TW201208597A - Process for joining together components, in particular in the production of shoes - Google Patents

Abstract

The present invention relates to a process for joining together at least two components with the aid of an adhesive and an assembled component which has been produced by this process. The pressure is exerted such that a flexible casing (4) at least partly enclosing the first (1) and second component (2) is contracted by an external stimulus. The external stimulus is based on a heat treatment and/or on an evacuation of the enclosing flexible casing (4). In particular, the process is suitable in the production of shoes. It furthermore relates to a component which has been joined together with the process according to the invention.

Description

201208597 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of bonding at least two components by means of an adhesive and an assembly which has been produced by the method. In particular, the method is suitable for use in the manufacture of shoes. Furthermore, there is a component that has been combined in accordance with the method of the present invention. [Preorder] Technology] When the two components are bonded by means of an adhesive, the fixing of the components is important for the dimensional precision of the adhesive bonding. In particular, where the adhesive bond is exposed to stress, the bond should be pressed or fixed in place until the dot polymer produces a sufficiently high bond strength. The bond strength can be produced by cooling the thermal adhesive layer or by polymerizing the adhesive. In this context, the assembly of the components can be mechanical, for example by means of a punch or a screw clamp. After mechanical fixation, the assembly remains held for a specified period of time until the adhesive polymer produces a sufficiently high bond strength. This causes extremely high time consumption during manufacturing. For example, the above method is used to manufacture footwear. The combined components are repackaged after fixing to protect the bonded components from environmental influences. Therefore, the manufacturing cost is increased. ^ Irregular shapes and flexible components to be bonded (for example) shoes and uppers. Thus, for example, DE 198 09 077 A1 describes a method for producing shoes having an upper, a lining and a sole, wherein the upper and the 〇201208597 are respectively joined to each other by the outer shoes* The individual components are joined to each other by bonding and in each case: the upper and the inner shoe are formed by heating the hand-prepared shoe blank onto the pure material to obtain the outer upper and the _= pad, and as already mentioned, the bonding method The shortcomings are that after fixing and hardening, the 岐B must be removed. The packaging of the affixed items in the other step must be carried out in the food technology towel, especially by the true two packaging. Here the food is placed in a bag and the bag is taken out of the vacuum. As a result of the vacuum, the bag sticks to the outline of the food. In this way, the food life can be extended and the food can be protected from freezing damage. This procedure is still unknown for fixed adhesive bonding. There is therefore a need for other methods for combining at least two components and thereby reducing the time and cost of the combination and subsequent manufacturing steps and components that can be combined using this method. SUMMARY OF THE INVENTION According to the present invention, a method for combining at least two components is provided which includes the steps of: providing first and second components; applying an adhesive to the first and/or second component; combining the first and second The assembly, the first and second components are at least partially joined to each other by an adhesive; 201208597 the pressure is at least partially 'and then the first and second components are introduced into the flexible cover for at least 1 minute; Applying pressure on the first and second components to the adhesive between the first and second components and the second component to be stored in the shrinkable flexible cover; ^pressure to at least partially enclose the second and second components The visible curved cover is shrunk by an external stimulus and the external contact is closed based on the reduction and/or deformation. Preferably, the first and second components are stored for a particularly good storage time of at least 1 G minutes and the second component is preferably stored in the shrinkable flexible cover until a stable adhesive bond has been formed between the first and second components. . The method according to the invention has the advantage that the irregularly shaped articles which are adhesively bonded to the stress can be fixed to each other until a sufficient bonding strength is obtained without the use of a specific pressurizing tool during the entire operation. In principle, the component has been configured for the next time after the flexible cover has been violently exposed to external stimuli. Another advantage is that the flexible cover can be used as a package for component configurations at the same time. To apply pressure to the assembled components, the flexible cover at least partially encloses the components. The flexible cover preferably completely encloses the components. In its simplest form, the cover can be a tube with an opening on either side or both sides. "Flexible" means that after the vacuum and/or heat is applied, the cover is accessible; the part is mounted to the outer contour of the component to be fixed.

S 6 201208597 has a flexible construction. After exposure to external stimuli, the hood shrinks around the component to be secured and applies the desired pressure in this manner. The pressure applied to the assembly can also be affected by the flexibility of the cover. If the external stimulus includes heat, the reactive adhesive can be activated simultaneously by this means. The material of the cover is not further specified at first and may conveniently comprise a thermoplastic polymer such as, for example, polyamine phthalic acid vinegar, polyamine, polyethylene, polyolefin, PVDF, PVS, PTFE and/or polymer composite film. . The cover preferably has a non-stick surface treatment (non-stick f~lnish). When the flexible cover is evacuated from around the assembly, it is preferred to remove air from the entire cover. If in the case of a concave component, this is not feasible, the final pressure in the cover can be (e.g. mbar or puppet mbar.) In the method according to the invention, the closure is preferably flexible after shrinking. The curved cover is welded or mechanically clamped to at least one end with a clip, so that the shrinking closed flexible cover completely closes the bonded assembly. The combined assembly can then be blocked from the environment. This prevents environmental influences such as contracted air or The dirty particles are prevented from entering the contracted closed flexible cover and reach the bonded component. Furthermore, the welding prevents the shrinking closure from re-expanding and no longer applies pressure to the bonded adhesive region. In the method according to the invention The single-piece or multi-piece closed flexible cover can be used to close the combined first and second components. If the combined component of the small number is manufactured, the flexible cover can be closed in a single piece* ·,,°, therefore, the device that provides the closed flexible cover does not require a large 7 201208597 space. In the case of a large number of pieces, it is better to close the flexible cover in multiple pieces. For example, the closed flexible cover can be Contains two Two webs of film °—The film is placed on a conveyor belt on which the bonded components are placed. The second film is passed over the bonded components and the film is placed on the bonded components. In another step The device welds the two rolls of film together and thus produces a closed flexible cover that contracts due to at least one external stimulus. [Embodiment] In one embodiment of the method according to the invention, the first component comprises a sole and The second component comprises an upper. Also included herein is a sole, a boot, and the like. In another embodiment of the method according to the present invention, the vacuum package is used as a package flexible cover. When the air in the vacuum package is in the open side and the air in the vacuum package is evacuated, the vacuum package shrinks and encapsulates the bonded components. Therefore, the vacuum package applies pressure to the adhesive region and is thus fixed. For example, the vacuum laminator can be used. In another embodiment of the method according to the invention, a shrink film, a hood and/or a shrink tube are used as the encapsulating flexible cover. These outer casings shrink when heated. Member may be (e.g.) is wound into a shrink film or shrink tube disposed in 'followed by heating of the cover and contraction of the heating and vacuum pump combination, of course also be used in accordance with the present invention party

