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    • 专利摘要:
    ready-to-use hotmelt adhesives with improved properties profile. the invention relates to ready-to-use hotmelt adhesives containing at least 95% by weight of one or more polyolefin copolymer waxes, which have been prepared with the aid of metallocene catalysts, characterized in that the polyolefin copolymer wax consists of in propylene and one or more selected monomers of ethylene and 1-alkenes branched or unbranched, containing 4 to 20 atoms of ce and the content of structural units derived from propylene in the copolymer waxes is 80 to 99.9% by weight, and the adhesives Hotmelts have a melt surface tension, measured at a temperature of 170°C, of a maximum of 23 mn/m.
    公开号:BR112015020987B1
    申请号:R112015020987-4
    申请日:2014-03-11
    公开日:2021-08-24
    发明作者:Timo Herrlich；Steib Christian；Hans-Friedrich Herrmann；Andreas Lang
    申请人:Clariant International Ltd；
    IPC主号:
    专利说明:

    [001] The invention relates to a ready-to-use hotmelt adhesive with improved spectrum of properties (resistance to hot molding, cohesion, adhesion, low VOC, open time), consisting of polyolefin waxes, which were prepared with metallocene catalysts .
    [002] Thermofusible adhesives or hot melts are thermoplastic raw materials that are solid at room temperature, which are applied in the molten state, in skeins or layers, on appropriate substrate surfaces and there, after curing/solidification, perform different functions. They are preferably constructed on the basis of resins, waxes, thermoplastic polymers and elastomers and contain, if appropriate, additions of fillers, pigments and additives such as stabilizers, etc.
    [003] Hotmelt adhesives can be used, for example, as solvent-free adhesives for gluing. This type of fusion adhesive, due to its various advantages, is used in a growing scope among others in the packaging industry, furniture industry, textile industry and shoe industry, as an economic and environmental alternative to the usual solvent-based adhesives . Constituents of common melt adhesive recipes are polar or non-polar polymers - typically ethylene-vinyl acetate copolymers, resins as well as waxes.
    [004] Polar or non-polar polymers serve here as structural substances. They guarantee the cohesion of the adhesive and at the same time contribute to the adhesion to the substrate. The resin additive improves the adhesion efficiency and can exert, if appropriate, a compatibilizing effect on the various components of the adhesive. Waxes are used for modification in fractions based on the melting adhesive, usually less than 10% by weight. They regulate very important physical properties of adhesive masses, such as hardness, melt viscosity and softening point, and with their effectiveness influence open time, adhesion, cohesion etc. and decisively the technical behavior. It has hitherto been found, as a rule, when using wax in amounts greater than 10% by weight, to worsen the adhesive strength of the melting adhesive.
    [005] As waxes, macrocrystalline and microcrystalline paraffin waxes, Fischer-Tropsch waxes as well as polyolefin waxes have been used in hotmelt adhesives so far. Polyolefin waxes are understood here, instead of plastics, as those polyolefins whose melt viscosity at 170°C is below 40,000 mPa.s.
    [006] Polyolefin waxes can be prepared by thermal decomposition of highly branched polymeric polyolefin plastics or by direct polymerization of olefins. As a polymerization process, for example, high-pressure technologies can be of interest, in which olefins, as a rule ethylene, are reacted at high pressures and temperatures to form waxes branched by radicals. Furthermore, there is the low pressure process or the Ziegler process, in which higher ethylene and/or 1-olefins are polymerized with the aid of organometallic catalysts at comparatively lower pressures and temperatures.
    [007] As a variant of the low pressure process, a form of operation was recently known in which metallocene compounds are used as organometallic catalysts. Finally, titanium, zirconium or hafnium complexes are used as active species and are, as a rule, in combination with cocatalysts, for example, organoaluminium compounds or boron compounds, preferably aluminoxane compounds. Polymerization takes place, if necessary, in the presence of hydrogen as a molar mass regulator. Metallocene processes are distinguished by the fact that, compared to the old Ziegler wax technology with narrow molar mass distribution, inclusion of uniform comonomers of defined tacticity (eg atacticity, isotacticity, syndiotacticity, hemiisotacticity) can be achieved etc.), lower melting points and greater effectiveness of the catalysts.
