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    • 专利摘要:
    aqueous dispersion, method for producing a dispersion comprising adhesive polymer, use of an aqueous dispersion, and self-adhesive article. the invention relates to an aqueous dispersion containing at least one water-dispersed polymerisate having an average molecular weight of less than 50,000 and a glass transition temperature of 40° to 0°C, which can be produced by emulsion polymerization in the presence of fur. minus one molecular weight regulator of a monomer blend containing at least 40% by weight of C1 to C2O alkyl (meth)acrylates, 0 to 30% by weight of vinyl aromatics, at least 0.1% by weight of acidic monomers and 0 to 50% by weight of additional monomers. the dispersion can in particular be used as a tackifying agent for adhesives.
    公开号:BR112014018254B1
    申请号:R112014018254-0
    申请日:2013-01-23
    公开日:2021-08-24
    发明作者:Matthias Gerst；Michael Gross
    申请人:Basf Se；
    IPC主号:
    专利说明:

    [0001] The invention relates to an aqueous dispersion comprising at least one polymer dispersed in water and having a low molecular weight and a defined glass transition temperature, which can be prepared by emulsion polymerization, in the presence of at least one agent chain transfer, of a mixture of monomers comprising C1 to C20 alkyl (meth)acrylates, acidic and optionally vinylaromatic monomers and also additional monomers. The invention also concerns uses of the dispersion as tackifiers for adhesives, for example.
    [0002] With pressure sensitive adhesives (PSAs) there is a desire not only for effective adhesion to the substrate, but also for sufficient internal strength in the adhesive layer (cohesion). Adhesion and cohesion are mutually opposite performance properties. Measurements that bring about an improvement in adhesion tend to lead to a deterioration in cohesion at the same time and vice versa. Many PSA polymers, at the same time having sufficiently high cohesion, despite lack of sufficient adhesion. By adding what are called tackifiers it is possible to achieve a significant increase in adhesion of adhesive compositions. Sticking agents are polymeric additives for adhesive polymers or, generally, for elastomers, which increase the self-adhesion (sticking, intrinsic adhesiveness, self-adhesion) of said polymers or elastomers, in such a way that after the quick and gentle application of pressure, the systems adhere firmly to surfaces. Commonly employed tackifiers include natural resin based tackifiers, terpene oligomers, coumarin-indene resins, aliphatic petrochemical resins, and modified phenolic resins. In the case of resins from natural sources, the naturally fluctuating availability and price can present problems. In the case of synthetic resins that are used as tackifiers for aqueous PSA polymer dispersions, good molecular miscibility of a portion or the total amount in the dry adhesive film is as important as a high compatibility with aqueous polymer dispersions. Good miscibility in polymer films is promoted by a molecular weight that is extremely low. In the case of synthetic tackifier polymers or oligomers, a problem is that in order to achieve low molecular weights, it is necessary in the preparation stage to use relatively high amounts of chain transfer agents. This can lead to a relatively high level of residual unpolymerized monomers which, on the one hand, is often undesirable from the safety aspect of the product and, on the other hand, may appear to be an inadequate molecular weight on the part of the polymers, which have a strong plasticizing effect. in adhesive polymers, which can lead to an undesirably strong adverse effect on cohesion. The use of low molecular weight polyacrylates as tackifiers for adhesive formulations is referred to in WO 2005/047342, for example. An example of a commercial product of this type is Acronal® A107 (former name: Acronal® 7D). Adhesive formulations produced in them have good tackiness and adhesion. For certain applications, however, gncu u«q owkVq “ocekcu”= go qwVtcu rcncxtcu. c eqgu«q fi kpcfgswcfco
    [0003] It was an aim of the present invention to provide substances that are suitable as tackifiers for aqueous PSA dispersions and with which it is possible to optimize the adhesive properties of PSAs, in particular for self-adhesive articles, such as adhesive labels, adhesive sheets or adhesive tapes and also floor stickers. In particular, in addition to good adhesion, extremely good cohesion must be achieved at the same time. In this way, aqueous polymer dispersions were observed, in more detail, based on defined synthetic acrylate polymers of low molecular weight.
    [0004] The invention provides an aqueous dispersion comprising at least one polymer dispersed in water and having an average molecular weight less than 50,000 and a glass transition temperature greater than or equal to -40°C to less than or equal to 0°C, preferably greater than or equal to -35°C to less than or equal to 0°C, which may be prepared by emulsion polymerization in the presence of at least one chain transfer agent and which may be prepared from a mixture of monomers comprising (a) at least 40% by weight of at least one C1 to C20 alkyl (meth)acrylate, (b) 0% to 30% by weight of at least one vinylaromatic, (c) at least 0.1% by weight of at least an acid monomer, (d) 0% to 50% by weight of additional monomers, for the amounts of monomer being based in each case on the sum of all monomers.
    [0005] The dispersion of the invention comprises as an essential constituent a polymer that can be prepared by emulsion polymerization; q rqníogtq fkurgtuq fi gpV«q wo rqníogtq fg gownu«qo Q Vgtoq "rqníogtq" hereafter encompasses not only polymers (low molecular weight) but also oligomers.