S 201208597 French. It is conceivable that the thermoplastic vacuum bag can be made flexible by thermal action, for example, prior to vacuuming. In another embodiment of the method according to the invention, the adhesive comprises an aqueous polyurethane dispersion. This is preferably an aqueous polyurethane dispersion containing polyaminoformic acid vinegar (A) wherein the polyamino phthalic acid ester (A) is of the following composition: A1) polyisocyanate, A2) having an average Molecular weight is moo gram / mol to ^ 8, gram / Moer polymer polyol and / or polyamine, A3) as the case has a molecular weight ^ 4 gram / Moer's single _ and / or polyol Or a reaction product of a mono- and/or polyamine or an amino alcohol with at least one compound selected from the group consisting of: A4) a compound having at least one ion or a latent ionic group and/or A5) a nonionic hydrophilic compound. Potential ionic groups can form groups of ionic groups. The polyamino phthalate (A) is preferably from > 7 wt% to 45% by weight of A1), 250 to S91 wt% of A2), > 0 to <15 wt% of A5), 20 It is made up to <12% by weight of ion or latent ionic compound A4) and optionally to S30% by weight of compound A3), wherein the sum of A4) and A5) is > 0.1 to <27% by weight and The sum of the components totaled 100% by weight. The polyamino phthalate (A) is particularly preferably from 21 Å to <3 〇% by weight of A1), from 65 to 90% by weight of A2), from 2 Å to <1% by weight of A5), > 3 to S9 wt% of ions or potential ionic compounds A4) and optionally 9 201208597 20 to < 10 wt% of compound A3), wherein the sum of A4) and A5) is 20.1 to 19% by weight and The sum of the components totaled 100% by weight. The polyamino phthalate (A) is particularly preferably from 3 to S27 wt% of A1), from 265 to <85 wt% of A2), from 20 to <8 wt% of A5), 23 to <8 The weight % of the ion or the latent ionic compound A4) and optionally 20 to 0% by weight of the compound A3), wherein the sum of A4) and A5) is from 20.1 to < 16% by weight and the total of the components is 100 weights. %. Suitable polyisocyanates (A1) are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates. Mixtures of such polyisocyanates can also be used. Examples of such suitable polyisocyanates are butyl diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2, 2, 4 and/or 2, 4, 4 · three Mercaptohexamethylene diisocyanate, isomeric bis(4,4'-isocyanatocyclohexyl)decane or a mixture of any desired isomer content, isocyanatoinyl-1,8- Octane diisocyanate, 1,4_cyclohexyl diisocyanate, 1,4-phenylene diisocyanate, 2,4- and/or 2,6·曱phenylene diisocyanate, 1,5-anthranyl Diisocyanate, 2,4'- or 4,4'-diphenyldecane diisocyanate, triphenyldecane-4,4',4"-triisocyanate or its amino phthalate, trimer isocyanate a derivative of a ureido phthalate, a biuret, a ureidodione or an imine oxadiazine ketone structure, and a mixture thereof, preferably a hexamethylene diisocyanate, an isophorone diisocyanate, and a different Bis(4,4'-isocyanatocyclohexyl)decane and mixtures thereof. 201208597 Preferred are polyisocyanates or polyisocyanates of the type described above having only aliphatic and/or cycloaliphatic bonded isocyanate groups. Ester mixture. Very good starting component (A1) is a mixture of HDI, IPDI and/or 4,4,-diiso-acid dicyclohexyl oxime. 0 Any desired polyisocyanate of at least two types of isocyanate is made by simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanate And having a ureidodione, a trimeric isocyanate, an amine phthalic acid, a urea guanidine g_, a double condensed gland, an imine oxadione, and/or an oxadiacetate The tank described in Chem 336 (1994) p.l85_2GG is suitable as polyisocyanuric acid (A1). The combined polymeric polyol or polyamine (A2) has an OH functionality of d.5 to 4S. Such as, for example, polyacrylate, polyester, polylactone, polysodium sulphate anti-I 酉曰, poly-g carbonate condensate, poly-sparing hydrocarbons and polyoxo-oxygen. Preferred molecular weight range from gram / Moer to 5 gram / Moer and the same as the polyol. 3 hydroxy possible polycarbonate can be by carbonic acid derivatives (such as diphenyl wei m reading phosgene) and diol The reaction is obtained. These possible glycols (for example) ethylene glycol, U· And U-propanol 1,3- and 1,4-butanediol, !, hexanediol, u-octanediol, neopentyl glycol: bishydroxydecylcyclohexane, 2-methyl- U-propanediol 2,2'^-mercapto pentane decathylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, A, Siqian (4) A and the binary transformation of the internal 201208597 ester The diol component preferably comprises from 5% by weight to < 100% by weight of hexanediol, preferably hexane 丨, 6 diol and/or hexane diol derivative, preferably And the like, further comprising an ether or ester group in addition to the terminal hydrazine H group, for example, by i mole hexanediol and at least i mole, preferably 1 to 2 moles of caprolactone according to DE-A 1 770 The 245 reaction is obtained by etherification of hexanediol itself to obtain di- or trihexylene glycol. The preparation of such derivatives is known, for example, from DE-A 1 57 〇 54 。. Polyether polycarbonate diols as described in DE-A3 717 060 can also be used. Preferably, the hydroxy polycarbonates should be linear. However, it may optionally be lightly branched by incorporating a polyfunctional component, particularly a low molecular weight polyol. For example, glycerol, trihydrocarbyl propane, hexane 4,2,6-alcohol, butane-1,2,4-triol, tri-propyl mercapto, pentaerythritol, hydrazine, 4·cyclohexanediol Mannitol, sorbitol, methyl glycoside and 1,3,4,6-dianhydrohexanol are suitable for use herein. Suitable polyether polyol-based polyamine phthalate chemistry is known per se, for example, by polymerizing a tetrahydrogenate by cationic ring opening. Further, a suitable polyether polyol-based polyether is, for example, a polyol made of oxidized stupid ethylene, propylene oxide, butylene oxide or epichlorohydrin, particularly propylene oxide, using a starting molecule. Suitable polyester polyols are, for example, polyfunctional, preferably di- and/or optionally trifunctional alcohols with polyfunctional, preferably monofunctional, citric acid. Can also use the corresponding aggregation of lower alcohols