    [008] Melting adhesive mixtures based on the aforementioned components (polymers, resins, waxes, etc.), in particular based on polyolefins catalyzed by metallocenes, are known and have long been state of the art. Thus, for example, in EP1631641 polyolefin waxes prepared by catalysis of metallocenes are used as components of minimal amounts, which contain, as other constituents, EVA polymers and hydrocarbon resins. EP1645608 describes melting adhesive mixtures, whose structural substance, and therefore more than 50% by weight, are based on a polyolefin copolymer prepared by a metallocene process, however, in the described embodiments they contain, like other constituent, carbohydrate resins. In EP2081609 the use of such melt adhesive mixtures for adhesive textile fibers to each other or with other smooth substrates in sanitary articles is described.
    [009] As is known, there is a growing desire to obtain melting adhesives without prior composting of the individual components. This implies that the matrix material unites the functions of resin, wax and carrier polymer in a single material. This is desirable both for reasons of simplifying the preparation (reducing the complexity) of such melting adhesives, and also from the point of view of environmental and climatic compatibility, by avoiding unnecessary energy-intensive process steps. Although EP1645608B1 with a polyolefin wax fraction > 50% by weight also involves the construction of hotmelt adhesives, which are constructed exclusively by single-component systems, a suitable single-component embodiment is still not described or the patent application provides the specialist with advice on how to prepare and respectively select a polyolefin wax with such properties, nor on how to best compensate for the loss of adhesion lost by a resin.
    [0010] It was surprisingly found that a ready-to-use hotmelt mass consisting exclusively of reactor-prepared polyolefin waxes, which were prepared with the aid of metallocene catalysts, which have a numerical average molar mass of 15,000 - 25,000 g /mol and a weight average molar mass of 25,000 to 35,000 g/mol, have a drop point or ring/sphere softening point between 100 and 120°C, melt viscosity, measured at a temperature of 170°C between 8000 and 15,000 mPa.s, a glass transition temperature of at most -15°C and a surface tension at 170°C of at most 23 mN/m, are particularly suitable in an especially advantageous manner as a hot melt adhesive. single component. These types of single-component hotmelt adhesives do not require any further energy-intensive composting, they are distinguished within polyolefin waxes by improved cohesion, reduced open time, and improved heat resistance and cold flexibility, and therefore have a wider spectrum of use. These type of single component hotmelt adhesives are especially suitable for gluing and laminating flat textile fabrics (carpets, mattress covers, spring bags) and especially for gluing low surface energy substrates (eg PE, PP, etc. .). Furthermore, this type of single-component hotmelt adhesive has been found to have organovolatile compounds in particularly low amounts (low VOC). Description
    [0011] Object of the invention are, therefore, ready-to-use hotmelt adhesives, containing at least 95% of one or more polyolefin waxes, which were prepared with the aid of metallocene catalysts, and the selected polyolefin copolymer waxes consist of propylene and one or more other monomers selected from ethylene and 1 branched or unbranched alkene with 4 to 20 C atoms, and the content of structural units from propylene in the copolymer waxes is 80 to 99.9% by weight, and the Hotmelt adhesive masses have a melt surface tension, measured at a temperature of 170°C, of at most 23 mN/m.
    [0012] The term "ready to use" means in this context, that a separate composting step adjusted separately to the polymerization process of the polyolefin waxes according to the invention, mixing with other material components, such as for example, is explicitly excluded mixing with resin, carrier polymer or wax. A normal additive with components in reduced amounts of up to at most 5% by weight, preferably up to at most 2% by weight, particularly preferred at most 0.5% by weight, provided this, in connection with the form (confection) , occurs after the polymerization process, on the contrary, it is not excluded. The term "single component" here refers to the class of materials polyolefin waxes and thus for example also implies reactor mixtures of different polyolefin waxes, otherwise mixtures of EVA and polyolefin waxes or resin and waxes are to be included. polyolefin as multi-component systems not according to the invention.
    [0013] In the polyolefin waxes contained in the ready-to-use hotmelt adhesives according to the invention, copolymers of propylenes with ethylene, and/or with higher 1-olefins, or their copolymers with each other may be mentioned. As higher 1-olefins, linear or branched olefins with 4 to 20 carbon atoms, and preferably with 4 to 6 carbon atoms, are preferably used. Examples are 1-butene, 1-hexene, 1-octene or 1-octadecene . The copolymers preferably consist of from 80 to 99.9, and particularly preferred from 85 to 95% by weight of an olefin type.
    [0014] In a preferred embodiment, the copolymers of the ready-to-use hotmelt adhesives according to the invention consist of 85 to 95% by weight of propylene and 5 - 15% by weight of ethylene.
