Patent Application
20110239593
The invention relates to the use of an activatable adhesive composition having a content of specific acid- or hydroxy-group-comprising (meth)acrylate or vinylaromatic copolymers for producing folding-carton blanks which are blocking-resistant at 25° C. with adhesive composition applied thereto, and also to the energy-activated production of folding cartons from corresponding folding-carton blanks.
Folding-carton blanks are industrially pre-produced blanks which are supplied space-savingly in the flat, collapsed state from the manufacturer to the processing enterprises, where they are erected to form cartons and are filled and sealed. In many cases, the erected portions opposite one another in each case are joined to one another by adhesive bonding and/or the cartons after filling are sealed by adhesive bonding. Conventionally, folding-carton blanks intended for adhesive bonding are supplied unglued, i.e., without applied adhesive, to the processing enterprise, in the form, for example, of carton type E according to the classification system of the European Carton Makers' Association. In that case, immediately prior to their entry into the erecting apparatus, the blanks are provided with a hotmelt adhesive and, following erection, are bonded adhesively. There is a risk here of the erecting machinery being compromised by glue deposits on the nozzles and tools, and, even when adhesive positioning is precise, of there possibly being unwanted, visible glue traces on the finished packaging. The desire, therefore, is for a technology which makes it unnecessary to apply adhesive at the processing enterprise immediately prior to folding-carton erection.
DE 3246325 describes a method for producing folding cartons where a dispersion-based varnish, which is not described in more detail, is applied to blanks and adhesive bonding is effected by exposure to ultrasound. WO 2004/076578 describes a reactivatable adhesive which is reactivated by exposure to radiative energy having a wavelength of 400 nm to 100 000 nm. The radiative energy is generated more particularly by NIR radiation, e.g., by a halogen-tungsten lamp, and the adhesive comprises an NIR absorber ingredient. The unspecific, undirected use of relatively high-energy NIR radiation may result in unwanted, extensive heating even of parts of the packaging that are not intended for adhesive bonding, or of the contents for packing, and this compromises the possibilities for filling of the packaging with heat-sensitive or radiation-sensitive contents before or immediately after irradiation, and, furthermore, consumes more energy than is needed for actual bonding.
It was an object of the present invention to provide, for folding-carton manufacture, a technology which is both energy-efficient and time-efficient and which makes it possible to do away with application of adhesive at the processing enterprise immediately prior to folding-carton erection. The technology ought ideally further to allow the adhesive bonding, or sealing effected by adhesive bonding, of folding cartons which are already filled with heat-sensitive or radiation-sensitive contents or which are to be filled with such contents immediately following the adhesive-bonding operation.
The invention provides for use of an activatable adhesive composition for producing folding-carton blanks. The folding-carton blanks have surface regions to which the activatable adhesive composition is applied and are blocking-resistant at 25° C. The adhesive composition at less than or equal to 25° C. has an Ig G′ value of greater than or equal to 6.0 and at greater than or equal to 120° C. has an Ig G′ value of less than or equal to 4.0, comprises at least one copolymer having a glass transition temperature of greater than 30° C., the copolymer being formed from at least one first monomer and from more than 3% and less than 40% by weight, based on the total amount of monomers, of at least one second monomer, which is different from the first monomer, the first monomer being selected from the group consisting of alkyl acrylates, alkyl methacrylates, and vinylaromatics, and the second monomer being selected from the group consisting of ethylenically unsaturated monomers having acid groups, hydroxyalkyl acrylates, and hydroxyalkyl methacrylates.
The invention also provides the folding-carton blanks produced according to the use of the invention, the use of the folding-carton blanks for the energy-activated production of folding cartons, and also folding cartons produced according to said use.
The invention also provides a method for producing folding cartons, in which
The term “activatable adhesive composition” means that the adhesive composition and folding-carton blanks with adhesive composition applied thereto, at room temperature (25° C.) and without energetic exposure (e.g., to electromagnetic radiation), are not adhesive or have only such slight adhesiveness that the folding-carton blanks, which are generally composed of cardboard, are blocking-resistant. On energetic exposure, the adhesive composition acquires adhesiveness.