S 12 201208597, an acid anhydride or a corresponding poly vinegar or a mixture thereof to replace the free poly-retensive acid to prepare a polyester. The polycarboxylic acid can be an aliphatic, cycloaliphatic, aromatic and/or heterocyclic nature and can optionally be substituted, e.g., substituted by (iv) atoms and/or unsaturated. Component A3) is suitable for terminating the polycarbamic acid g prepolymer. Monofunctional alcohols and monoamines are secretive. Preferred units—aliphatic unit alcohols having from 1 to 18 C atoms, such as, for example, ethanol, n-butanol, ethylene glycol monobutyl hydrazine, diethyl hexanol, 1-octyl alcohol, and budecyl alcohol Or cetyl alcohol. Preferred are monoamine aliphatic monoamines such as, for example, diethylamine, dibutylamine, ethanolamine, N-mercaptoethanolamine or N,N-diethanolamine and Jeffamin®® % ^ (Huntsman Corp. Europe, Belgium) ^ Amine or amine functional polyethylene oxide and polypropylene oxide. Most of the τ, ol, amine or polyamines having a molecular weight of less than 400 g/mol as described in the appropriate literature are also suitable as component (A3). Preferred component (A3) is, for example, if not: a) 1,3-propanediol, 1,4-1,3-dimercaptopropanediol, alcohol alkanediol or triol, such as ethylene 2 and 2 , 3-butanediol, 1,5-pentanyl-hexanediol, neopentyl glycol, 1,4-cyclohexanedhenol, 2-mercapto-1,3-propanediol, 2-ethylbutyl Propylene glycol, tridecyl pentanediol, positional isomer diethyl octylene glycol, 1,2_ and 1,4-cyclohexanol, hydrogenated double-branched A[2,2-bis(4-carbyl) Cyclohexyl)propane], 2,2-dimethyl-3-transpropionic acid (2,2-didecyl-3•propylidene vinegar), tris-thiopyrene, triterpenoid Propylene or glycerin, 13 201208597 b) Diols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol or hydrogen divinyl c) ester diols of the formula (I) and (II), H0-(CH2)x-C0-0-(CH2)y-0H (I) H0-(CH2)x-0-C0- R-C0-0(CH2)x0H (II) wherein R is 1 to 10 C atoms, preferably 2 to 6 C atoms of an alkyl or aryl group, X is 2 to 6 and y is 3 to 5, Such as, for example, [δ]-pyridyl-[ε]-p-hexanoate, [ω]-ylhexyl-[γ]-hydroxybutyrate, Diacid ([β]-hydroxyethyl) ester and bis([β]-hydroxyethyl)terephthalate and d) di- and polyamines such as, for example, 1,2-diaminoethane , i, 3-diaminopropane, 1,6-diaminohexane, 1,3 and 1,4-phenylenediamine, 4,4'-diphenylmethanediamine, isophorone An isomer mixture of amine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentenylenediamine, diethylenetriamine, 13- and 14-Extenient diamine, [a], [a], [cx'], [a']-raf*-l, 3jl, 4, |*: amine, 4,4-diaminodicyclohexyl A decane, amine functional poly Ethylene bromide or polyepoxypropylene, available under the name Jeffamin® D series (Huntsman Corp. Europe, Belgium), diethylenetriamine and triethylenetetramine. Also applicable in the background of the present invention is 201208597 Amine hydrazine, hydrazine hydrate and substituted hydrazine, such as (for example, methyl phenanthrene, anthracene, fluorene-methyl arson and its homologues and acid distilling, adipic acid , adipic acid, sebacic acid, 3-hydroxypropionic acid and terephthalic acid, semicarbazido-stretching base, such as, for example, [β]-semicarbaryl propionate肼 (for example, described in DE-A 1 770 591), semi-carved basal base, such as, for example, 2 _ carbazine ethyl carbazine ester (for example, described in DE -A 1 918 504) or an amine-based semi-carboxylidene compound, such as, for example, [β]-aminoethylcarbacarbyl carbonate (for example, as described in DE-A 1 902 931). Α 4) contains an ionic group which may be cationic or anionic in nature. Compounds having a cationic or anionic dispersion may contain, for example, ruthenium, ammonium, squama, carboxylate, sulfonate or phosphonate or may be salted Forming a group which is converted into the above group (potential ionic group) and can be incorporated into the macromolecule by the isocyanate-reactive group present. The trans group and the amine group are preferably suitable. Cyanate g is a reactive group. Suitable ionic or latent ionic compounds (A4) are, for example, mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and Diaminosulfonic acid and mono- and dihydroxyphosphonic acid or mono- and diaminophosphonic acid and salts thereof, such as dicarboxymethyl propionic acid, di-mercaptobutyric acid, trans-trimethylacetic acid, N- (2-Aminoethyl)-[β]-alanine, 2-(2-aminoethylamino)-ethanesulfonic acid, 1,2- or 1,3-propanediamine-[β ]-Ethylsulfonic acid, exoethylaminopropyl- or butyl acid, rhodopsin, bar acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5 -diamino 15 201208597 benzoic acid and an addition product of IPDA and acrylic acid (Ep_A 〇 916 647 'Example 1) and its alkali metal and/or ammonium salt; sodium hydrogen sulfite to but-2-ene-1, a propoxylated adduct of a 4-diol adduct, a polyether sulfonate, 2-butanediol and NaHS〇3, for example DE-A 2 446 440 (page 5-9 'Formula I a unit described in -III) and which can be converted into a cationic group, such as N-decyldiethanolamine as a hydrophilic builder component. Where the ionic compound has a carboxyl group or a carboxylate group and/or a sulfonate group and/or an ammonium group, the particularly preferred ionic compound contains a carboxyl group and/or a sulfonate group as an ion or a latent ionic group, such as N- (2-Aminoethyl)-[β]-alanine, 2-(2-aminoethylamino)-ethanesulfonic acid or an addition product of IPDA and acrylic acid (EP_A 0 916, example 1) And a salt of dimethylolpropionic acid. A suitable compound (A5) having a nonionic hydrophilic action is, for example, a polyoxyalkylene ether containing at least one hydroxyl group or an amine group. These polyethers comprise from 30% to 100% by weight of the units derived from ethylene oxide. Possible compounds are poly-structures with a linear structure of 1 to 3 functionalities and compounds of the general formula (III) R3 (ΠΙ)