    [0015] Preferably the copolymers used according to the invention of the ready-to-use hotmelt adhesives according to the invention have a surface tension of the melt, measured at a temperature of 170°C, of at most 23 mN/m, preferably maximum 22.5 mN/m.
    [0016] The polyolefin waxes contained in the ready-to-use hotmelt adhesives according to the invention preferably have a numerical average molar mass Mn between 15,000 and 25,000 g/mol, particularly preferred between 17,000 and 22,000 g/mol, and preferably a weight average molar mass Mw between 25,000 and 35,000 g/mol, particularly preferred between 28,000 and 32,000 g/mol.
    [0017] The polyolefin waxes contained in the ready-to-use hotmelt adhesives according to the invention have a drip point or ring/sphere softening point between 100 and 120°C, preferably between 110 and 120°C, a heat of melting of 0 to 60 J/g, preferably between 40 and 60 J/g, a melt viscosity, measured at a temperature of 170°C, between 8000 and 15,000 mPa.s, preferably between 8000 and 11,000 mPa. s, and a glass transition temperature (DSC) of at most - 5°C, preferably at most -20°C.
    [0018] For the preparation of the polyolefin waxes used according to the invention, metallocene compounds of formula (I) are used.

    [0019] This formula also comprises compounds of formula (la),
    of formula (Ib)
    and the formula (Ic)

    [0020] In formulas (I), (la) and (Ib) M1 is a metal of groups IVb, Vb or VIb of the periodic system, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten , preferably titanium, zirconium, hafnium.
    [0021] R1 and R2 are the same or different and represent a hydrogen atom, a C1-C10-alkyl group, preferably a C1-C3-alkyl group, in particular methyl, a C1-C10-alkoxy group, preferably a group C1-C3-alkoxy, a C6-C10-aryl, preferably a C6-C8-aryl group, a C6-C10-aryloxy group, preferably a C6-C8-aryloxy group, a C2-C10-alkenyl group, of preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C7-C10-arylalkyl group, a C7-C40-alkylaryl group, preferably a C7-C12-alkylaryl group, a C8-C40 group -arylakenyl, preferably C8-C12-arylalkenyl or a halogen atom, preferably a chlorine atom.
    [0022] R3 and R4 are the same or different and represent a hydrocarbon radical with one or more nuclei, which with the central atom M1 can form a sandwich structure. Preferred are R3 and R4 cyclopentadienyl, indenyl, tetrahydroindeyl, benzoindenyl, or fluorenyl, wherein the base body still bears additional substituents or may be bridged to each other or to each other. Furthermore, one of the radicals R3 and R4 can be a substituted nitrogen atom, where R24 has the meaning of R17, and preferably methyl, tert-butyl or cyclohexyl.
    [0023] R5, R6, R7, R8, R9 and R10 are the same or different and represent a hydrogen atom, a halogen atom, preferably a fluorine atom, chlorine atom or bromine atom, a C1-C10 group -alkyl, preferably a C1-C4-alkyl group, a C6-C10-aryl group, preferably a C6-C8-aryl group, a C1-C10-alkoxy group, preferably a C1-C3-alkoxy group, a radical - NR162, a -SR16 radical, a -OSiR163 radical, a -SiR163 radical or a -PR162 radical, where R16 is a C1-C10-alkyl group, preferably a C1-C3-alkyl group or a C6-C10-aryl group, preferably a C6-C8-aryl group or in the case of a radical containing Si or P, it is also a halogen atom, preferably a chlorine atom, or each two neighboring radicals R5, R6, R7, R8, R9 or R10 form a ring with the C atoms attached to them. Particularly preferred binders are the substituted compounds of the cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl base bodies.
    [0024] R13 is

    [0025] =BR17, =AIR17, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR17, =CO, =PR17 or =P(O)R17, where R17 , R18 and R19 are the same or different and represent a hydrogen atom, a halogen atom, preferably a fluorine atom, chlorine atom, or bromine atom, a C1-C30-alkyl group, preferably C1-C4-alkyl, in particular a methyl group, a C1-C10-fluoroalkyl group, preferably a CF3 group, a C6-C10-fluoroaryl group, preferably a pentafluorophenyl group, a C6-C10-aryl group, preferably C6-C8-aryl, a C1-C10-alkoxy group, preferably a C1-C4-alkoxy group, in particular a methoxy group, a C2-C10-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-aralkyl group, preferably a C7-C10-aralkyl group, a C8-C40-arylalkenyl group, preferably a C8-C12-arylalkenyl group or a C7-C40-alkylaryl group, preferably a C7-group C12-alkylaryl, or R17 and R18 or R17 and R19 form a ring respectively with the atoms thereto connected.