The term “adhesive composition” encompasses the active adhesive-bonding ingredients and any adjuvants and solvents present.
Blocking-resistant for the purposes of the specification means that, when an individual blank is lifted from a stack of two or more blanks, no further blank adheres. In the stack there may be a pressure of up to 2 g/mm2.
The terms “energy-activated”, “activated by energy exposure” or “energetic exposure” denote exposure to energy in the form of radiation or ultrasound, more particularly in the form of electromagnetic radiation. Electromagnetic radiation may be, for example, IR radiation with a wavelength of 0.4 to 1000 μm, NIR radiation with a wavelength of 0.4 to 100 μm, microwave radiation with a wavelength of 1 mm to 1 m, or radiowaves with a wavelength of 1 m to 10 km.
The adhesive composition has a temperature-dependent adhesiveness profile. At room temperature (25° C.), the adhesiveness of the composition is low or zero. At temperatures above room temperature, the composition is adhesive.
Unless indicated otherwise, physical parameters and properties relate to conditions at room temperature (25° C.) and relative atmospheric humidity typical of this sector (30-90%).
Preferably the adhesive composition at less than or equal to 25° C. has an Ig G′ value of greater than or equal to 6.0, preferably of 6.0 to 8.0, and at temperatures of greater than or equal to 120° C. has an Ig G′ value of less than or equal to 4.0, preferably of 2.5 to 3.9, as measured by means of a deformation-controlled rheometer with parallel-plate geometry (diameter 8 mm; sample thickness 0.9-1.2 mm) and torsion-rectangular geometry (sample width 6 mm; sample length 21 mm, sample thickness 0.9-1.2 mm). The parameter measured is the dynamic shear modulus G′ at a measurement frequency of 1 Hz with the torsion-rectangular geometry at 25° C. and with the parallel-plate geometry at 120° C. For the measurements, films are cast from the adhesives and are dried to constant weight.
The Ig G′ values of the invention can be adjusted through the monomer composition of the adhesive polymers or through addition of plasticizer. Where the monomer composition of the polymers does not itself give the adhesive composition the Ig G′ values, the Ig G′ values can be adjusted in accordance with the invention by addition of the plasticizers described in more detail below.
The adhesive composition may be (before application to the blanks and drying where appropriate) a meltable solid composition, a polymer solution or a polymer dispersion. Aqueous polymer solutions and aqueous polymer dispersions are preferred. Included preferably is at least one polymer which has a glass transition temperature Tg of greater than 30° C., preferably of greater than 35° C. or of greater than 40° C. The glass transition temperature can be determined by typical methods such as Differential Scanning Calorimetry (see, for example, ASTM 3418/82, midpoint temperature). In the case of aqueous polymer dispersions, the dispersion preferably includes solids contents of 15% to 75% by weight, preferably from 40 to 75% by weight. In one embodiment the adhesive composition comprises at least 40% by weight of dispersed polymer.
By copolymers in the sense of the invention are meant polymers of two or more different monomers. In the text below, the designation (meth)acrylate and similar designations are used as an abbreviated notation for “acrylate or methacrylate”.
The copolymers used in the adhesive composition may be obtained by free-radical polymerization of ethylenically unsaturated compounds. The copolymer is composed preferably to an extent of at least 10% or at least 20%, or at least 40%, more preferably at least 60%, by weight of the first monomers, which are preferably selected from C1 to C20 alkyl (meth)acrylates and vinylaromatics having up to 20 carbon atoms. The alkyl (meth)acrylate monomers are preferably selected from C1-C20 alkyl (meth)acrylates, more particularly C1 to C10 alkyl acrylates and C1 to C10 alkyl methacrylates, or C1 to C8 alkyl (meth)acrylates. Suitable monomers are, for example, methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate, n-hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Also suitable in particular are mixtures of the (meth)acrylic acid alkyl esters. Vinylaromatics contemplated include vinyltoluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, and—preferably—styrene. In one embodiment the copolymers of the invention comprise styrene in amounts from 10% to 60% by weight, preferably 20-50% by weight.