'Into the 〆. H wherein R 1 and R 2 each independently mean a divalent aliphatic, cycloaliphatic or aromatic group having 1 to 18 C atoms, which may be interrupted with oxygen and 201208597 or a nitrogen atom and R 3 represents an alkoxy group. Polyethylene oxide base. The compound having a nonionic hydrophilic action is, for example, a monofunctional polyalkylene oxide polyether alcohol having an average of 25 to 1, and preferably 7 to about alkane units per statistically, as in the form known per se. It can be obtained by suitable filamentization of the starting molecule (10), for example, Encyclopadie der technischen Chemie, 4th edition, Vol. 19, Verlag Chemie, Weinheim, pp. 31-38). ~ Suitable starting molecules are, for example, saturated unit alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, isomeric pentanol, hexanol, octanol And decyl alcohol, n-nonanol, n-dodecanol, n-tetradecyl alcohol, n-hexadecanol, n-octadecyl alcohol, cyclohexylmethylcyclohexanol or hydroxymethylcyclohexane, 3_ Ethyl_3_hydroxymethylepoxypropane or tetrahydrogenate, diethylene glycol monoalkyl, such as (Example J) diethylene glycol monobutyl ether, unsaturated alcohol, such as allyl Alcohol, hydrazine, 1-dimethyl allyl alcohol or oleyl alcohol, aromatic alcohols such as hydrazine, isomeric methoxy or methoxy aryl, aryl aliphatic alcohols such as phenyl decyl alcohol, macro alcohol or cinnamon Alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis(2-ethylhexyl)amine, hydrazine methyl and & Ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morphine, pyrrolidine, piperidine or 1H-pyrazole. Preferably, the starting molecule is a saturated unit alcohol. Tetraethylene glycol monobutyl ether is used as a starting molecule. Suitable alkylene oxides for alkoxylation are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any desired order or also in a mixture. 201208597 Polycyclic St. Court: _ is pure polyethylene oxide 垸 或 or existing = _, its alkylene oxide unit contains at least 3 〇 mol% of the two 'better than at least 40 mol% Cyclohexane unit. Preferably, the nonionic compound is a monofunctional: propylene oxide unit having at least 4 G mole % of more than 60 mole % of propylene oxide units. Preferably, a combination of a nonionic (A4) and an ionic (A5) hydrophilic agent is used to prepare the polyaminophthalic acid ester (A). A combination of a nonionic and a negative two hydrophilic agent is used. The preparation of the aqueous polyamino phthalate (A) can be carried out in part or in a dispersed phase in one or more stages in a homogeneous or multistage reaction. The step of dispersing, emulsifying or dissolving is carried out after the polyaddition has been completely or partially carried out. Thereafter, another polyaddition or modification is carried out in the dispersed phase as appropriate. All methods known from the prior art can be used to prepare polyamino phthalate (A) 'such as emulsifier shear, acetone, prepolymerization, melt emulsification, _imine and solid spontaneous dispersion method and its derivatization method . A summary of these methods is found in NIethoden der organischen Chemie (Houben-Weyl, 4th edition, Supplement and Supplementary Volume, Volume e20, Η·Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pp. 1671-1682). . Preferred are melt emulsification, prepolymerization, and C-method. Very good is the acetone method. For the preparation of the polyamino phthalate prepolymer, the components (A2) to (A5) and the polyisocyanate 201208597 (A1) which do not contain the primary or secondary amine groups are usually initially introduced into the reactor and the mixture is introduced into the reactor. It is heated to a higher temperature, preferably from 50 to 120. In the range of (:, as appropriate, it is diluted with a solvent which is miscible with water but inert to the isocyanate group, but preferably does not contain a solvent. Suitable solvent systems (for example, acetone, methyl ethyl ketone, tetrahydrofuran, No. 0, Acetonitrile, dipropylene glycol dimethyl _ and 1 曱 _2 _ _ _ 咯 咯 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Or a higher pressure, such as a solvent, such as, for example, a reaction of acetone at a normal pressure boiling point temperature. Further, a catalyst known to accelerate the isocyanate addition reaction such as, for example, triethylamine, 1 may also be used. , 4_diazabicyclo-[2,2,2]-octane, monobutyltin oxide, tin dioctoate or dibutyltin dilaurate, bis-(2-ethylhexanoate) tin or other organometallic compounds Introduced or metered in later. It is preferably dibutyltin dilaurate. Then it is metered into the component (Al), (Α2), which does not contain the primary or dibasic amine group and is not added at the beginning of the reaction, as appropriate. (A3) and (Α4) and/or (Α5). Preparation of polyamino phthalate pre- In the case of a polymer, the ratio of the mass of the isocyanate group to the isocyanate-reactive group is Μ.90 to 幻', preferably from 0.95 to <2.5, and particularly preferably from 21.05 to 2.0. Component (Α2) to (Α5) The reaction is partially or completely relative to the total amount of isocyanate-reactive groups which do not contain a primary or di-amino group in (Α1) to (Α5), but is preferably carried out completely. The degree of conversion is conventionally monitored by monitoring. The NCO content of the reaction mixture is monitored. For this, a spectral measurement of 201208597 can be performed, such as infrared or near-infrared spectroscopy, refractive index determination or chemical analysis, such as titration of the sample taken. Free isocyanate groups can be obtained in the form of a substance or solution. Polyamino phthalate prepolymer. After or during the preparation of the polyaminophthalate prepolymer from (A1) and (A2) to (A5), if it has not been carried out in the starting molecule, it has an anion and / or cationically dispersed groups partially or completely form a salt. In the case of anionic groups, 'can be tested' as many, carbonic acid or hydrogencarbonate, dinonylamine, diethylamine, tributylamine, two Isopropylethylamine, dimercaptoethanolamine, diethyl Ethanolamine, triethanolamine, potassium hydroxide or sodium carbonate is used herein, preferably triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine. The mass of the base is from 5 to 100%. Preferably, the mass of the anionic group is from 60 to 90%. In the case of a cationic group, dinonyl sulfate or succinic acid can be used. If only the nonionic hydrophilizing compound (A5) having an ether group is used, The neutralization step may be omitted. The neutralization may also be carried out simultaneously with the dispersion, wherein the dispersed water already contains a neutralizing agent. Possible amine components are (A2), (A3) and (A4) ' The reaction may be carried out as the case may be. The elongation of the bond may be carried out in water in the dispersion in the solvent, during the dispersion or after the dispersion. The right amine group is preferably used as the (A4)' bond elongation before the dispersion. The amine component (A2), (A3) or (A4) may be added to the reaction mixture in the form of an organic solvent and/or water. It is preferred to use >70 weight/twist to <95 weight 1% solvent and/or water. If several amine components are present, the reaction can be carried out sequentially in any desired order or by the addition of the mixture 20 201208597. For the purpose of preparing the polyamine phthalate dispersion (A), the polyurethane prepolymer is optionally introduced into the dispersed water under high shear force, such as, for example, under vigorous agitation or by means of a jet disperser. Or, conversely, the dispersed water is stirred into the prepolymer. The molecular weight can then be increased by reacting the isocyanate groups which may be present with the components (A2), (A3), if this has not been done in a homogeneous phase. The amounts of polyamines (A2) and (A3) used depend on the unreacted isocyanate groups still present. Preferably, the isocyanate group of 5% to < 100%, particularly preferably 275 to <95% of the mass is reacted with the polyamines (A2) and (A3). The organic solvent may be distilled off as the case may be. The dispersions have a solids content of from 21 Torr to S70 wt%, preferably from 225 to <65 wt%, particularly preferably from y 〇 to % 重量 by weight. Polyaminophthalate dispersions may be used by themselves or with known binders, auxiliary substances and additives, especially light stabilizers such as UV absorbers and sterically hindered amines (HALS), other antioxidants, fillers and lacquer auxiliary substances. 'For example, anti-settling agents, antifoaming and/or wetting agents, flow agents, reactive diluents, plasticizers, catalysts, auxiliary solvents and/or network extenders and additives such as, for example, dispersions, pigments, dyes Or use a combination of delustering agents. In particular, it may be combined with a hydroxy-functional polyaminophthalate dispersion or a polyacrylate dispersion, as the case may be, without problems. Additives can be added directly to the PU dispersion prior to processing. However, at least a portion of the additive may also be added before or during the dispersion of the binder or binder/crosslinker mixture. The selection and metering of such materials which may be added to individual components and/or 21 201208597 total mixtures are known to those skilled in the art. In another embodiment of the method according to the invention, the additive comprises a polyurethane thermal fusion adhesive. These adhesives are also known as hot melts. It is preferably a hot melt adhesive film or a reactive hot melt adhesive. For reactive hot melt adhesives, the linear polyester and/or polyether polyol is preferably used in combination with an excess of polyisocyanate, preferably diisocyanate. The advantage of this product category is that in the absence of solvent, a hot product having a relatively low viscosity can be applied, while still obtaining high initial strength and obtaining an adhesive bond after a relatively short period of time due to further reaction with moisture and much higher than application. Extremely high temperature resistance and excellent solvent resistance. Examples of the reactive hot-melt adhesive include: A') at least one aromatic, aliphatic, araliphatic and/or cycloaliphatic isocyanate' which preferably has a weight of from 5 to 60. /. The free NCO group content (in a) and B') a polyol or polyol mixture containing at least one polyester polyol. The preparation of the compositions is preferably carried out, for example, by the following procedure: Polyol B') is mixed with isocyanate A'), and the ratio of A to B' is selected to make NCO to OH Mohrby> 丨, preferably u 2 to < 4.0, especially 1.3 to <3·〇' and fill the homogeneous mixture into a container or stir until a fixed NCO value is obtained' then fill in In the container. Choose 260Ϊ to U50°C ‘better>8〇°c to U3 (TC is preferred