    [0006] Polymers can be prepared by conventional emulsion polymerization using not normally large amounts of chain transfer agents. The resulting tackifier dispersions then can be combined, as a blending component, with adhesive polymers to form PSA dispersions. Instead of their use as a blending component, tackifier dispersions can also be prepared in situ by a staged procedure by the emulsion polymerization of a PSA dispersion in the presence of an adhesive polymer.
    [0007] Pq VgzVq c ugiwkt. q Vgtoq “*oeV+cetücVq” and fgukipc>õgu ukoknctgu u«q wucfqu eqoq woc pqVc>«q cdtexkcfc rctc “cetücVq qw oevcetkncvq”0
    [0008] A pressure sensitive adhesive (PSA) is a viscoelastic adhesive whose film of adjustment to room temperature (20°C) in the dry state remains permanently tacky and adhesive. Adhesion to substrates is accomplished immediately by gentle application of pressure. A PSA dispersion is a composition comprising a polymer, dispersed in water or an aqueous medium, that has pressure sensitive adhesive properties.
    [0009] An adhesive polymer in the sense of the invention is a polymer having a glass transition temperature in the range of -60°C to -20°C.
    [00010] The glass transition temperature of polymers can be determined by differential scanning calorimetry (ASTM 3418/82, 20 k/min, average temperature).
    [00011] A tackifier is a polymeric or oligomeric additive for adhesive polymers or generally for elastomers that increases the self-adhesion (sticking, inherent adhesiveness, self-adhesion) of such systems, in such a way that they are firmly adhered to the surfaces after pressure Quick and smooth applied.
    [00012] The candidate tackifier polymer is composed to some extent of at least 40% by weight, more particularly 60% to 99.9% by weight or 60% to 99.7% by weight or 70% at 98% by weight of at least one C1 to C20 alkyl (meth)acrylate, C1 to C10 alkyl acrylates and C1 to C10 alkyl methacrylates are preferred. Examples of suitable monomers include methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate, ethyl methacrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate. In particular, mixtures of (meth)acrylic acid alkyl esters are also suitable. Especially preferred are 2-ethylhexyl acrylate, n-butyl acrylate and methyl methacrylate.
    [00013] The candidate polymer tackifier optionally can be composed of vinylaromatics. The vinylaromatic monomers (b) can be used in amounts from 0% to 30% by weight, more particularly from 0.5% to 25% by weight or from 2% to 20% by weight, based on the total amount of monomers. Preferred vinylaromatics are those having up to 20 C atoms. Vinyl aromatic compounds contemplated include vinyltoluene, alpha- and para-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and - preferably - styrene.
    [00014] The candidate tackifier polymer is formed to an extent of at least 0.1% by weight, preferably in amounts of 0.1% to 20% by weight, more preferably 0.2% to 10% by weight , most preferably 0.5% to 7% by weight, based on the total amount of monomers, of acid monomers. Acid monomers are ethylenically unsaturated, radically polymerizable monomers that have at least one acid group. Examples of acidic monomers include ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and vinylphosphonic acid. The ethylenically unsaturated carboxylic acids used are preferably alpha,beta-monoethylenically unsaturated monocarboxylic and dicarboxylic acids which have 3 to 6 C atoms in the molecule. Examples of these are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid and vinylatic acid. Examples of suitable ethylenically unsaturated sulfonic acids include vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate. The acidic monomers are preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinylatic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and methacrylate sulfopropyl and mixtures of these monomers. Particularly preferred are acrylic acid and methacrylic acid and a mixture thereof.
    [00015] The candidate tackifier polymer optionally can be composed of additional monomers (d) other than monomers (a) to (c). The additional monomers (d) are preferably used in amounts from 0% to 50% by weight, more particularly from 0.1% to 40% by weight, or from 1% to 30% by weight, based on the total amount of monomers . Additional monomers (d) may be selected from C1 to C20 hydroxyalkyl (meth)acrylates, vinyl esters of carboxylic acids comprising up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds, or mixtures of these monomers. Examples of carboxylic acid vinyl esters having 1 to 20 C atoms are vinyl laurate, vinyl stearate, vinyl propionate, versatic acid vinyl esters and - preferably - vinyl acetate. Examples of nitriles are acrylonitrile and methacrylonitrile. Vinyl halides are chloride-, fluoride- or bromide-substituted, ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride. Examples of vinyl ethers include vinyl methyl ether and vinyl isobutyl ether. Preferred vinyl ethers are those of alcohols comprising 1 to 4 C atoms. Hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds include ethylene, propylene, isoprene and chloroprene. Particularly preferred as additional monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, C1-C10 hydroxyalkyl (meth)acrylates and (meth)acrylamide and also mixtures of these monomers.
    [00016] In an embodiment of the invention the polymer can be prepared from a mixture of monomers comprising (a) 60% to 99.7% by weight of at least one C1 to C10 alkyl (meth)acrylate, (b) 0% to 30% by weight of styrene, (c) 0.2% to 20% by weight of at least one acid monomer selected from acrylic acid and methacrylic acid, (d) 0.1% to 30% by weight of additional monomers selected of C1 to C10 hydroxyalkyl (meth)acrylates and vinyl acetate, the figures for monomer amounts being based in each case on the sum of all monomers.