    [0026] M2 is silicon, germanium or tin, preferably silicon and R13 CP17P18 QiP17P18 -HftP1^18germanium. R is preferably =CR R , =SIR R , =GeR R , -O-, -S-, =SO, =PR17 or =P(O)R17.
    [0027] R11 and R12 are the same or different and have the meaning mentioned for R17, men are the same or different and represent zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, of preference is zero or 1.
    [0028] R14 and R15 have the meaning of R17 and R18.
    [0029] Examples for the appropriate metallocenes are:
    [0030] Bis(1,2,3-trimethylcyclopentadienyl) zirconium dichloride,
    [0031] Bis(1,2,4-trimethylcyclopentadienyl) zirconium dichloride,
    [0032] Bis(1,2-dimethylcyclopentadienyl) zirconium dichloride,
    [0033] Bis(1,3-dimethylcyclopentadienyl) zirconium dichloride,
    [0034] Bis(1-methylindenyl) zirconium dichloride,
    [0035] Bis(1-n-butyl-3-methyl-cyclopentadienyl) zirconium dichloride,
    [0036] Bis(2-methyl-4,6-di-i.propyl-indenyl) zirconium dichloride,
    [0037] Bis(2-methylindenyl) zirconium dichloride,
    [0038] Bis(4-methylindenyl) zirconium dichloride,
    [0039] Bis(5-methylindenyl) zirconium dichloride,
    [0040] Bis(alkylcyclopentadienyl) zirconium dichloride,
    [0041] Bis(alkylindenyl) zirconium dichloride,
    [0042] Bis(cyclopentadienyl) zirconium dichloride,
    [0043] Bis(indenyl) zirconium dichloride,
    [0044] Bis(methylcyclopentadienyl) zirconium dichloride,
    [0045] Bis(n-butylcyclopentadienyl) zirconium dichloride,
    [0046] Bis(octadecylcyclopentadienyl) zirconium dichloride,
    [0047] Bis(pentamethylcyclopentadienyl) zirconium dichloride,
    [0048] Bis(trimethylsilylcyclopentadienyl) zirconium dichloride,
    [0049] Dibenzyl biscyclopentadienylzirconium,
    [0050] Dimethyl biscyclopentadienyl zirconium,
    [0051] Bistetrahydroindenyl zirconium dichloride,
    [0052] Dimethylsilyl-9-fluorenylcyclopentadienyl zirconium dichloride,
    [0053] zirconium, Bis(4-methylindenyl) zirconium dichloride, Bis(5-methylindenyl) zirconium dichloride, Bis(alkylcyclopentadienyl) zirconium dichloride, Bis(alkylindenyl) zirconium dichloride, Bis(cyclopentadienyl) zirconium dichloride (indenyl) zirconium dichloride, Bis(methylcyclopentadienyl) zirconium dichloride, Bis(n-butylcyclopentadienyl) zirconium dichloride, Bis(octadecylcyclopentadienyl) zirconium dichloride, Bis(pentamethylcyclopentadienyl) dichloride of zirconia Biscyclopentadienylzirconium, Dimethyl biscyclopentadienyl zirconium, Bistetrahydroindenyl zirconium dichloride, Dimethylsilyl-9-fluorenylcyclopentadienyl zirconium dichloride, Dimethylsilyl-bis-1-(2,3,5-trimethylcyclopentadienyl) dichloride
    [0054] zirconium, Dimethylsilyl-bis-1-(2,4-dimethyl-cyclopentadienyl) dichloride
    [0055] Conium, Dimethylsilyl-bis-1-(2-methyl-4,5-benzoindenyl) zir-dichloride
    [0056]
    [0057]nio, Dimethylsilyl-bis-1-(2-methyl-4-ethylindenyl) zirconium dichloride, Dimethylsilyl-bis-1-(2-methyl-4-i-propylindenyl) zirconia dichloride
    [0058]
    [0059]
    [0060] Conium, Dimethylsilyl-bis-1-(2-methyl-4-phenylindenyl) zirconium dichloride, Dimethylsilyl-bis-1-(2-methyl-indenyl) zirconium dichloride, Dimethylsilyl-bis-1-(2- methyltetrahydroindenyl) zir-
    [0061]
    [0062] Dimethylsilyl-bis-1-indenyl zirconium dichloride, Dimethylsilyl-bis-1-indenyl dimethyl zirconium,
    [0063] Dimethylsilyl-bis-1-tetrahydroindenyl zirconium dichloride,
    [0064] Diphenylmethylene-9-fluorenylcyclopentadienyl zirconium dichloride,
    [0065] Diphenylsilyl-bis-1-indenyl zirconium dichloride,
    [0066] Ethylene-bis-1-(2-methyl-4,5-benzoindenyl) zirconium dichloride,
    [0067] Ethylene-bis-1-(2-methyl-4-phenylindenyl) zirconium dichloride,