S 22 201208597 Reaction temperature. The preparation of the formulations can also be carried out continuously in a series of transfer tanks or in suitable mixing units, such as, for example, a fast rotary mixer or static mixer by the stator-rotor principle. It is also possible to A, the insufficiently modified polyol or polyol mixture b, or a part thereof and react the amino phthalate-containing polyol with an excess of A') at the end of the reaction to obtain a combination of isocyanate groups. Things. The reaction of polyol B,) with isocyanate A,) can likewise be carried out in up to 5% by weight of terpolymers of aliphatic and/or aromatic diisocyanates, for example (for example in the presence of singapore or at the end of prepolymerization) Tim: This trimer is carried out. In accordance with Shu Ming New, the (4) agent includes a wet messenger (m_ure) hardened 1 CPU adhesive. The same pre-polymer can be used to blend the prepolymer into 2C PU adhesive X. , the monomeric diisocyanate used to prepare the prepolymer is less than 500 g / mol of aromatic, aliphatic or cycloaliphatic second-class brewer. Suitable aromatic diisocyanate: 'or Isocyanate I or a mixture of several isomers, isomer of the pure isomer form acid group (TDI), and the naphthyl group is a 5-n-methylphenylene diisocyanate. Base {4-diisocyanate (NDI), 'dicyanate (NDI), cyanate (MDI), diphenylnonane-2 4: lymethane·4,4'-diisophenyl W Diisocyanate _ and 2,4, isomerism; and 4, diisocyanuric acid vinegar (XDI), 4,4,-diphenyl sulfonium _ σ, one acetal vinegar, two- and four-wire two Kejiabi 2 = methyl diisocyanate diisocyanate, 1,3_phenylene diiso T曰, 4, diphenyl, 曰, U-phenylene 23 201208597 Isocyanate. Examples of suitable cycloaliphatic diisocyanates are hydrogenated products of the above aromatic diisocyanates, such as, for example, 4,4'- Dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, hydrogenated deuterated diisocyanate (H6XDI), 1-mercapto-2,4-diisocyanatocyclohexane a dimer of an alkane, m- or p-tetradecyl-decyl diisocyanate (m-TMXDI, p-TMXDI) and a fatty acid diisocyanate. An example of an aliphatic diisocyanate is tetradecyloxybutane-1,4- Diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), 1,6-diisocyanato-2,2,4-trimethyl hexane, 1, 6-Diisocyanato-2,4,4-trimethyl hexane, octadecyl diisocyanate and 1,12-dodecane diisocyanate (C12DI). by tri- or poly-polymerization of diisocyanate or The polyisocyanate formed by reacting a diisocyanate with a polyfunctional low molecular weight compound containing a hydroxyl group or an amine group is also suitable as an at least trifunctional isocyanate. The product obtained is, for example, isocyanate HDI, MDI or IPDI as a tripolymerized product of biuret, ureidodione or carbodiimide. In particular, isocyanates containing isocyanate groups of different functionalities can also be used. Examples of such aromatic asymmetric diisocyanates are all isomers of anthraquinone diisocyanate (TDI) in the form of a pure isomer or in the form of a mixture of several isomers, anthranyl-1,5 -diisocyanate (NDI), naphthyl-1,4-diisocyanate (NDI), diphenylnonane-2,4'-diisocyanate (MDI) and 4,4'-diphenylnonane-two Isocyanate and