The polymer to be used according to the invention is furthermore formed from more than 3% by weight and up to 40% by weight, based on the total amount of monomers, of monomers which are selected from ethylenically unsaturated monomers with acid groups, hydroxyalkyl acrylates and hydroxyalkyl methacrylates. Monomers with acid groups are more particularly ethylenically unsaturated compounds which have at least one carboxylic, sulfonic or phosphonic acid group. Carboxylic acid groups are preferred. Examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. The acid groups may be present in the form of their salts. Preferred hydroxyalkyl (meth)acrylates are the C2 to C12 hydroxyalkyl (meth)acrylates, and more particularly the C2 to C6 or the C2 to C4 hydroxyalkyl (meth)acrylates. Especially preferred are hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate or hydroxybutyl methacrylate. The amount of acid monomers and hydroxyl monomers in the copolymer can be, for example, 4% to 15% by weight in the case of aqueous dispersions, or in the case of aqueous solutions, up to 40%, e.g., 24% to 40%, by weight, based on the polymer.
Besides the principal monomers the polymer may comprise further monomers, examples being vinyl esters of carboxylic acids comprising up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising from 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds, or mixtures of these monomers. Vinyl esters of carboxylic acids having 1 to 20 C atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, Versatic acid vinyl esters, and vinyl acetate. Examples of nitriles are acrylonitrile and methacrylonitrile. The vinyl halides are chlorine-, fluorine- or bromine-substituted, ethylenically unsaturated compounds, preferable vinyl chloride and vinylidene chloride. Examples of vinyl ethers include vinyl methyl ether or vinyl isobutyl ether. Those preferred are vinyl ethers of alcohols comprising 1 to 4 C atoms. Suitable hydrocarbons having 4 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.
Further monomers are, for example, also (meth)acrylamides, phenyloxyethylglycol mono(meth)acrylate, glycidyl (meth)acrylate, and aminoalkyl (meth)acrylates such as, for example, 2-aminoethyl (meth)acrylate. Alkyl groups have preferably from 1 to 20 C atoms. Crosslinking monomers may also be recited as further monomers. The further monomers are used generally in minor amounts, their total proportion being preferably below 10% by weight, more particularly below 5% by weight.
The proportion of the monomers relative to one another is preferably set such that the glass transition temperature of the polymer is greater than 30° C., or greater than 35° C. or greater than 40° C.
The free-radically polymerized polymers may be prepared by conventional emulsion polymerization. In emulsion polymerization, ionic and/or nonionic emulsifiers and/or protective colloids and/or stabilizers, as surface-active substances, and also suitable initiators and, if desired, molecular-weight regulators are used. The emulsion polymerization takes place in general at 30 to 130° C., preferably at 50 to 90° C. The polymerization medium may be composed either of water alone, or of mixtures of water and water-miscible liquids such as methanol. It is preferred to use just water. In the polymerization it is possible to include a polymer seed in the initial charge for the purpose, for example, of more effectively setting the particle size. The emulsion polymerization affords aqueous dispersions of the polymer generally with solids contents of 15% to 75% by weight, preferably of 40% to 75% by weight. Dispersions having a very high solids content are preferred. In one embodiment the dispersion or adhesive composition comprises at least 60% by weight of dispersed polymer. In order to be able to obtain solids contents >60% by weight, the particle size set ought to be bimodal or polymodal, since otherwise the viscosity becomes too high and the dispersion can no longer be managed. Generating a new generation of particles can be accomplished by adding seed, by adding excess amounts of emulsifier, or by adding miniemulsions, for example. Generating one or more new particle generations can take place at any desired point in time. Said point in time is guided by the target particle-size distribution for a low viscosity. The polymer thus prepared is used in the form of its aqueous dispersion. The size distribution of the dispersion particles may be mono-modal, 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 200 nm. With particular preference the average particle size is between 140 and 200 nm. By average particle size here is meant the d50 value 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 value. The particle-size distribution can be determined in a known way 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 may be up to 1000 nm. The pH of the polymer dispersion is adjusted preferably to a pH of more than 4.5, more particularly to a pH of between 5 and 8.
