WO2011017388A2 - Copolymères en émulsion pour adhésif de joint thermique - Google Patents

Copolymères en émulsion pour adhésif de joint thermique Download PDF

Info

Publication number
WO2011017388A2
WO2011017388A2 PCT/US2010/044333 US2010044333W WO2011017388A2 WO 2011017388 A2 WO2011017388 A2 WO 2011017388A2 US 2010044333 W US2010044333 W US 2010044333W WO 2011017388 A2 WO2011017388 A2 WO 2011017388A2
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
grams
acrylate
waterborne
acrylate copolymer
Prior art date
Application number
PCT/US2010/044333
Other languages
English (en)
Other versions
WO2011017388A3 (fr
Inventor
Shui-Jen Raymond Hsu
Leander H. Bauer
Stephan A. Horvath
Original Assignee
Lubrizol Advanced Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Advanced Materials, Inc. filed Critical Lubrizol Advanced Materials, Inc.
Publication of WO2011017388A2 publication Critical patent/WO2011017388A2/fr
Publication of WO2011017388A3 publication Critical patent/WO2011017388A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • This application relates to waterborne copolymer dispersions having utility as heat seal coatings having good moisture resistance for food packaging and related uses.
  • the copolymer dispersions are the result of a multi-stage (e.g., two- stage) polymerization that produces one rubbery copolymer with a low glass transition temperature and a second hard copolymer with a higher glass transition temperature.
  • Heat seal adhesives for high moisture food and condiments have traditionally been partially crystalline polymers applied from solvent based solutions to the lidding material.
  • the lidding material with applied adhesive is stored until needed to package food or condiments. It is desirable that the adhesive applied to the lidding not adhere to any other portion of the lidding (adjacent lidding, etc.) while stored in warehouses awaiting use (this is referred to as having blocking).
  • the food or condiments are added to a plastic container on a filling line, the lidding material is cut to shape and positioned over the container, the lidding and container are brought together in the presence of a heated platen (typically applied to the outside surface of the lidding) that melts and activates the adhesive (between the lidding and the container) to secure the lidding to the container and seal the package.
  • a heated platen typically applied to the outside surface of the lidding
  • the adhesive needs to have low moisture sensitivity so it does not swell, whiten or otherwise produce a weakened bond between the container and lidding during storage of the food or condiment.
  • the adhesive has to be approved for food and condiment contact as the food or condiment can come into direct contact during shipping, sale, and post sale with the adhesive. When a consumer opens a heat sealed package of food or condiment, they generally prefer that the lidding with the adhesive attached thereto cleanly delaminate from the container and contained food or condiment.
  • U.S. 7,189,461 discloses aqueous based ethylene-vinyl acetate polymers emulsions containing crystalline segments resulting from ethylene linkages are useful in heat seal applications.
  • solvent based partially crystalline polymers provide a distinct melting/softening temperature that can be selected to be a few degrees above the storage temperature of the adhesive prior to use and a few degrees below the heat seal temperature.
  • U.S. 6,368,707 discloses a polymer for a heat-sensitive adhesive sheet comprising a substrate having formed thereon an adhesive layer comprising a polymer "A" having a glass transition temperature of -1O 0 C or below obtained by emulsion-polymerizing alkyl(meth)acrylates and copolymer "B" having a glass transition temperature of 2O 0 C or more and being a water-soluble or water- dispersible copolymer from unsaturated carboxylic acid with other radically polymerizable monomers, wherein part of the entire amount of carboxyl groups in the copolymer are neutralized with a base having a boiling point of HO 0 C or below.
  • U.S. 6,258,887 discloses a multi-stage emulsion-polymer suitable for use in dirt pickup resistant coatings.
  • U.S. 5,385,967 discloses aqueous dispersions for heat-seal applications with a copolymer A having a glass transition of 50-150 0 C and copolymer B with a glass transition of -50 to 5O 0 C and at least one of the two copolymers containing from 3 to 70% by wt. of an ethylenically unsaturated C3-C5 mono- or dicarboxylic acid or the anhydride thereof.
  • the examples of the patent generally showed the high glass transition temperature polymer with high amounts of ethylenically unsaturated C3-C5 mono- or dicarboxylic acid or the anhydride thereof.