S 24 201208597 2, a mixture of 4'-MDI isomers and 1,3-phenylene diisocyanate. Examples of suitable cycloaliphatic asymmetric diisocyanates are hydrogenated products of isophorone diisocyanate, 1-nonyl-2,4-diisocyanatocyclohexane or the abovementioned aromatic diisocyanates, in particular pure Hydrogenated MDI in the form of an isomer, preferably hydrogenated 2,4'-MDI. Examples of aliphatic asymmetric diisocyanates are 1,6-diisocyanato-2,4,4-trimercaptohexane and isocyanuric acid diisocyanate. Aromatic isocyanates are particularly suitable as isocyanates. These materials have high reactivity and rapid reaction rates in the adhesive. In this context, a large amount of a higher molecular weight polyhydroxy compound can be used as the polyol for synthesizing the PU prepolymer. Suitable polyols are preferably polyhydroxy compounds having two or three hydroxyl groups per molecule and having a molecular weight in the range of from 200 to 4,000 g/mole, preferably in the range of from 400 to 2,000 g/mole. Examples are di- and/or trifunctional polypropylene glycols and also random and/or block copolymers of ethylene oxide and propylene oxide. Another group of polyethers to be used is a polybutanediol (poly(oxytetradecyl)ethylene glycol, polyTHF) which is obtained by polymerization of tetrahydrofuranoic acid. In addition, it may be by a di- or tricarboxylic acid such as adipic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, undecanedioic acid, dodecanedioic acid, 3,3-di Methyl glutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid or a mixture thereof and a low molecular weight diol or triol, such as ethylene glycol, propylene glycol, diethylene glycol, Triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,1〇-nonanediol, U2-dodecanediol, fat Alcohol dimers, glycerol, trihydrocarbyl propane or 25 201208597 The polyesters obtained by the condensation of their mixtures are suitable as polyols. Another group of polyols which can be used in accordance with the invention is a polyester based on caprolactone, also known as polycaprolactone. In this context, the molecular weight of such polyester polyols should be less than 2,000 g/mole. However, polyester polyols of oleochemical origin can also be used. Such polyester polyols can be completely ring opened, for example, by epoxidized diglyceride containing at least a portion of an olefinically unsaturated fatty acid with one or more fatty acid mixtures of alcohols having from 1 to 12 C atoms and then triglycerides The derivative is partially transesterified to obtain an alkyl hydrazine polyol having an alkyl group of 1 to 12 C atoms. Other suitable polyols are polycarbonate polyols, monool dimers, and castor oil and derivatives thereof. It is also possible to use a polybutadiene of a hydroxy group B such as a polyol which can be obtained as a composition according to the present invention, as the one obtained under the trade name of j>〇ly bd. In addition, it is possible, for example, by an acrylate or a mercapto acrylate with a trans-g-energy acrylic acid and/or a mercapto acrylate compound, such as a benzylic acid or a hydroxypropyl group. A linear and/or weakly branched acrylate copolymer polyol obtained by radical polymerization of methyl methacrylate is suitable as a polyol. Because of this preparation process, these multiple