The adhesive composition preferably comprises at least one electromagnetic-radiation absorber, more particularly microwave-radiation absorber. This component is preferably itself not adhesive or tacky, and is present preferably in an amount of 2% to 30%, more particularly of 5% to 15%, by weight, based on the overall composition.
A component is an electromagnetic-radiation absorber or microwave-radiation absorber in the sense of the invention if on irradiation with electromagnetic waves it absorbs energy, heats up in doing so, and emits the absorbed energy to the surroundings, in the form of heat. The electromagnetic-radiation absorber is selected, for example, from the group consisting of carbon black, graphite, organic color pigments, and mixtures thereof.
The adhesive composition preferably comprises at least one plasticizer. The plasticizers are present preferably in an amount of 5% to 50%, more particular of 5% to 35%, by weight, based on the overall composition. Examples of plasticizers are phthalic esters, trimellitic esters, acyclic dicarboxylic esters, polymeric plasticizers, phosphoric esters, fatty acid esters, hydroxycarboxylic esters, epoxy plasticizers, polyamide plasticizers, and polyalkylene glycols. Phthalic esters and trimellitic esters are, for example, the esters of phthalic acid, isophthalic acid or mellitic acid, respectively, with C1-C10 alkanols, e.g., di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, diisononyl phthalate, di-n-decyl isophthalate, di(2-ethylhexyl) phthalate, di-n-butyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, dimethyl phthalate, diethyl phthalate, and tris(2-ethylhexyl) trimellitate. Acyclic dicarboxylic esters are, for example, diesters of dicarboxylic acids with alkanols, more particularly the diesters of C4 to C10 dicarboxylic acids with C1 to C10 alkanols, examples being the diesters of adipic acid, decanedioic acid, glutaric acid, and succinic acid, e.g., dimethyl adipate, diethyl adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl glutarate, diethyl glutarate, di-n-butyl glutarate, diisobutyl glutarate, dimethyl succinate, diethyl succinate, di-n-butyl succinate, and diisobutyl succinate, and also mixtures of the aforementioned compounds. Polymeric plasticizers are, for example, the polyesters of dicarboxylic acids and alkanediols, more particularly of C4 to C10 dicarboxylic acids and C2 to C10 diols with molecular weights Mr of 1800 to 13 000, e.g., polyesters of adipic acid, decanedioic acid, azelaic acid or phthalic acid with diols such as butane-1,3-diol, propane-1,2-diol, butane-1,4-diol, hexane-1,6-diol, and others. Phosphoric esters are, for example, phosphoric acid compounds esterified at least once with alkanol, examples being C1-C10 alkyl di-C6-C14 aryl phosphates. Examples are isodecyl diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, diphenyl acetyl phosphate, tris(2-ethylhexyl) phosphate, and tris(2-butoxyethyl) phosphate. Hydroxycarboxylic esters are, for example, citric esters, such as tributyl O-acetyl citrate, for example, and corresponding esters of tartaric acid and of lactic acid. Polyamide plasticizers are, for example, benzenesulfonamides and methylbenzenesulfonamides.
Particularly preferred plasticizers are polyalkylene glycols, more particularly polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymers, more particularly the block copolymers, and also polypropylene glycols etherified with two different alcohols. Suitable polyalkylene glycols are more particularly those having a molecular weight of 100 to 2000. Examples of suitable plasticizers include polyethylene glycols which are available commercially under the brand name Puriol® E. Preferably included is at least one polyethylene glycol, more particularly having a molecular weight of 100 to 2000. The polyethylene glycols are present preferably in an amount of 5% to 35%, more particularly of 10% to 30%, by weight, based on the overall composition.