  • Such high glass transition temperature polymers with high amounts of carboxylic resins are generally known as support resins and while providing good colloidal stability tend to impart unacceptable moisture sensitivity in applications where exposure to moisture occurs.
  • U.S. 5,306,743 discloses an aqueous synthetic resin dispersion comprising latex particles having an average diameter below 145 or 100 nm consisting of a core material with a glass transition temperature above 6O 0 C and a shell material with a glass transition temperature below 8O 0 C, provided that the glass transition temperature of the shell is at least 20 K below that of the core (indicating a softer shell and harder core).
  • Heat seal adhesive is a broad category of materials. Some heat seal adhesives are applied as a hot fluid adhesive to one or more substrates to form an adhesive bond between two or more substrates. This adhesive type does not need blocking resistance as the adhesive typically is heated immediately before application to two or more substrates and is not stored in contact with several substrates where it may prematurely cause an adhesive bond.
  • a subset of adhesives for seals is those products where an adhesive is applied to one substrate (typically cardboard, paper, or plastic packaging) and the adhesive and substrate is further processed or stored and later during final assembly a substrate near the adhesive is heated above an activation temperature at which temperature the heat seal adhesive then forms a bond between the original substrate and one or more additional substrates. In many cardboard, paper and plastic adhesive uses, the adhesive can have moisture sensitive components without having adhesion adversely affected (because they are used in relatively dry environments where the moisture effect on the adhesive is minimal).
  • This invention discloses a copolymer film for a heat seal adhesive desirably having an estimated interfacial activation temperature between 100 and 200 0 C for forming an adhesive bond, said film comprising a principal copolymer being derived from drying an emulsion copolymer in latex form in water
  • the two principal copolymers in the heat seal adhesive are a soft and a hard acrylate copolymer.
  • the term acrylate copolymer is used understanding that the copolymer can have repeating units from various alkyl acrylates, alkyl methacrylates, and acrylic acid.
  • the acrylic copolymers can include other ethylenically unsaturated monomers such as C3-C10 mono or dicarboxylic acids, allyl methacrylate, vinyl aromatic, vinyl ester, nitrile, vinyl halide, etc.
  • acrylic copolymer is a term used to describe a copolymer with at least 10 or 20 wt. % (more desirably at least 30 or 40 wt. %) repeating units derived from an acrylic or acrylate monomer.
  • alkyl acrylate monomer and/or an alkyl methacrylate monomer is making the copolymers of this invention.
  • These monomers can include alkyl acrylates, alkyl methacrylates, and alkyl ethacrylates.
  • the alkyl group many contain from 1 to 15 carbon atoms and more desirably from 1 to 10 carbon atoms.
  • Desirable acrylates include n-butyl acrylate, n-butyl methacrylate, ethylhexyl acrylate, ethyl acrylate, ethyl
  • the polymer from the multi-step polymerization comprises the various alkyl (meth or eth) acrylates.
  • the use of (meth) or (eth) or (meth or eth) indicates (through out this specification) that the item in parentheses is optionally present.
  • the composition of the soft acrylate copolymer is adjusted so that the Tg (glass transition temperature) is from about -60 to about O 0 C, more desirably from about -50 to about -1O 0 C, and preferably from about -45 to about -30 or -15 0 C.
  • the composition of the hard acrylate copolymer is adjusted so that the Tg is from about 50 to about 12O 0 C, more desirably from about 55 to about HO 0 C, and preferably from about 60 to about 100 0 C.
  • the soft acrylate copolymer be prepared in the first stage of the polymerization and the hard acrylate copolymer be prepared in the second stage of the polymerization, i.e., in the presence of the soft acrylate copolymer. Additional copolymers may be made during the multi-stage polymerization. If they have the appropriate Tg value, the amount of such copolymers can be included in the soft or hard copolymer. If their Tg value falls outside the appropriate Tg range, they will be considered to be neither the soft or hard copolymer.
  • ethylenically unsaturated monomers examples include mono vinyl aromatic monomers, alpha-beta ethylenically-unsaturated carboxylic acid ester monomers, unsaturated monomers with carboxylic acid groups, vinyl ester monomers, and various combinations of these.