^The base is generally distributed randomly, so it has a linear or weakly branched polyol with an average 〇H of two degrees. While the polyol is preferably a dilute compound, it is also possible to use at least a minimum amount of a higher functionality polyol. More than 2 ancient elements should be based on liquid. The molecular weight should generally be lower than that of moules, especially below 1,200 g/mole. In this background

Under S 26 201208597, it is preferred to use a diol or a triol. In = compound. It is also possible to use a higher official < 2, _ g / Mo (4) diol two::: two to make: points: amount - in the examples, additionally using up to ^, Yuan Tu 70 in another special oil chemical polyol Or polyether. *% of the trifunctional alcohol's reaction of the ether-isocyanate monomer with the polyol, by the addition of an aprotic solvent: The formation of 'preferably' is relative to the binary:::r atmosphere. Extremely high levels of branching should be avoided. At the end of the reaction, the reaction product should be as far as possible, "day + body." Purification Steps The known method is, for example, by selective extraction, for example, using supercritical two-dimensional supercritical aprotic _ silk heterogeneous = using volatile diisocyanate sl monomer, > TDI, Preferably, IPDI, XDI, MDI' is by evaporation of excess diisocyanate S monomer. In this regard, steaming is aided by thin-layer evaporators or thin-film evaporators: the second is described in the literature. In addition, the polyaminocarboxylic acid used in the present invention: the substance 'in the case of 2C adhesive, all or two in the case of 1C sticking, the meaning of which can be mixed into the pre-understanding substance is - It is generally added to improve the properties of the necessary components in the desired direction 27 201208597 to adjust its processability, storage stability, and to use the properties in specific application fields. The solids of these materials are subdivided fillers, flow agents, deaerators, thixotropic agents, catalysts, resins, anti-aging agents, stabilizers, dyes, adhesion promoters and wetting agents. If the polyamino phthalate prepolymer consists essentially of a polyether unit, most of the antioxidants in combination with the uv stabilizer are required. If the essential component of the polyamino phthalate prepolymer is composed of polyester units, it is preferred to use a hydrolysis stabilizer such as a carbodiimide type. The choice of such stabilizers depends, on the one hand, on the major components of the composition, and on the other hand, depending on the conditions of application and the expected exposure stress of the hardened product. The P U prepolymer may additionally comprise a resin. These resin-based liquid to solid organic products' are characterized by having a broader or narrower relative molecular weight distribution. They generally have an amorphous structure. Known resins can be used, whether natural or synthetic. Natural resins can be green for plants or animals. Examples of such materials are shellac and rosin resins such as pine oil resins, scented resins or root resins. Not only natural resins, but also derivatives thereof such as hydrogenated, acetated or neutralized resins. Synthetic resins are generally obtained by polymerization or polycondensation. Examples of such materials are urea, melamine, hydrazine, hydrazine, coumarone/indole, lycoxan, acid, ketone, ketone/pan, cyclamate, alkyd, glyceride, polyester, epoxy Resin, polyamine and isocyanurate resin. These resins may contain isocyanate-reactive groups or may not contain such groups. The adhesive can be formulated from pu prepolymer. In this context,

