylate ou encore le triméthylol propane triacrylate.La proportion d'activateur radicalaire peut être comprise entre 5 et 2O% en poids par rapport au polymère thermofusible.It is for example, but not exclusively, an activator of the acrylic type, such as trimethylol propane trimethacrylate or else trimethylol propane triacrylate.The proportion of radical activator can be between 5 and 20% by weight relative to the hot-melt polymer.
Dans un premier exemple de réalisation, après avoir effectué le
dépôt de la dispersion aqueuse de polymère thermofusible puis le
traitement thermique de celle-ci en vue d'évaporer l'eau contenue dans la
dispersion et d'agglomérer le mélange polymère thermofusible et activateur,
on procède à un bombardement électronique de la face envers 2b du
support d'entoilage 2, c'est-à-dire la face qui ne comporte pas les points 3
de polymère. Les électrons passent à travers les filaments ou fibres 4 du
support 2 et pénètrent dans le point de polymère 3 où ils rencontrent
l'activateur radicalaire. Sous l'effet de ces électrons, l'activateur radicalaire
engendre des radicaux libres qui développent des réactions de réticulation
dans la zone 3a du polymère thermofusible. In a first exemplary embodiment, after having carried out the deposition of the aqueous dispersion of hot-melt polymer and then the heat treatment of the latter in order to evaporate the water contained in the dispersion and to agglomerate the mixture of hot-melt polymer and activator, electron bombardment is carried out on the
Dans cette variante de réalisation, la profondeur de pénétration des
électrons, la quantité et le choix de l'activateur radicalaire sont déterminés
de manière à ce que seule la zone 3a du polymère thermofusible qui est en
contact ou à proximité immédiate des fibres ou filaments 4 du support et
soumise à l'action des électrons subisse la modification recherchée des
propriétés physico-chimiques à savoir augmentation de la température de
fusion ou de la viscosité du polymère thermofusible. Sur la figure 2 on a
représenté schématiquement la séparation de cette première zone 3a, à
structure modifiée, d'avec la seconde zone 3b à structure non modifiée par
une ligne discontinue 5. En réalité l'action est graduelle dans l'épaisseur
du point. Quoi qu'il en soit, il se crée, sous l'action contrôlée du
bombardement électronique, une différenciation dans l'épaisseur de chaque
point de polymère 3. Cette différenciation due à une certaine réticulation,
se traduit dans ce premier exemple par une augmentation de la
température de fusion du polymère thermofusible constitutif de la première
zone 3a, cette température de fusion restant inchangée en ce qui concerne
la seconde zone 3b non significativement modifiée par l'action des
électrons.In this variant embodiment, the penetration depth of the electrons, the quantity and the choice of the radical activator are determined so that only zone 3 a of the hot-melt polymer which is in contact or in the immediate vicinity of the fibers or filaments 4 of the support and subjected to the action of the electrons undergoes the desired modification of the physicochemical properties, namely an increase in the melting temperature or in the viscosity of the hot-melt polymer. In FIG. 2 is shown schematically the separation of this first zone 3 a , with modified structure, from the
Il est à noter que chaque point de polymère thermofusible, dans lequel pénètrent les électrons, constitue un milieu solide. De ce fait, les réactions de réticulation, générées grâce aux radicaux libres, ne se propagent que très faiblement, contrairement à ce qui pourrait se produire s'il s'agissait d'un milieu liquide.It should be noted that each point of hot-melt polymer, in which penetrate the electrons, constitutes a solid medium. Therefore, the cross-linking reactions, generated by free radicals, do not propagate only very weakly, unlike what might happen if it was a liquid medium.