    [00017] The polymer is prepared in the presence of at least one chain transfer agent in order to achieve the low molecular weight according to the invention. The amount of chain transfer agent used in this case is set such that the average molar mass is less than 500,000, preferably 1500 to 45,000 or 2000 to 20,000. Typical chain transfer agent amounts are, for example, at least 1 part by weight, preferably more than 1 part by weight, such as, for example, 2 to 30 parts by weight, per 100 parts by weight of monomers.
    [00018] Chain transfer agents are generally low molecular weight compounds with a molar weight of less than 2000, more particularly less than 1000 g/mol. Examples of chain transfer agents include organic compounds comprising sulfur in bonded form, more particularly compounds having a thiol or sulfite group, such as alkyl mercaptans, thiocarboxylic acids, thiocarboxylic esters, mercaptoalkanols, mercaptoalkyltrialkoxysilanes, thioglycols, dialkyl sulfites, diaryl sulfites, dialkyl disulfites or thiourea. Examples are tert-butyl mercaptan, tert-dodecyl mercaptan, thioglycoic acid ethyl ester, mercaptoethanol, mercaptopropyltrimethoxysilane, thiodiglycol, ethylthioethanol, di-n-butyl sulfite, di-n-octyl sulfite, diphenyl sulfite, disulfite 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioacetic acid and thiourea. The chain transfer agent is preferably selected from the group consisting of tert-dodecyl mercaptan, n-dodecyl mercaptan and (2-ethylhexyl)thioglycolate. Particularly preferred is (2-ethylhexyl) thioglycolate (EHTG).
    [00019] The nature and amounts of the monomers and of at least one chain transfer agent are established in such a way that the glass transition temperature (Tg) of the polymer is greater than or equal to -40°C, preferably greater than or equal to at -35°C, the less than or equal to 0°C. The Tg here is the actually measurable Tg, which may differ from the theoretical Tg calculable using the equation known as the Fox equation. The theoretical Tg of the polymer, calculated using the Fox equation for a polymerization without chain transfer agent, is preferably greater than -25°C. It is also preferred that the theoretical Tg calculated using the Fox equation is greater than the Tg actually measured for the polymer. The difference of theoretical Tg minus actual Tg is more preferably greater than 3°C, more particularly greater than 5°C. The glass transition temperature can be determined by differential scanning calorimetry (eg ASTM 3418/82, 20 K/min, average temperature).
    [00020] The theoretical Tg can be calculated using the Fox equation. The theoretical glass transition temperature Tg here means the threshold value of the glass transition temperature towards which it tends with increasing molecular weight. According to Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 3. raikpc 345 g fg ceqtfq eqo Ullocpn's Gpekelqr"fkg fgt technischen Chemie, Volume 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980), the glass transition temperature of copolymers with no more than a very low degree of crosslinking is given in good approximation by:
    where x1, x2, xn are the mass fractions of monomers 1, 2, n and Tg1, Tg2, Tgn are the glass transition temperatures of the polymers composed in each case of only one of the monomers 1, 2, n, in degrees Kelvin. Tg values for the homopolymers of most monomers are known g"u"q"nkuvcfqu."rqt"gzgornq."go"WnnocppOu"Gpekenqrgfkc"qh"Kpfwuvtkcn" Chemistry, Volume 5, Volume A21, page 169, VCH Weinheim, 1992; other sources of glass transition temperatures for homopolymers include, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1st Ed., J. Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, and 3rd Ed. , J. Wiley, New York 1989).
    [00021] The polymers can be prepared by emulsion polymerization and are then emulsion polymers, with the aforementioned radically polymerizable ethylenically unsaturated monomers being polymerized by radically initiated emulsion polymerization in water. In order to aid in the dispersion of the monomers in the aqueous medium, it is possible to use the emulsifiers and/or protective colloids which are commonly used as dispersants.
    [00022] A comprehensive description of suitable protective colloids is found in Houben-Weila, Methoden der organischen Chemie, Volume XIV/1, Makromolekulare Stoffe [Macromolecular Compounds], Georg-Thieme-Verlag, Stuttgart, 1961, pages 411 to 420. Emulsifiers contemplated include anionic, cationic and non-ionic surface active compounds whose number average molecular weight is typically below 2000 g/mol or preferably below 1500 g/mol, while the number average molecular weight of protective colloids is above 2000 g /mol, from 2000 to 100,000 g/mol, for example, more particularly from 5000 to 50,000 g/mol. It is preferred to use anionic and non-ionic emulsifiers as surface active substances. Examples of suitable emulsifiers include ethoxylated C8 to C36 fatty alcohols having a degree of ethoxylation from 3 to 50, mono-, di- and tri-ethoxylated alkylphenols having a degree of ethoxylation from 3 to 50, alkali metal salts of dialkyl sulfosuccinic acid esters, alkali metal salts and ammonium salts of C8 to C12 alkyl sulfates, alkali metal salts and ammonium salts of C12 to C18 alkylsulfonic acids and alkali metal salts and ammonium salts of C9 to C18 alkylarylsulfonic acids . Examples of cationic emulsifiers are compounds having at least one amino or ammonium and at least one C8-C22 alkyl group. If group emulsifiers and/or protective colloids are among the auxiliaries used to disperse the monomers, the amounts of which are used are, for example, 0.1% to 5% by weight, on the basis of the monomers. Trade names of emulsifiers include, for example, Dowfax®2 A1, Emulan® NP 50, Dextrol® OC 50, Emulgator 825, Emulgator 825 S, Emulan® OG, Texapon® NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25. The surface active substance is typically used in amounts of 0.1% to 10% by weight, based on the monomers to be polymerized.