    [0068] Ethylene-bis-1-(2-methyl-tetrahydroindenyl) zirconium dichloride,
    [0069] Ethylene-bis-1-(4,7-dimethyl-indenyl) zirconium dichloride,
    [0070] Ethylene-bis-1-indenyl zirconium dichloride,
    [0071] Ethylene-bis-1-tetrahydroindenyl zirconium dichloride,
    [0072] Indenyl-cyclopentadienyl-zirconium dichloride
    [0073] isopropylidene(1-indenyl)(cyclopentadienyl) zirconium dichloride,
    [0074] isopropylidene(9-fluorenyl)(cyclopentadienyl) zirconium dichloride,
    [0075] Phenylmethylsilyl-bis-1-(2-methyl-indenyl) zirconium dichloride,
    [0076] as well as respectively the alkyl or aryl derivatives of these metallocene dichlorides.
    [0077] For activation of monocentric catalyst systems, appropriate cocatalysts are used. Suitable cocatalysts for metallocenes of the formula (I) are organic aluminum compounds, in particular alumoxanes, or also alumin-free systems +OQ nnmn p20 KIII pn21 p20 n|_| pp21 p20 ppp21 ni| pp21 nio, such as R XNH4-XBR 4, R XPH4-XBR 4, R 3CBR 4 or BR 3. In these formulas x represents a number from 1 to 4, the radicals R20 are the same or different, preferably the same, and represent C1 -C10-alkyl or C6-C18-aryl or two radicals R20 form together with the atom to which they are attached a ring, and the radicals R21 are the same or different, preferably the same, and represent C6-C18-aryl, which can be substituted by alkyl, haloalkyl or fluorine. In particular R20 represents ethyl, propyl, butyl or phenyl and R21 represents phenyl, pentafluorophenyl, 3,5-bis-trifluoromethylphenyl, mesityl, xylyl or tolyl.
    [0078] Additionally, a third component is often required to maintain protection against polar catalyst poisons. For this purpose, organic aluminum compounds, such as triethylaluminum, tributylaluminum and others, as well as mixtures, are suitable.
    [0079] Depending on the process, supported monocentric catalysts can also be used. Catalyst systems are preferred, in which the residual content of carrier material and cocatalyst does not exceed a concentration of 100 ppm in the product.
    [0080] In the process described above it is also possible to use mixtures of different stereoselectivities and/or different single center catalysts in the supported form, as well as in the unsupported form. Products prepared in such a process variant are called reactor mixes. The polymers obtained by this process variant, due to the same monomeric construction elements, are considered to be a uniform material class and can therefore be considered as single components. The polyolefin waxes according to the invention therefore also include reactor mixtures. In the present invention the polyolefin waxes are based on metallocenes, in particular, for example, ethylene-propylene copolymers.
    [0081] The ethylene-propylene-based copolymer waxes prepared according to the process described above have a particularly advantageous property profile for ready-to-use hotmelt adhesives according to the invention. They belong to the profile of advantageous properties: high cohesion, without being fragile in use; a broad spectrum of wear temperature, limited below by the glass transition temperature and above by the softening temperature; a melting surface tension at 170°C < 23 mN/m for improved wetting, in particular of low-surface energy surfaces such as polyolefin surfaces; a short open time, for high processing speeds.
    [0082] Object of the present invention are, therefore, ready-to-use single-component hotmelt adhesives based on metallocenecatalytically prepared polyolefin waxes. Preferably, single-component ready-to-use hotmelt adhesives correspond in their physical and chemical properties exactly to polyolefin waxes or polyolefin wax reactor mixtures.