Lorsqu'on réalise l'application sous pression à chaud de l'entoilage
thermocollant 1 sur la pièce d'habillement, à la température habituellement
mise en oeuvre pour le polymère thermofusible en question, seule la
seconde zone 3b de chaque point 3 est amenée à réagir, c'est-à-dire à
exercer son pouvoir adhérent par fusion du polymère thermofusible. La
température d'application est insuffisante, du fait de l'augmentation de sa
température de fusion, pour faire réagir le polymère contenu dans la
première zone 3a. Ainsi lors de l'application sous pression, le polymère de
la seconde zone 3b ne peut pas fluer à travers les fils ou filaments 4 du
support 2, ce fluage étant empêché par la première zone 3a du point 3, qui
ne réagit pas et fait office de barrière.When the hot-
De manière à ce que cet effet barrière puisse être efficace tout en
ne diminuant pas outre mesure l'action adhérente de chaque point 3, les
conditions opératoires, et en particulier la profondeur de pénétration des
électrons, sont déterminées pour que l'épaisseur relative de la première
zone 3a soit comprise entre 1O et 5O% de l'épaisseur totale du point de
polymère 3, de préférence entre 10 et 20%.So that this barrier effect can be effective while not unduly reducing the adherent action of each
On a utilisé comme polymères thermofusibles des polyamides ou des polyéthylènes haute densité ou des polyuréthannes et comme activateurs radicalaires le triméthylol propane triméthacrylate ou le triméthylol propane triacrylate à raison de 5 à 20% en poids de polymère. Le dépôt de polymère thermofusible était réalisé à raison de 9 à 16g/m2 sur le support d'entoilage. On a mis en oeuvre un canon à électrons, avec des doses comprises entre 10 et 75 KGy et des tensions d'accélération de 100 à 200 kV. Le réglage de la profondeur de pénétration des électrons s'est fait en interposant des filtres en papier de grammage compris entre 50 et 100 g/m2.Polyamides or high density polyethylenes or polyurethanes have been used as hot melt polymers and as radical activators trimethylol propane trimethacrylate or trimethylol propane triacrylate in an amount of 5 to 20% by weight of polymer. The hot melt polymer deposition was carried out at a rate of 9 to 16 g / m 2 on the interlining support. An electron gun was used, with doses between 10 and 75 KGy and acceleration voltages from 100 to 200 kV. The electron penetration depth is adjusted by interposing paper filters weighing between 50 and 100 g / m 2 .
Les meilleurs résultats ont été obtenus avec un mélange de polyéthylène haute densité, comme polymère thermofusible, et de triméthylol propane triméthacrylate, comme activateur radicalaire, ce dernier étant présent à raison de l'ordre de 20% en poids par rapport au polymère thermofusible, dans le cas où le mélange de ces deux composants est réalisé initialement dans la dispersion aqueuse servant au dépôt de points de polymère. Ces meilleurs résultats ont été obtenus en mettant en oeuvre une dose d'électrons de 50 kGy et un filtre de 56 g/m2. Les tests de collage ont montré une augmentation sensible des forces de collage, dans les mêmes conditions et à même température, par rapport à un échantillon témoin n'ayant pas subi de bombardement électronique. De plus on a réalisé des tests de traversée dans lesquels on replie un échantillon d'entoilage sur lui-même de manière à appliquer l'une contre l'autre deux faces envers, ne portant pas de point de polymère thermofusible et on mesure la force nécessaire pour séparer ces deux faces après application d'une pression sous une température comprise entre 150 et 170°C. Ces tests ont montré une quasi disparition des forces de séparation, significatives de la traversée du polymère thermofusible à travers le support d'entoilage, pour les échantillons soumis au bombardement électronique. Par contre ces forces de séparation restaient importantes pour l'échantillon témoin, non soumis au bombardement électronique ; elles étaient, pour une température d'application de 150°C, de l'ordre de 25 à 30% des forces de collage, c'est à dire des forces nécessaires pour séparer la face endroit de l'échantillon appliquée sur un article de référence.The best results have been obtained with a mixture of high density polyethylene, as hot-melt polymer, and trimethylol propane trimethacrylate, as free radical activator, the latter being present in the order of 20% by weight relative to the hot-melt polymer, in the case where the mixing of these two components is carried out initially in the aqueous dispersion used for the deposition of polymer dots. These best results were obtained by using a dose of electrons of 50 kGy and a filter of 56 g / m 2 . The bonding tests showed a significant increase in the bonding forces, under the same conditions and at the same temperature, compared to a control sample which had not undergone electronic bombardment. In addition, crossing tests were carried out in which a sample of interlining was folded back on itself so as to apply two reverse sides against each other, not carrying a point of hot-melt polymer and the force was measured. necessary to separate these two faces after applying pressure at a temperature between 150 and 170 ° C. These tests showed a virtual disappearance of the separation forces, significant from the crossing of the hot-melt polymer through the interlining support, for the samples subjected to electron bombardment. On the other hand these forces of separation remained important for the control sample, not subjected to the electronic bombardment; they were, for an application temperature of 150 ° C., of the order of 25 to 30% of the bonding forces, that is to say the forces necessary to separate the right side of the sample applied to an article of reference.