    [00023] In emulsion polymerization it is usual to use water-soluble initiators for the radical polymerization of monomers. Water-soluble initiators for emulsion polymerization are, for example, ammonium salts and alkali metal salts of peroxydisulfuric acid, for example, sodium peroxodisulfate, hydrogen peroxide or organic peroxides, for example, tert-butyl hydroperoxide. Also suitable are so-called reduction-oxidation (redox) initiator systems. Redox initiator systems are composed of at least one reducing agent, usually inorganic, and an organic or inorganic oxidizing agent. The oxidizing component comprises, for example, the emulsion polymerization initiators already identified above. The reducing component comprises, for example, alkali metal salts of sulfurous acid, such as, for example, sodium sulfite, sodium hydrogen sulfite, alkali metal salts of diensulfuric acid, such as sodium disulfite, bisulfate addition compounds with aliphatic aldehydes and ketones, such as acetone bisulphate, or reducing agents, such as hydroxymethanesulfinic acid and its salts, or ascorbic acid. Redox initiator systems can be used in conjunction with soluble metal compounds whose metal component is capable of existing in a plurality of valence states. Examples of typical redox initiator systems include ascorbic acid/iron(II) sulfate/sodium peroxydisulfate, tert-butyl hydroperoxide/sodium disulfite and tert-butyl hydroperoxide/Na-hydroxymethanesulfonic acid. The individual components, for example the reducing component, can also be mixtures, an example being a mixture of the sodium salt of hydroxymethanesulfinic acid with sodium disulfite. The established compounds are normally used in the form of aqueous solutions, with the lower concentration being determined by the amount of water that is acceptable in the dispersion and the higher concentration by the solubility of the respective compound in water. Generally, the concentration is 0.1% to 30% by weight, preferably 0.5% to 20% by weight, more preferably 1.0% to 10% by weight, based on the solution. The amount of initiators is generally 0.1% to 10% by weight, preferably 0.5% to 5% by weight, based on the monomers to be polymerized. It is also possible to use two or more different initiators in emulsion polymerization.
    [00024] Emulsion polymerization generally takes place at 30 to 130, preferably 50 to 90°C. The polymerization medium can be composed of either water alone or mixtures of water and water-miscible liquids such as methanol, ethanol or tetrahydrofuran. It is preferred to use only water. In polymerization it is also possible, for a more effective establishment of the particle size, for example, to include a seeding of the polymer in the initial charge.
    [00025] The manner in which the initiator is added to the polymerization vessel in the course of aqueous radical emulsion polymerization is known to a person skilled in the art. It can be included in its entirety in the initial charge to the polymerization vessel, or it can be introduced continuously or in stages according to its consumption in the course of the aqueous radical emulsion polymerization. In each individual case, this will depend on the chemical nature of the initiator system and also on the polymerization temperature. It is preferred to include a portion of the initial charge and supply the remainder to the polymerization zone at the rate at which it is consumed. The chain transfer agent can also be included in part in the initial charge or added completely or partially during the polymerization or towards the end of the polymerization.
    [00026] Monomers are preferably added at least partially continuously during polymerization. In part it is also possible that monomers are included in the initial charge in the polymerization vessel prior to starting the polymerization. It is preferred to include no more than 30% by weight of the total amount of the monomers, more preferably no more than 20% by weight, most preferably no more than 10% by weight of the monomers, in the initial charge in the polymerization vessel. The remaining monomers - i.e. preferably at least 70% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight - are added continuously during the polymerization. In a particular embodiment no monomers are included in the initial charge - in other words, the full amount of monomers is run through during polymerization. The individual components can be added to the reactor, in the case of the feed process, before, on the side or above, through the reactor base.
    [00027] In order to remove residual monomers it is also possible to add additional initiator (chemical deodorization) after the end of the appropriate emulsion polymerization, ie after a conversion of all monomers. In the case of emulsion polymerization, aqueous polymer dispersions are generally obtained with solids contents of 15% to 75% by weight, preferably 40% to 75% by weight. The polymer thus prepared is preferably used in the form of its aqueous dispersion.
    [00028] The particle size distribution of the dispersion can be monomodal, bimodal or multimodal. In the case of monomodal particle size distribution, the average particle size of the polymer particles dispersed in the aqueous dispersion is preferably less than 400 nm, more particularly less than 300 nm. With particular preference the average particle size is between 140 and 300 nm. By mean particle size here is meant the d50 of the particle size distribution, i.e. 50% by weight of the total mass of all particles have a particle diameter smaller than the d50. The particle size distribution can be determined in a known manner using the analytical ultracentrifuge (W. Machtle, Makromolekulare Chemie 185 (1984), pages 1025-1039). In the case of bimodal or multimodal particle size distribution, the particle size can quantify up to 1000 nm. The pH of the polymer dispersion is preferably set at a level greater than 4.5, more particularly at a level between 5 and 8.