The adhesive composition may comprise a tackifier (tackifying resins). Tackifiers are known, for example, from Adhesives Age, July 1987, pages 19-23, or Polym. Mater. Sci. Eng. 61 (1989), pages 588-592. Tackifiers are, for example, natural resins, such as rosins and their derivatives formed by disproportionation or isomerization, polymerization, dimerization or hydrogenation. These derivatives may be present in their salt form (with, for example, monovalent or polyvalent counterions (cations)) or, preferably, in their esterified form. Alcohols used for the esterification may be monohydric or polyhydric. Examples are methanol, ethanediol, diethylene glycol, triethylene glycol, 1,2,3-propanethiol, and pentaerythritol. Also employed are hydrocarbon resins, examples being coumarone-indene resins, polyterpene resins, hydrocarbon resins based on unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, a-methylstyrene, and vinyltoluene. Also increasingly used as tackifiers are polyacrylates which have a low molar weight. These polyacrylates preferably have a weight-average molecular weight Mw of below 30 000. The polyacrylates are preferably composed to an extent of at least 60%, more particularly at least 80%, by weight of C1-C8 alkyl (meth)acrylates. Preferred tackifiers are natural or chemically modified rosins. Rosins are composed predominantly of abietic acid or derivatives of abietic acid. The tackifiers can be added in a simple way to the polymer dispersion. In this context, the tackifiers themselves are preferably in the form of an aqueous dispersion. The amount by weight of the tackifiers is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, relative to 100 parts by weight of polymer (solids/solids).
The adhesive composition may be composed solely of the polymer, or of the aqueous dispersion of the polymer, but may also further comprise the above-stated adjuvants, and also further adjuvants, examples being fillers, dyes, flow control agents, thickeners, preferably associative thickeners, defoamers, pigments or wetting agents. For improved surface wetting, the adhesive compositions may more particularly comprise wetting assistants, examples being fatty alcohol ethoxylates, alkylphenol ethoxylates, nonylphenol ethoxylates, polyoxyethylenes/-propylenes or sodium dodecylsulfonates. The amount of adjuvants is generally 0.01 to 5 parts by weight, more particularly 0.1 to 3 parts by weight, per 100 parts by weight of polymer (solids).
The folding-carton blanks may be made of a material suitable for producing folding cartons. Examples of suitable materials include paperboard, cardboard, corrugated card or plastic. The surface may have paper stuck to it, may be laminated with films/foils, may be coated with plastic, may be printed with ink, primed or varnished. The surface of the blanks may be coated, for example, with PP, OPP, PVC, PE or with waxes. The thickness of the blank material is preferably 0.5 to 10 mm.
Application of the adhesive composition to the folding-carton blanks may take place by means of customary application or coating methods, as for example using a size press, film press, blade coater, air brush, knife coater, a curtain-coating method or a spray coater. In one preferred embodiment, application takes place by means of a print application technology, e.g., flexographic, offset or screen printing. Flexographic printing is preferred. After the print-applied adhesive coating has dried, its blocking resistance is such that the printed flat folding-carton blanks can be stacked without adhering to one another. In particular the blocking-resistance of the print-applied adhesive is such that a stack of the flat blanks, generally cartons, that are printed with the adhesive can be stored under a weight of 2 t/m2 for up to one year without individual cartons adhering to one another when separated.
In one embodiment, the adhesive composition is applied to the raw material intended for blanks but not yet cut to size, after which the blanks are produced, by punching or cutting, for example.
The blanks may have a complete or partial coating of the adhesive composition. The adhesive composition is preferably applied only in those, limited regions which are actually adhesively bonded. The amount applied (wet) is preferably 10 to 300 g/m2. The layer thickness of the applied and dried adhesive is preferably from 5 to 200 μm.