  • the acrylate monomers are preferably selected from the group consisting of esters of acrylic and methacrylic acid (e.g., those with 4 to 30 carbon atoms) such as n-butyl (meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, 2-ethylhexyl- (meth)acrylate, cycloalkyl(meth)acrylates, such as isobornyl(meth)acrylate and cyclohexyl(meth)acrylate.
  • Choices among the acrylate monomers are typically made to achieve the preferred glass transition temperatures (Tg) for the soft and hard copolymers.
  • Tg glass transition temperatures
  • Acrylic and methacrylic acid have fairly high Tg values.
  • the vinyl aromatic based monomers include styrene, i.e., styrene or substituted styrenes, for instance alpha-methyl styrene or t-butylstyrene; and vinyltoluene.
  • the diene monomers include dienes such as 1,3-butadiene or isoprene, and mixtures thereof.
  • the ethylenically unsaturated monomers can include vinyl esters with 4 to 25 carbon atoms, such as vinyl acetate, vinyl alkanoate or their derivatives or mixtures thereof can be used in the monomer composition.
  • Nitriles such as (meth)acrylonitrile, or olefmically unsaturated halides, such as vinyl chloride, vinylidene chloride, and vinyl fluoride can also be used.
  • Preferred vinyl ester monomers include vinyl esters of versatic acids such as the monomers commercialized by Hexion Specialty Chemicals under the trade names VEOV A® 9, 10 and 11.
  • Unsaturated monomers with acid (e.g., carboxylic acid) functionality which include monomers of which the acid groups are latent as, for example, in maleic anhydride, are suitably selected from, but not limited to: acrylic acid, methacrylic acid, oligomerized acrylic acids such as beta-carboxyethyl acrylate or its higher analogues (commercially available from Rhodia as SipomerTM B-CEA), itaconic acid, fumaric acid, maleic acid, citraconic acid, or the anhydrides thereof.
  • acid type monomers include styrene p-sulfonic acid, ethylmethacrylate-2- sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid.
  • An acid bearing monomer could be polymerized as the free acid or as a salt, e.g., the NH 4 or alkali metal salts.
  • Monomers with carboxylic acid functionality are preferred over other acid monomers, e.g., sulfonic acid.
  • Other monomers that may be present in amounts up to 5, 10, 15, or 20 weight percent based on the total monomers in the polymers of the multi-stage polymerization include acrylonitriles, vinyl chlorides, vinylidene chlorides, and amide functional monomers.
  • Amide-functional comonomers include, but are not limited to, acrylamide and methacrylamide.
  • polar non-ionic monomers such as hydroxyalkyl (meth)acrylates, (meth)acrylamides and substituted (meth)acrylamides (e.g., N-methyl acrylamide), N-vinyl-2-pyrrolidone, N-vinyl caprolactam, 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (4-hydroxymethylcyclohexyl)-methyl (meth)acrylate, l-(2-((2- hydroxy-3-(2-propenyloxy)propyl)amino)ethyl)-2-imidazolidinone, N-methylol (meth)acrylamide, Sipomer® WAM, WAM II (from Rhodia) and other urido- containing monomers, dimethylaminoethyl (meth)acrylate,
  • polar non-ionic monomers such as hydroxyalkyl (meth)acrylates,
  • dimethylaminopropyl (meth)acrylamide dimethylaminopropyl (meth)acrylamide.
  • Mixtures of polar monomers also may be used.
  • Those hydrophilic monomers should be used at appropriate levels, which do not impair the earlier water resistance.
  • Vinyl aromatic monomers can also be employed as the copolymerizable monomer.
  • the total amount of vinyl aromatic monomers utilized in one embodiment for food contact for making the copolymer of this invention will typically not exceed about 50 weight percent and in another embodiment not to exceed 33 weight percent of the total weight of monomers employed in making the first and second copolymer (total polymers in multi-stage polymerization).
  • a multi-stage emulsion polymerization process usually results in the formation of at least two mutually incompatible polymer compositions, thereby resulting in the formation of at least two phases.
  • the mutual incompatibility of two polymer compositions and the resultant multiphase structure of the polymer particles may be determined in various ways known in the art. The use of scanning electron microscopy using staining techniques to emphasize the difference between the phases.