    [00029] The invention also provides an adhesive dispersion, that is, an aqueous dispersion which in addition to the low molecular weight polymer described above comprises at least one dispersed adhesive polymer. The adhesive polymer has a higher average molecular weight than the low molecular weight polymer. An adhesive polymer for the purposes of the invention is a polymer having a glass transition temperature in the range of -60°C to -20°C. The glass transition temperature of the polymer is preferably greater than the glass transition temperature of the adhesive polymer, more particularly greater by at least 1°C or by at least 2°C.
    [00030] In the adhesive dispersion, the adhesive polymer is present in amounts preferably from 60% to 95% by weight, more particularly from 70% to 90% by weight and the low molecular weight polymer is present in amounts from 5% to 40% % by weight, more particularly from 10% to 30% by weight, the amounts being based in each case on solids content.
    [00031] Adhesive polymers can be polymers obtained by radical polymerization of ethylenically unsaturated compounds (monomers) or can be polymers obtained by polycondensation, such as polyurethanes, for example. The adhesive polymer preferably consists to some extent of at least 40% by weight or at least 60% by weight, or at least 80% by weight, more preferably at least 90% by weight, of the so-called main monomers. The main monomers are preferably selected from C1-C20 alkyl (meth)acrylates, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds, or mixtures of these monomers. Suitable adhesive polymers are more particularly poly(meth)acrylates, ethylene/vinyl acetate copolymer, polyurethanes, polyamide resins, saturated polyesters, polyolefins, styrene/butadiene block copolymers, styrene/isoprene block copolymers, polyimides, PVC and polyvinylpyrrolidone.
    [00032] Preferred adhesive polymers are (meth)acrylate polymers and vinyl acetate polymers. (Meth)acrylate polymers are formed from at least one (meth)acrylate monomer, which can be copolymerized with additional monomers. Vinyl acetate polymers are formed from at least one vinyl acetate monomer, which can be copolymerized with additional monomers; ethylene/vinyl acetate copolymer is an example. Suitable monomers are, for example, alkyl esters of (meth)acrylic acid having a C1-C10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethyloxy acrylate. In particular, mixtures of (meth)acrylic acid alkyl esters are also suitable. Vinyl esters of carboxylic acids having 1 to 20 C atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl esters of versatic acid and vinyl acetate. EqorquVqu xkpüctqoávkeq eqpVgorncfqu kpenwgo xkpknvqnwgpq. g- and p- ogvknguvktgpq." g-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and - preferably - styrene. Examples of nitriles are acrylonitrile and methacrylonitrile. Vinyl halides are compounds of chloride-, fluoride- or bromide-substituted, ethylenically unsaturated, preferably vinyl chloride and vinylidene chloride Examples of vinyl ethers include vinyl methyl ether and vinyl isobutyl ether Preferred vinyl ethers are those of alcohols comprising 1 to 4 C atoms. to 8 C atoms and two olefinic double bonds are, for example, butadiene, isoprene and chloroprene. Hydrocarbons having 2 to 4 C atoms are, for example, ethylene, propylene or butene. Suitable main monomers are C1 to C10 alkyl acrylates and C1 to C10 alkyl methacrylates, more particularly C1 to C8 alkylacrylates and methacrylates and vinylaromatics, more particularly styrene and mixtures thereof. methyl acrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, styrene and also mixtures of these monomers.
    [00033] As well as the main monomers, the adhesive polymer can comprise additional monomers, examples being acidic monomers, monomers containing hydroxyl groups, more particularly C1-C10 hydroxyalkyl (meth)acrylates, or (meth)acrylamide. Additional monomers also include phenyloxyethylglycol mono(meth)acrylate, glycidyl(meth)acrylate, aminoalkyl(meth)acrylates, such as, for example, 2-aminoethyl(meth)acrylate. Alkyl groups preferably have from 1 to 20 C atoms. Other additional monomers include crosslinking monomers. Additional monomers are generally used in smaller amounts; its fraction in total is preferably below 10% by weight, more particularly below 5% by weight.
    [00034] Preferred adhesive polymers of the adhesive composition are acrylate or methacrylate polymers which are formed not only from acrylic ester and/or methacrylic ester monomers, but also from monomers having acid groups. Monomers having acidic groups are preferably present in not less than 0.1% by weight, for example 0.1% to 15% by weight, preferably in amounts from 0.1% to 5%, more preferably 0.2% to 4%, most preferably 0.5% to 3% by weight, based on the total amount of monomers. Examples of monomers having acidic groups are monomers having carboxylic, sulfonic or phosphonic acid groups. Carboxylic acid groups are preferred. Examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Acid groups can be present in the form of their salts.