Il serait possible de diminuer la quantité relative d'activateur radicalaire par rapport au polymère thermofusible en procédant à une opération de mélange préalable destiné à avoir un contact plus intime entre l'activateur radicalaire et le polymère thermofusible. Pour cela on mélange le polymère thermofusible et l'activateur radicalaire, sous forme de poudres, on soumet ce mélange à des opérations successives de fusion, extrusion et broyage de manière à obtenir une poudre qui est ensuite mise en dispersion aqueuse pour former la pâte servant au dépôt de points de polymère thermofusible sur la face endroit du support d'entoilage.It would be possible to decrease the relative amount of activator radical with respect to the hot-melt polymer by carrying out a preliminary mixing operation intended to have a more intimate contact between the radical activator and the hot-melt polymer. For that we mix the hot-melt polymer and the radical activator, in the form of powders, this mixture is subjected to successive operations of fusion, extrusion and grinding so as to obtain a powder which is then put in aqueous dispersion to form the paste used for the deposition of hot-melt polymer on the right side of the stabilizer support.
Il est de plus à noter que cet effet d'augmentation de la température de fusion du polymère thermofusible peut également être obtenue en ajoutant dans la dispersion de polymère une charge durcissable, c'est-à-dire une charge qui sous l'action du bombardement électronique va polymériser et durcir de manière irréversible, n'étant plus de ce fait réactivable thermiquement comme c'est le cas du polymère thermofusible. Les monomères acryliques font partie des charges durcissables. Ainsi s'il est lui-même du type acrylique l'activateur radicalaire peut constituer également en partie une charge durcissable.It should also be noted that this effect of increasing the temperature of the hot-melt polymer can also be obtained by adding a curable filler to the polymer dispersion, i.e. a charge which under the action of electronic bombardment will polymerize and harden irreversibly, thus no longer being reactivated thermally as is the case with the hot-melt polymer. The acrylic monomers are part of the curable fillers. So if he is itself of the acrylic type, the radical activator can also constitute partly a curable filler.
Dans un autre exemple de réalisation, le bombardement électronique intervient sur la face endroit 2a du support 2.Les conditions opératoires du bombardement électronique, les polymères thermofusibles, et les activateurs sont sélectionnés en sorte d'avoir l'effet inverse de celui du premier exemple, à savoir une diminution de la température de fusion et/ou de la viscosité des polymères sous l'action du bombardement électronique. A cette différence près, les considérations données ci-dessus restent valables.In another embodiment, the electron bombardment takes place on the two facing support 2.The operating conditions of the electron bombardment, the thermofusible polymers, and the activators are selected so to have the opposite effect to that of the first example, namely a decrease in the melting temperature and / or the viscosity of the polymers under the action of electron bombardment. With this difference, the considerations given above remain valid.
Dans ce cas, on part d'un copolymère ayant une température de fusion de 14O°C pour l'amener, dans la zone soumise au rayonnement EB, à une température de 1OO/12O°C.In this case, we start from a copolymer having a temperature of fusion of 140 ° C. to bring it into the zone subjected to EB radiation, at a temperature of 100/120 ° C.