    [0083] Preferably the ready-to-use hotmelt adhesives according to the invention have a dropping point or ring/sphere softening point between 100 and 120°C, a melt viscosity, measured at a temperature of 170°C, between 8000 and 15,000 mPa.s, a glass transition temperature (DSC) of a maximum of -15°C, as well as a melt surface tension measured at a temperature of 170°C of a maximum of 23 mN/m.
    [0084] Particularly preferably the ready-to-use hotmelt adhesives according to the invention have a dropping point or ring/sphere softening point between 110 and 120°C, a melt viscosity, measured at a temperature of 170°C, between 8000 and 11,000 mPa.s, a glass transition temperature (DSC) of at most -20°C, as well as a melt surface tension, measured at a temperature at 170°C, of at most 23 mN/m.
    [0085] According to the invention, ready-to-use hotmelt adhesives are distinguished by a melting adhesive with a particularly wide temperature usage spectrum compared to the EVA-based melting adhesive. This is expressed by an elastic entropy range of 80 to 110°C for ready-to-use hotmelt adhesives. The elastic entropy range ΔTentropieel (tan δ) is determined from the difference between the maximum loss factor tan δmax and the softening point in the DMA (loss factor tan δonset onset). The course of the loss module is measured by measuring the DMA according to DIN ISO 6721-1. The maximum loss factor tan δmax is determined according to ASTM D 4065-99 during the onset (threshold) of the loss factor at the softening point by the method of tangents (see figure 1).
    [0086] The ready-to-use hotmelt adhesives according to the invention may additionally contain polyolefin plastics, resins, waxes, softeners, polar or non-polar polymers, pigments, fillers, stabilizers and/or antioxidants in usual additive concentrations.
    [0087] Another object of the invention is the use of ready-to-use hotmelt adhesives according to the invention as a melt adhesive. Preferably the ready-to-use hotmelt adhesives consist of 95 to 100% by weight, preferably from 98 to 100% by weight, particularly preferred from 99 to 100% by weight of the polyolefin waxes described above.
    [0088] The ready-to-use hotmelt adhesives according to the invention are used to glue, laminate, fix, and coat flat textile fabrics of all types, such as, for example, the coating of the back of carpets, the coating of the back of artificial grass , glue for spring bags (mattresses), non-woven or fleece materials. The ready-to-use hotmelt adhesives according to the invention are also suitable for the manufacture of the most diverse hygiene articles, such as infant diapers, diaper-pants, incontinence products, panty protectors, sanitary absorbents, in particular for laminating materials of fiber, such as fleece materials with film.
    [0089] Due to the improved mechanical properties, the ready-to-use hotmelt adhesives according to the invention can also be used as binders for the preparation of road pavements.
    [0090] Particularly advantageously the ready-to-use hotmelt adhesives according to the invention are suitable for gluing, laminating and fixing substrates with a total surface energy of yges < 30 mN/m, the so-called "low surface energy" substrate. These include in particular polypropylene, polyethylene. Preferably those substrates have a low polar content yP < 2 mN/m of the total surface energy. Finally, the sum of the polar and dispersed surface energy fractions is the sum of the polar and dispersed surface energy fractions: yges = yp + Yd
    [0091] The following examples should clarify the invention in more detail, without however limiting it to them.Examples
    [0092] Melting viscosities were determined according to DIN 53019 with a rotating viscometer, the drip points according to DIN 51801/2, and the ring/ball softening points according to DIN EN 1427. The glass transition temperatures as well as the melting enthalpies were determined by differential thermoanalysis according to DIN EN ISO 11357-1 from -50 to 200 °C at a heating rate of 10K/min under nitrogen.
    [0093] The weight average of the molar mass Mw, the arithmetic average of the molar mass Mn and the resulting quotient Mn/Mw (PDI) were determined by chromatography by gel permeation at 135 °C in 1,2-dichlorobenzene by means of of a PP standard.
    [0094] The determination of the surface tension of the hotmelt adhesives or of the polyolefin waxes took place by methods of "pendant drip" by means of a heated measuring chamber as well as a ceramic cannula heated to 170°C. The melting densities required for that measurement were also determined at 170°C.
    [0095] Volatility was determined thermogravimetrically by TGA measurements under nitrogen. For this, about 10 mg of the sample was heated at a heating rate of 5 K/min to 300°C and the mass loss was recorded. The measurement took place under a nitrogen atmosphere with a N2 flow rate of 50 ml/min.