Folding cartons can be produced from the folding-carton blanks provided with the adhesive composition, using erecting machines that are known per se for that purpose, said machines having preferably been modified to include at least one source of electromagnetic radiation, for example an installed microwave generator or to allow the irradiation of the blanks with an external radiation source. The irradiation which activates the adhesive can be accomplished before the areas intended for adhesive bonding are brought into contact with one another, or, preferably, while the areas are being brought into contact. Generally speaking, this is done with an applied pressure which is suitably high for a durable, firm bond. The time of radiative activation of the adhesive layer in the erecting machine is preferably less than 2 seconds, less than 1 second or less than 0.5 second. Within the activation time, the layer of adhesive becomes sufficiently tacky to effect secure adhesive bonding of the folding cartons in the erecting machine, if desired with subsequent or simultaneous application of an applied pressure. Adhesive bonding is considered sufficiently reliable if, in the case of adhesively bonded cartons, the adhesive bond can be parted only with complete fiber extraction.
In the case of adhesive bonding in the erecting machine, the layer of adhesive that is applied to a first region of the surface of the blank may be bonded either against a layer of adhesive applied to a second region of the surface of the blank, or against an adhesive-free region of the blank. At the site intended for adhesive bonding, the adhesive-free region may also be printed with ink, primed or varnished.
Activation of the layer of adhesive takes place preferably with electromagnetic radiation, more particularly microwave radiation with a wavelength in the 1 mm to 1 m range, preferably from 5 mm to 0.5 m.
Examples of radiation sources are IR lamps, lasers, and radiowave or microwave generators. One preferred radiation source is a microwave concentrator, with which microwaves can be focused, locally concentrated for the site-specific treatment of a workpiece, and/or made useful for the excitation of plasmas. An arrangement for the concentration of microwave energy in a local sphere of action is described in DE 10 2006 034084, for example. Another device for generating microwaves for the treatment of workpieces is described in WO 00/75955. A portable microwave device for local applications is described in JP 08-019620.
In one embodiment of the invention, the packs are filled with the packaging contents before, immediately after or at the same time as the energy-activated adhesive-bonding operation. It is particularly advantageous if the contents for packaging are heat-sensitive or radiation-sensitive and if a microwave concentrator is used as radiation source. Activation of adhesive can then take place within a very short time and in a locally, narrowly confined region, without detrimental effect on heat-sensitive or radiation-sensitive contents of the pack. Sensitive contents are, for example, chocolate, ice cream, fatty or waxy products, pharmaceuticals, cosmetics and similar products.
In one embodiment of the invention, the adhesive composition comprises
Abbreviations used are as follows:
MMA: Methyl methacrylate
BA: Butyl acrylate
AA: Acrylic acid
MAA: Methacrylic acid
aMS: alpha-Methylstyrene
Pluriol: Polyethylene glycol
The Ig G′ values were measured as described above.
Adhesive was applied at 20 g/m2 (solids) to each of two strips of card, and then the two strips were placed against one another, adhesive layer against adhesive layer, under a pressure of 15 g/cm2, and were activated by microwave in such a way as to produce a temperature of 120° C. in the adhesive layer for half a second. The adhesive bond was then left to cool to room temperature, after which the strength of the bond was assessed.
The adhesive-bonding properties were assessed by manually separating the mutually bonded cardboard test pieces at the site of adhesive bonding.
“+” denotes difficult separation at the bonding site, with cardboard fiber extraction
“−” denotes easy separation at the bonding site, without fiber extraction.
The blocking resistance was assessed by means of a test in which the cardboard coated with the adhesive and dried was stored against a second coated cardboard at 40° C. for 3 days under a weight of 2 g/mm2. In this arrangement, the two layers of adhesive were placed against one another.
“+” denotes that, after storage, it was possible to separate the cards from one another without blocking.
“−” denotes adherence of the layers of adhesive to one another (blocking) after storage.
Polymers used are as follows (amounts in parts by weight):
Adhesive compositions in dispersion or solution in water (amounts in parts by weight):
| Number | Date | Country | |
|---|---|---|---|
| 61311410 | Mar 2010 | US |