    [00035] The radically polymerized adhesive polymers can be prepared, in the same way as for the preparation of low molecular weight polymers, by emulsion polymerization. To prepare the adhesive dispersion it is possible to mix an aqueous dispersion which does not comprise any adhesive polymer, but comprises the low molecular weight polymer with an aqueous dispersion which comprises an adhesive polymer. In a preferred embodiment of the invention, the low molecular weight polymer described above is prepared in situ in the presence of at least one adhesive polymer dispersed in water.
    [00036] The adhesive dispersion of the invention is preferably a PSA dispersion and may comprise additives. Additives are selected, for example, from fillers, colorants, flow control aids, thickeners, preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents, UV protectants and optionally other tackifiers. Preferably, however, no other tackifiers are included. For more effective wetting of surfaces, adhesive dispersions may in particular comprise wetting aids, examples being fatty alcohol ethoxylates, ethoxylated alkylphenols, sulfosuccinic esters, ethoxylated nonylphenol, polyoxyethylenes/propylenes or sodium dodecylsulphonates. The amount is generally 0.05 to 5 parts by weight, more particularly 0.1 to 3 parts by weight, per 100 parts by weight of polymer (solid).
    [00037] The invention also provides use of the aqueous dispersion of low molecular weight polymer as an additive in adhesive or coating compositions as, for example, tackifying agent for adhesives and more particularly for the production of self-adhesive articles, more particularly for the production of adhesive labels, adhesive sheets or adhesive tapes, examples being adhesive tapes for fixing components, especially in automobile construction, for electronic items or in construction applications and also for floor adhesives.
    [00038] The invention also provides self-adhesive articles obtainable by coating a carrier material with an aqueous dispersion of the invention comprising at least one adhesive polymer.
    [00039] Adhesive dispersions of the invention can be used for production of adhesive articles and self-adhesive treated articles. The adhesive article can be a label. A preferred label is a self-adhesive paper label or film label, the adhesive being applied to paper or a film as carrier material. The adhesive article may also be an adhesive tape, where the adhesive is applied to a tape-like carrier material. The adhesive tape carrier material may comprise woven or non-woven fabrics, films, paper, felts, foams and coextrudates, or combinations thereof. Fields of application are single-sided and double-sided, carrier-free adhesive tapes, medical adhesive tapes, adhesive packaging tapes, cable coating tapes, carpet laying tapes, adhesive mounting tapes, adhesive tapes for securing sheets of felt. roof, self-adhesive treated carrier materials such as foams, eg bitumen sheets and the like.
    [00040] For production of adhesive articles, a layer of adhesive can be applied to the carrier material in a customary manner, for example, by rolling, spatula coating, spreading, etc. Where an aqueous adhesive dispersion is used, water can be removed by drying at 50 to 150°C, for example. The coated substrates obtained in this way are used, for example, as self-adhesive articles, such as adhesive labels, tapes or sheets. Carriers can, for this purpose, be cut before or after application of the adhesive, to form adhesive tapes, labels or sheets. For the latter use, the PSA coated side of the substrates can be coated with a release paper, such as a siliconized paper, for example.
    [00041] The invention also provides an adhesive tape that has at least one carrier layer and is coated on one or both sides with at least one PSA dispersion of the invention. Preferred carrier materials for producing adhesive tapes are polyethylene (PE), oriented polypropylene (oPP), polyethylene terephthalate (PET), PE foam and polyurethane foam (PU foam).
    [00042] For the production of adhesive tapes, the application weight of the PSA dispersion, based on the solids content, is preferably at least 20 g/m2 or at least 30 g/m2, for example, 60 to 80 g/ m2.
    [00043] An embodiment of the invention is an adhesive tape where the carrier layer material is selected from PE, oPP, PET, PE foam or PU foam and/or the adhesive tape has at least one peelable protective layer that coats the adhesive layer .
    [00044] The adhesive article may be a film label or an adhesive sheet, more particularly a decorative sheet or a protective sheet, with the adhesive being applied to a polymer film carrier material. The adhesive articles are then preferably self-adhesive and generally consist of a polymeric carrier material and a layer of adhesive applied to one or both sides, preferably one side. The carrier material can comprise, for example, transparent polymer films. Transparent polymer films can consist, for example, of polyolefins, such as polyethylene or polypropylene, which can be biaxially or monoaxially oriented, or of polyesters, polyethylene terephthalate, polyvinyl chloride, polystyrene or polyamide. Especially suitable are transparent carriers made, for example, from polyolefins, more particularly polyethylene or oriented polypropylene (oPP), or from polyesters. The film thickness is generally not more than 0.5 mm, preferably not more than 0.3 mm or not more than 0.2 mm. Polyethylene films can have a film thickness, for example, from 70 to 130 micrometers or from 80 to 130 micrometers. Polyethylene terephthalate films can have a film thickness, for example, from 15 to 50 micrometers or from 20 to 40 micrometers. oPP films can have a film thickness, for example, from 40 to 130 micrometers or from 50 to 100 micrometers. Transparent polymer films have a light transmission of generally at least 85%, preferably at least 88% or at least 90%, measurable, for example, in accordance with ASTM D 1003-07.