Claims (11)
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FR9700704A FR2758443B1 (en) | 1997-01-20 | 1997-01-20 | PROCESS FOR MANUFACTURING THERMAL-STICKING LINING AND THERMAL-STICKING LINING OBTAINED |
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CN102697213B (en) * | 2012-06-30 | 2014-02-26 | 杭州奥科服装辅料有限公司 | Double-point coating production line for hot-melt adhesive padding cloth |
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-
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- 1998-01-15 KR KR10-1998-0000933A patent/KR100456919B1/en not_active IP Right Cessation
- 1998-01-16 AR ARP980100186A patent/AR014618A1/en active IP Right Grant
- 1998-01-16 MY MYPI98000186A patent/MY124650A/en unknown
- 1998-01-19 CN CN98104282A patent/CN1122467C/en not_active Expired - Lifetime
- 1998-01-19 AU AU52142/98A patent/AU729178B2/en not_active Ceased
- 1998-01-19 RU RU98101817/04A patent/RU2161007C2/en not_active IP Right Cessation
- 1998-01-19 NO NO980237A patent/NO980237L/en not_active Application Discontinuation
- 1998-01-19 SK SK70-98A patent/SK284794B6/en not_active IP Right Cessation
- 1998-01-19 BR BR9800358-5A patent/BR9800358A/en not_active IP Right Cessation
- 1998-01-19 US US09/008,742 patent/US5993918A/en not_active Expired - Lifetime
- 1998-01-19 UA UA98010278A patent/UA42846C2/en unknown
- 1998-01-20 PT PT98490005T patent/PT855146E/en unknown
- 1998-01-20 EP EP98490005A patent/EP0855146B1/en not_active Expired - Lifetime
- 1998-01-20 AT AT98490005T patent/ATE209865T1/en active
- 1998-01-20 CZ CZ0018498A patent/CZ297505B6/en not_active IP Right Cessation
- 1998-01-20 CA CA002227397A patent/CA2227397C/en not_active Expired - Lifetime
- 1998-01-20 PL PL324377A patent/PL191374B1/en not_active IP Right Cessation
- 1998-01-20 HU HU9800093A patent/HUP9800093A3/en unknown
- 1998-01-20 ES ES98490005T patent/ES2172105T3/en not_active Expired - Lifetime
- 1998-01-20 ZA ZA98444A patent/ZA98444B/en unknown
- 1998-01-20 JP JP02270898A patent/JP4271744B2/en not_active Expired - Lifetime
- 1998-01-20 TR TR1998/00081A patent/TR199800081A2/en unknown
- 1998-01-20 DK DK98490005T patent/DK0855146T3/en active
- 1998-01-20 DE DE69802717T patent/DE69802717T2/en not_active Expired - Lifetime
- 1998-11-17 HK HK98112059A patent/HK1010819A1/en not_active IP Right Cessation
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1314366A1 (en) * | 2001-11-26 | 2003-05-28 | Lainiere de Picardie BC | Method for making a fusible interlining with dots of thermally fusible polymer and thermally fusible polymer used thereby |
FR2832595A1 (en) * | 2001-11-26 | 2003-05-30 | Lainiere De Picardie Bc | METHOD FOR MANUFACTURING A THERMOCOLLATING WEAR WITH POINTS OF THERMOFUSIBLE POLYMER AND THERMOFUSIBLE POLYMER SPECIALLY DESIGNED FOR CARRYING OUT SAID METHOD |
US6991832B2 (en) | 2001-11-26 | 2006-01-31 | Lainiere De Picardie Bc | Method of producing a fusible interfacing with dots of hot-melt polymer, and hot-melt polymer designed especially for carrying out said method |
EP1749451A1 (en) | 2005-08-05 | 2007-02-07 | Arkema France | Method for bonding textiles by means of a thermofusible adhesive |
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