    [0096] The metallocene polyolefin waxes indicated in Table 1 were prepared according to the process specified in EP-A-0 571 882. The control of the molecular weight in the indicated catalyst system and in the proportion of comonomer indicated occurred with the partial pressure of hydrogen as molar mass regulator.
    [0097] Examples 1 to 13 show a typical selection of ethylene-propylene-based copolymer waxes and their property profile (melting viscosity, EWP, surface tension, melting enthalpy, glass transition temperature), classified according to the increasing softening temperature. The softening temperature has, in subsequent use as a melting adhesive, a direct influence on the heat resistance and thus on the maximum operating temperature after adhesion has occurred. The glass transition temperature has a direct influence on the cold flexibility of an adhesion. Furthermore, the enthalpy of fusion limits (as a measure of crystallinity) the toughness and cohesion of the adhesive after an adhesion. The melt viscosity and melt surface tension are, in contrast, high for the applicability of the liquid melt adhesive. A low surface tension here leads to better surface wetting.
    [0098] Examples 5, 6, 9, 10 and 11 show, given a constant propylene content of 89% by weight and 11% by weight of ethylene, a modification of the property profile with increasing molecular weight. The molecular weight was thus controlled with the partial pressure of hydrogen during polymerization. Thus, increasing molecular weight leads to an increase in melt viscosity, softening point, crystallinity in the form of melt enthalpy, and melt surface tension. At the same time volatility decreases with increasing molecular weight. Table 1: Properties of Various Ethylene-Propylene Polyolefin Copolymer Waxes

    [0099] It is shown below that the ethylene-propylene polyethylene copolymer wax according to the invention (example 5) meets the technical requirements of using a ready-to-use melt adhesive in the sense of the present invention in a way particularly appropriate.A. Use in Fusion Adhesive Recipes
    [00100] Using the waxes shown in table 1, melting adhesive masses were prepared according to the mixing ratios shown in table 2. The components were melted together and stirred for 1 hour at 180°C.
    [00101] To test the cohesion, specimens were poured from the mixture in accordance with DIN 53455 and its mechanical stability was tested in a tensile test.
    [00102] The usage temperature spectrum was determined along the entropy-elastic range ΔTθntropieel (tan δ) and results from the difference of the maximum loss factor (tan δmax) and the loss factor threshold (tan δonset):
    [00103] ΔTθntropieel = T(tan δonset) - T(tan δmax). The loss factor was determined using DMA measurement according to DIN ISO 6721 -1 . The maximum loss factor (tan δmax) was determined according to ASTM D 4065-99, while the onset of the loss factor was determined at the softening point using the tangent method (see figure 1). The heating rate of the DMA measurement was 3 K/min, the amplitude 20 µm, and the measurement frequency was 1 Hz. The specimen geometry was continuously 2 mm x 3.5 mm x 12.82 mm.
    [00104] The determination of the open time occurred after the melting of the melting adhesive mass shown in table 2 at 140°C, by means of a cast film of 500 μm applied by spatula on a coated cardboard surface. For this purpose strips of paper (1 cm x 5 cm) were pressed every second into the fusing film which is cooling down. After complete curing of the fusing adhesive, the paper strips were removed. When a complete breakage of the fibers at the adhesion site has occurred, the end of the open time will have been reached.
    [00105] The relevant determination for the use of the maximum tensile strength (pull strength) of adhesion between two bags of a mattress of bagged springs, and with it the adhesion, occurred through bags of springs glued to the machine by a test of traction in analogy with ASTM D751. For this, a surface of 10 cm x 10 cm was cut from the bags glued to the glued surface and measured under traction. The bag material consisted of a PP-based non-woven fabric. Table 2: Melting adhesive as well as recipe mixes for use
    Table 3: Relevant use technical properties of reactor-ready melt adhesives in the examples: Bonding of spring mattress bags as well as coating on the rear side of artificial grass

    [00106] Melting adhesives nos. 5 and 9 satisfy the profile of properties according to the invention of a ready-to-use melt adhesive with a broad spectrum of use temperatures in the sense of this invention, with a short open time , as well as a high cohesion of the fusion adhesive. A melt surface tension < 23 mN/m at 170 °C results in good wettability of the surface to be glued. Comparative examples 1 - 4, 6 - 8 as well as 10 - 13 do not fulfill the required property profile in at least one property (open time, toughness, strength, flexibility, usage temperature spectrum).