    [00045] The aqueous polymer dispersions of the invention have very good tackifying properties when used in combination with adhesive polymers and allow the production of adhesive articles having very good adhesive properties, particularly in relation to the combination of good adhesion and good cohesion. Examples Compounds used: AA acrylic acid MAA methacrylic acid AM acrylamide MMA methyl methacrylate nBA n-butyl acrylate VAc vinyl acetate EHTG (2-ethylhexyl) thioglycolate Performance tests
    [00046] PSA dispersions were applied to Laufenberg NSA 1370 silicone paper, dried and transferred to Herma label paper (75 g/m2, unprinted), to give an application rate of 18 g/m2 of the dry adhesive. After conditioning the laminates under standard conditions (23°C, 50% relative humidity) for at least 16 hours, determinations were made for peel strength (adhesion), shear strength (cohesion) and rapid tackiness at 23° Ç. The PSA coated carrier was cut into 25 mm wide test strips. a) Quick sticky
    [00047] In determining fast tackiness (sticky surface, also called tacky loop), a determination is made of the force with which an adhesive applied to a carrier material bonding without pressure on a substrate opposite to removal of the substrate at a removal rate defined. Carrier material is 75 g/m2 label paper, substrate is cardboard. A test strip 25mm wide and 250mm long is cut from the adhesive coated carrier and stored at standard conditions (23°C, 50% relative humidity) for at least 16 hours. The two ends of the test strip are folded over a length of approximately 1 cm with the sticky side inwards. A loop is formed from the adhesive strip with the adhesive side out and the two ends are placed together and stapled to the upper jaw of a stress testing machine. The assembled test substrate is stapled to the lower jaw and the test substrate is inserted. The adhesive strip loop is moved down by the tension testing machine at a speed of 300mm/minute and then the adhesive side of the test strip binds to the substrate without additional pressure. The tension testing machine is stopped and is immediately moved up again when the base edge of the upper jaw is 40 mm above the substrate. The test result is reported in N/25mm width. The maximum value on the screen (Fmax) is read as the sticky surface measurement. An average is formed from at least two individual results. b) Shear strength (cohesion)
    [00048] For the determination of shear strength, the test strips were adhered to the steel plate with a bonded area of 25 x 25 mm, rolled down once using a roller weighing 1 kg and, after 10 minutes, loaded in suspension with a weight of 1 kg. Shear strength (cohesion) was determined under standard conditions (23°C; 50% relative humidity). The measurement of shear strength is the time in hours until the weight drops; the mean was calculated from at least 3 measurements in each case. c) Resistance to peeling (adhesion)
    [00049] For the determination of peel strength (adhesion), a 25 mm wide test strip was adhered to a cardboard specimen and rolled down once using a 1 kg weight roller. It was then stapled by one end to the upper jaws of a strain-strain testing apparatus. The adhesive strip was removed from the test surface at an angle of 180° and at 300 mm/min - the adhesive strip was bent around and removed parallel to the specimen and the dispatch of the force required to achieve this was recorded. The peel strength measurement was the force in N/25 mm which was obtained as the mean value of at least two measurements. Peel strength was measured 1 minute after bonding. After this time, bond strength has fully developed. Test methods essentially correspond to Final Test Methods (FTM) 1, 8 and 9. Examples
    [00050] Aqueous polymer dispersions were prepared by emulsion polymerization of the components reproduced in table 1, with the properties identified in table 1. Additionally used in each emulsion polymerization were 1 part by weight of Disponil® FES 77 (emulsifier), 0 0.2 part by weight of Dowfax® 2A1, 0.4 part by weight of sodium persulfate (initiator), 0.16 part by weight of acetone bisulfite and 0.1 part by weight of tert-butyl hydroperoxide. The solids content was approximately 52-56% by weight. The pH was adjusted to approximately 57.
    [00051] Examples D1 to Dx are inventive, while examples C1 to Cx are non-inventive, comparative examples. Table 1: Components for preparing polymer dispersions and properties thereof; amounts in parts by weight


    Comparative example C6
    [00052] The commercial product Acronal® A 107 was used as comparative example C6.
    [00053] This product is an anionic polyacrylate (copolymer of nBA and (meth)acrylic acid). Tg: -46°C Average molecular weight Mw = 148,000 g/mol PSA dispersions
    [00054] Dispersions of PSA (pressure sensitive adhesive) were prepared, in each case, from approximately 20 parts by weight of dispersions D1 to D21 or comparative dispersions C1 to C11 as tackifiers, approximately 80 parts by weight of Acronal® V 215 as an adhesive polymer and 0.5 part by weight of Lumiten® I-SC (wetting agent), the amounts being based, in each case, on the solids present in the respective dispersions.
    [00055] The test results for fast tack, shear strength and peel strength are summarized in table 2. Table 2: test results for fast tack, shear strength and peel strength


    [00056] The results show that for C1-C3 and for C7-C11, the values of fast stickiness and peeling resistance are very low. For C4, C5 and C6 the shear strength values are too low. The desire here is for shear strength values of at least 15 hours, preferably at least 20 hours.