S 28 201208597 A 1C PU adhesive can be prepared, which then comprises 95.5 to 70 weights of lanthanum/niobium polyurethane prepolymer containing NCO groups and suitable for use according to the invention and 0.5 to 30% by weight of dryness and/or Or semi-dry oil. These 1C pU adhesives may optionally contain up to 25% by weight of adhesives and auxiliary substances. In particular, it preferably comprises from 1 to 2 by weight. / Catalyst 'which may contain a catalyst for the polyurethane reaction and an additional catalyst for the crosslinking reaction of the dried or semi-dried oil. In a preferred embodiment, from 2 to 20% by weight of dry oil in terms of prepolymer is present. Further, a 2C PU adhesive can be formulated from a pu prepolymer having an NCO group and being applied according to the present invention, and a drying oil. In this context, the NCO-reactive PU prepolymer component may optionally contain up to 25% by weight of the binder and auxiliary materials, but in particular these may be added to the OH group-containing component. The amount of the component containing an OH group should be as high as 50% by weight based on the pu prepolymer, and the NCC^〇H ratio having a low excess of the isocyanate group is selected. For example, the NCO:OH ratio should be from 1.2 to 2, especially from 1.05 to 1.5. These two components are stored separately prior to use and mixed directly prior to use and then used as an adhesive. A liquid polyol having a functionality of 2 to 5 can be selected as the group containing the hydrazine H group. These may be one or more of the above polyols. However, in this context, the molecular weight can be higher and can be, for example, up to 1 Torr, gram per mole. These polyols preferably have more than two functionalities and optionally increase the crosslinking density. This component may also contain a 〇H-containing tree 29 201208597 lipid. The corresponding functional groups should be considered in the amount of isocyanate groups. The viscosity of the adhesive according to the invention should be from 100 to 100,000 mPa (measured according to EN ISO 2555, Brookfield viscometer) at the application temperature. This should be in particular between 15 and 4 (TC, in particular the viscosity should be It is present at room temperature (20-30 ° C.) The PU adhesive can be coated on a variety of different substrates according to the present invention. Due to its low viscosity, it can be processed at room temperature and can flow on the substrate and can be coated. In a thin layer, the adhesive is crosslinked by moisture in the atmosphere or a second component containing OH groups. In this context, crosslinking can be accelerated by higher temperatures. In another embodiment of the method according to the invention The pressure can be applied to the curved cover by a shrinkage seal to apply a pressure of from 0.1 bar to < 2 bar to the combined first and second components. The pressure is preferably in the range of > 5 bar to the magic bar. This is sufficient to secure the adhesive joint. In another embodiment of the method according to the invention, the plurality of combined first and second components are closed by a closure flexible cover and are sealed by external stimuli. The flexure cover is divided into individual packages of the first and second components that have been combined This has the advantage that when this method is used, the combined components are not individually shrunk in the skirt, but several bonded components can be simultaneously shrunk. To separate several bonded components from each other, a separate device is used, such as (for example) a cutting edge which separates the shrink-closed flexible cover after the components have been joined. The invention also provides a combined assembly of 201208597 obtainable by the method according to the invention, wherein - the closure is flexible The cover at least partially seals the assembly and applies at least a portion of the pressure to the first and second component doors: an adhesive. Details relating to the method according to the invention have been described, with reference to such details to avoid repetition. In one embodiment of the assembly, a set of footwear has been incorporated. In particular, the footwear can be a shoe or a boot. ', Figure 1 shows a diagram of the first and second components 2 that have been combined. The second component 2 is further processed. The adhesive 3 is applied to the decorative side of the second component 2 in each case in Fig. 2. It is also conceivable that the adhesive is applied only to the second component 2. The adhesive agent based on the polyurethane or the polyamine-based heat-adhesive adhesive is used. The sentence stick 3 shows how the first and second components 2 are combined and how At least partially joined to each other by the adhesive 3. 哎 and according to the present invention, the bonded assembly is placed in a closed flexible cover in Fig. 4. The structure of the closed flexible cover 4 is as shown in Figure 5 and It may be a vacuum package, a shrink film or a film. The closure flexible cover 4 may be made of a thermoplastic material such as polyamide, polyethylene, polyolefin, PVDF, PVC, PTFE and/or a composite film. In the device, the closed flexible cover 4 is contracted by an external stimulus, so that the closed flexible cover 4 is closed around the two pieces. In this context, the external stimulus consists of evacuation; sealing the air in the flexible cover 4 and/or heat treating the closed flexible 31 201208597. The closed interchangeable cover 4 is shown in Figure 4 by the closure of the flexible cover 4 on the second component 2. In this context, the pressure of the production - 1 and the second component 2 * 4: = - omitting the compression of the -1 and the - component 2 ^ _ the deflection cover can be kept in the closed elastic cover: two =叮 = the fitting still produces a high enough height before the hood 4 is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In addition, it can be seen that the closure of the flexible cover 4, such as dirty particles or air: external seals, the multi-piece shrink-closed flexible cover 4 is shown in Figure 6. The advantages of this number: for example, in a device not described and displayed, the components can be simultaneously introduced into the external stimulus, and then the device can be separated by means of a skirt, for example, the components are combined and each has a combined -1 and the individual packages of the second component 2. The multi-piece shrink-sealing flexible cover 4 pressure can also act on the -i and second components 2, so that the adhesive can produce a sufficiently high bond strength. An example of the use of this method is shown in Figure 7. In the article of footwear 5, the sole has been adhered to the upper. It can be seen how the shrink-closed flexible cover 4 itself closes around the article of footwear 5. Therefore, sufficient pressure is applied to the upper and the sole' so that the adhesive 3 can produce a sufficient bonding strength. Therefore, the device for pressurization and associated waiting time can be omitted.

In addition to S 32 201208597, the article of footwear 5 can be transported by enclosing the flexible cover 4, so that repeated packaging can be omitted. BRIEF DESCRIPTION OF THE DRAWINGS The invention has been described in detail with the aid of the preferred embodiments and the associated drawings. The figures show: Figure 1 is the first and second components. Figure 2 is the first and second components to which the adhesive has been applied. Figure 3 is the first and second components that have been combined. Figure 4 is the closed component. Closed flexible cover Figure 5 is a combination of a single-piece shrink-closed flexible cover around the assembly Figure 6 is a two-part shrink-closed flexible cover around the assembly Figure 7 is a closed closed flexible cover Articles of footwear [Main component symbol description] First component Second component Adhesive flexible cover Footwear 1 2 3 4 5 33

Claims (1)

201208597 VII. Patent Application Range: 1. A method for combining at least two components (1, 2), comprising the steps of: providing a first (1) and a second component (2); applying an adhesive (3) to First (1) and/or second component (2); combining the first (1) and the second component (2), the first (1) and the second component (2) are by an adhesive (3) At least partially engaging each other; introducing the first (1) and second component (2) into a flexible cover (4); applying pressure on the first (1) and second component (2), the pressure being at least partially Acting on the adhesive (3) between the first (1) and the second component (2), and then storing the first (1) and second component (2) in the shrinkable flexible cover for at least 1 a minute of time; applying pressure to cause the flexible cover (4) at least partially enclosing the first (1) and second component (2) to contract by external stimulation and the external stimulus is based on heat treatment and/or evacuation Flexible cover (4). 2. The method of claim 1, wherein the first component (1) comprises a sole and the second component (2) comprises an upper. 3. The method of claim 1, wherein the storage of the first and second components (2) is performed for at least 5 minutes. 4. The method of claim 1, wherein the vacuum bag S 34 201208597 is used as the closed flexible cover (4). 5. The method of claim 5, wherein a shrink film, a shrink hood, and/or a shrink tube are used as the package flexible cover (4). 6. The method of claim 1, wherein the adhesive (3) comprises an aqueous polyamino acid S dispersion. 7. The method of claim 1, wherein the adhesive (3) comprises a polyurethane hot melt adhesive. 8. The method of claim 1, wherein the adhesive (3) is a moisture-hardening 1C PU adhesive or a 2C PU adhesive. 9. The method according to claim 1, wherein the contraction closing flexible cover (4) applies a pressure of 20.1 bar to S2 bar on the combined first (1) and second component (2) . 10. The method of claim 1, wherein the first combined first (1) and second component (2) are closed by the closed flexible cover (4) and externally stimulated, The shrink-closed flexible cover (4) is dispensed into individual packages of the first (1) and second component 35 201208597 (2) that have been combined. 11. A bonded assembly obtainable by the method of claim 1 wherein a closed flexible cover (4) at least partially encloses the bonded component and applies a pressure at least partially to the first (1) And the adhesive (3) between the second component (2). 12. The assembled component according to claim 11 of the scope of the patent application, wherein the bonded component is an article of footwear (5). S 36