    [00107] The examples for the ethylene-propylene polyolefin copolymer waxes in tables 1 and 3 show that an increase in the softening point, and with it in the heat resistance, is most often linked to an increase in crystallinity and at the same time to a loss of flexibility. Until now this problem can only be tackled by means of corresponding composting.
    [00108] Fusion adhesive no. 5 shows, also without composting, an optimal combination of properties for use (figure 1).
    权利要求:
    Claims (10)
    [0001]
    1. Ready-to-use hotmelt adhesive, characterized in that it contains at least 95% by weight of one or more polyolefin copolymer waxes, which has been prepared with the aid of metallocene catalysts, wherein the polyolefin copolymer wax - consists of propylene and one or more other monomers selected from ethylene and 1-alkenes, branched or unbranched, with 4 to 20 C atoms, - comprises propylene and ethylene units, and the amount of structural propylene units in the originating copolymer waxes is between 85 to 95% in weight,- it has a numerical average molar mass Mn in the range of 15,000 and 25,000 g/mol and a weight average molar mass Mw in the range 25,000 and 35,000 g/mol, a drip point or point of ring/ball softening in the range of 100 and 120°C, a heat of fusion of a maximum of 60 J/g, a melt viscosity, measured at a temperature of 170°C, from 8,000 to 15,000 mPa.s, and a glass transition temperature of at most -15°C and the hotmelt adhesive has a melt surface tension, measured at a temperature of 170°C, of at most 23 mN/m, where the hotmelt adhesive has an elastic entropy temperature range ΔTθntropy-el (tan δ), measured as the difference of the glass transition temperature Tg (tan δmax) from the loss factor and the softening temperature (threshold (onset) of the tan δonset loss module) from 80 to 110°C.
    [0002]
    2. Ready-to-use hotmelt adhesive according to claim 1, characterized in that the copolymeric polyolefin wax(s) has a heat of fusion in the range of 40 to 60 J /g, a melt viscosity, measured at a temperature of 170°C, between 8000 and 11,000 mPa.s, and a glass transition temperature of at most -20°C.
    [0003]
    3. Ready-to-use hotmelt adhesive according to claim 1 or 2, characterized in that it is prepared directly in the polymerization reactor without further composting and, when two or more different polyolefin waxes are used, it is prepared as one reactor mix.
    [0004]
    4. Ready-to-use hotmelt adhesive according to any one of claims 1 to 3, characterized in that it further comprises one or more substances selected from polyolefin polymers, resins, waxes, plasticizers, polar or non-polar polymers, pigments, fillers, stabilizers and antioxidants in additive amounts.
    [0005]
    5. Use of ready-to-use hotmelt adhesive as defined in any one of claims 1 to 4, characterized in that it is for gluing, laminating and fixing low surface energy substrates, with a surface energy less than < 30 mN / m.
    [0006]
    6. Use according to claim 5, characterized in that polyolefin waxes are present in thermofusible adhesives in fractions between 95 and 100% by weight.
    [0007]
    7. Use according to claim 5 and/or 6, characterized in that the polyolefin wax or polyolefin waxes correspond to the ready-to-use hotmelt composition.
    [0008]
    8. Use according to any one of claims 5 to 7, characterized in that it is as a binder for the preparation of road markings.
    [0009]
    9. Use according to any one of claims 5 to 8, characterized in that it is a fusion adhesive for coating the back of flat fabrics.
    [0010]
    10. Use according to any one of claims 5 to 9, characterized in that it is to glue, laminate, fix and coat flat textile fabrics (carpets, artificial grass, mattress coverings, spring bags, diapers, nonwovens) .
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    同族专利:
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    US20160053149A1|2016-02-25|
    US20190225846A1|2019-07-25|
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    KR20150135448A|2015-12-02|
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    DE102013005089A1|2014-09-25|
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    JP2016518479A|2016-06-23|
    CN105247001A|2016-01-13|
    PL2976403T3|2018-01-31|
    MX2015013522A|2016-02-05|
    US10287467B2|2019-05-14|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102013005089.8|2013-03-23|
    DE102013005089.8A|DE102013005089A1|2013-03-23|2013-03-23|Ready-to-use hot-melt adhesive with improved property profile|
    PCT/EP2014/000648|WO2014154328A1|2013-03-23|2014-03-11|Ready-to-use hot melt adhesive having an improved property profile|
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