    权利要求:
    Claims (15)
    [0001]
    1. Aqueous adhesive dispersion, comprising at least one water-dispersed adhesive polymer and at least one water-dispersed tackifier polymer, wherein the tackifier polymer is a polymer having a glass transition temperature as measured by Differential Scanning Calorimetry of according to ASTM 3418/82 as the midpoint temperature at a heating rate of 20K/min, greater than or equal to -40°C and less than 0°C, preferably greater than or equal to -35°C and less than 0° C, preparable by emulsion polymerization in the presence of at least one chain transfer agent and preparable from a mixture of monomers comprising (a) at least 40% by weight of at least one C1 to C20 alkyl (meth)acrylate , (b) 0% to 30% by weight of at least one vinyl aromatic, (c) at least 0.1% by weight to 7% by weight of at least one acidic monomer, (d) 0% to 50% by weight of additional monomers, the amounts of monomer being based in each case on the sum of all the monomers ros, characterized by the fact that the theoretical glass transition temperature of the polymer tackifier, calculated for a polymerization without a chain transfer agent, is greater than -25°C, and the at least one chain transfer agent is a organic compound comprising sulfur in bonded form, and the chain transfer agent is used in an amount such that the average molecular weight of the tackifying agent polymer is less than 50000.
    [0002]
    2. Dispersion according to claim 1, characterized in that the average molecular weight of the polymer is from 1500 to 45000, preferably from 2000 to 20000.
    [0003]
    3. Dispersion according to claim 1 or 2, characterized in that the monomers (a) are used in an amount of 60% to 99.9% by weight and are selected from one or more (meth)acrylates of C1 to C10 alkyl.
    [0004]
    4. Dispersion according to any one of claims 1 to 3, characterized in that the monomers (b) are selected from vinyltoluene, alpha-methylstyrene, para-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4- n-decylstyrene and - preferably - styrene.
    [0005]
    5. Dispersion according to any one of claims 1 to 4, characterized in that the acidic monomers (c) are used in an amount of 0.1% to 7% by weight and are selected from acrylic acid, methacrylic acid , itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinylatic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate and mixtures of these monomers.
    [0006]
    6. Dispersion according to any one of claims 1 to 5, characterized in that the additional monomers (d) are used in an amount of 0.1% to 40% by weight and are selected from (meth)acrylates of C1 to C20 hydroxyalkyl, vinyl esters of carboxylic acids comprising up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds, (meth)acrylamide or mixtures of these monomers.
    [0007]
    7. Dispersion according to any one of claims 1 to 6, characterized in that the polymer is preparable from a mixture of monomers comprising (a) 60% to 99.7% by weight of at least one (met ) C1 to C10 alkyl acrylate, (b) 0% to 30% by weight of styrene, (c) 0.2% to 7% by weight of at least one acidic monomer selected from acrylic acid and methacrylic acid, (d) 0.1% to 30% by weight of additional monomers selected from C1 to C10 hydroxyalkyl (meth)acrylates and vinyl acetate, the monomer amounts being based in each case on the sum of all monomers.
    [0008]
    8. Dispersion according to any one of claims 1 to 7, characterized in that the chain transfer agent is used in an amount of at least 1 part by weight per 100 parts by weight of monomers and is preferably selected from group consisting of tert-dodecyl mercaptan, n-dodecyl mercaptan and 2-ethylhexyl thioglycolate.
    [0009]
    9. Dispersion according to any one of claims 1 to 8, characterized in that the adhesive polymer is present in amounts from 60% to 95% by weight, more particularly from 70% to 90% by weight and the polymer of low molecular weight is present in amounts from 5% to 40% by weight, more particularly from 10% to 30% by weight, the amounts being based in each case on the solids content.
    [0010]
    10. Dispersion according to any one of claims 1 to 9, characterized in that the glass transition temperature of the polymer is greater than the glass transition temperature of the adhesive polymer, measured by Differential Scanning Calorimetry according to ASTM 3418 /82 as the midpoint temperature at a heating rate of 20K/min.
    [0011]
    11. Dispersion according to any one of claims 1 to 10, characterized in that the low molecular weight polymer is prepared in situ by a staged procedure in the presence of the adhesive polymer.
    [0012]
    12. Method for producing the dispersion comprising adhesive polymer as defined in any one of claims 1 to 11, characterized in that it comprises mixing an aqueous dispersion of the tackifying agent polymer which does not comprise adhesive polymer with an aqueous dispersion comprising an adhesive polymer, or comprises preparing the tackifying polymer in the presence of an adhesive polymer dispersed in water.
    [0013]
    13. Use of the aqueous dispersion as defined in any one of claims 1 to 11, characterized in that it is for the production of adhesive labels, adhesive sheets or adhesive tapes.
    [0014]
    14. Self-adhesive article, characterized in that it can be obtained by coating a carrier material with a dispersion comprising adhesive polymer as defined in any one of claims 1 to 11.
    [0015]
    15. Use of the aqueous dispersion as defined in any one of claims 1 to 11, characterized in that it is to produce floor adhesives.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09J 133/08 (2006.01), C09J 133/10 (2006.01), C09J |
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-07-13| 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 23/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12153979|2012-02-06|
    EP12153979.5|2012-02-06|
    PCT/EP2013/051188|WO2013117428A1|2012-02-06|2013-01-23|Aqueous polymer dispersion that can be used as a tackifier for adhesives and can be produced by emulsion polymerisation based on c1 to c20 alkyl acrylates|
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