  • Such particles are composed of two or more phases of various geometries such as, for example, core/shell or core/sheath particles, core/shell particles with shell phases incompletely encapsulating the core, raspberry (three or more nodules per particle) morphology, core/shell particles with a multiplicity of cores, and interpenetrating network particles. It is believed that the morphology of the examples is raspberry rather than core shell.
  • Tg values used herein are those calculated by using the Fox equation; see T. G. Fox, Bull. Am. Physics Soc, Volume 1, Issue No. 3, page 123, (1956).
  • crosslinking monomers are present in the structure of the soft acrylate copolymer in an amount from 0.1 or 0.15 to 3, preferably 0.3 or 0.5 to 2 percent by weight based on the weight of the soft acrylate copolymer.
  • the crosslinking is chosen just high enough so that the extensibility of the copolymer film is only slightly decreased in comparison with that of a corresponding non- crosslinked soft acrylate copolymer, but the resistance to blocking is increased slightly due to the molecular weight increase.
  • the degree of crosslinking is directed toward a particular use. For this purpose, a low content of crosslinking monomer is sufficient. It should be understood that to minimize blocking either crosslinking of the soft acrylate or raising the Tg of the hard acrylate copolymer can impart the desired result.
  • the crosslinking monomers have at least two ethylenically unsaturated, free radically polymerizable groups, suitable groups such as allyl, acryl, or methacryl groups, in the molecule.
  • suitable groups such as allyl, acryl, or methacryl groups
  • Compounds having at least three such groups which may be the same or different, but preferably are the same, are preferred.
  • crosslinking monomers are diol and polyolesters of acrylic acid and/or of methacrylic acid reacted with di- or poly-functional alcohols, such as ethylene glycol diacrylate and dimethacrylate, butylene glycol diacrylate and di methacrylate, dipropylene glycol dimethacrylate, propylene glycol dimethacrylate, pentaerythritol tri- or tetra- acrylate and methacrylate, trimethylolpropane triacrylate and trimethacrylate, and allyl acrylate and methacrylate, divinylbenzene and
  • di- or poly-functional alcohols such as ethylene glycol diacrylate and dimethacrylate, butylene glycol diacrylate and di methacrylate, dipropylene glycol dimethacrylate, propylene glycol dimethacrylate, pentaerythritol tri- or tetra- acrylate and methacrylate, trimethylolpropane tri
  • graft crosslinking monomers which contain at least two ethylenically unsaturated, free radically polymerizable groups, among which is at least one allyl group, are particularly advantageous.
  • Typical anionic emulsifiers include alkali or ammonium alkyl sulfates, alkyl sulfonates, salts of fatty acids, esters of sulfosuccinic acid salts, alkyl diphenylether disulfonates, and the like, and mixtures thereof.
  • Typical nonionic emulsifiers include polyethers, e.g., ethylene oxide and propylene oxide condensates, including straight and branched chain alkyl and alkylaryl polyethylene glycol and polypropylene glycol ethers and thioethers, alkyl phenoxypoly(ethyleneoxy) ethanols having alkyl groups containing from about 7 to about 18 carbon atoms and having from about 4 to about 100 ethyleneoxy units, and polyoxy-alkylene derivatives of hexitol, including sorbitans, sorbides, mannitans, and mannides; and the like, and mixtures thereof.
  • polyethers e.g., ethylene oxide and propylene oxide condensates, including straight and branched chain alkyl and alkylaryl polyethylene glycol and polypropylene glycol ethers and thioethers, alkyl phenoxypoly(ethyleneoxy) ethanols having alkyl groups containing from about 7 to about 18 carbon atoms
  • Preferred surfactants include DextrolTM OC-60, sodium lauryl sulfate, DowfaxTM 2Al, AerosolTM OT, and dodecylbenzene sulfonate.
  • Surfactants approved for food contact are listed in 21 CFR ⁇ 177.1010 Subpart B.
  • Co-surfactants typically are employed in the
  • compositions of the present invention at levels of about 0 wt. % to about 3 wt. %.
  • the emulsion polymerization employed in synthesizing the copolymer(s) of this invention is carried out in a conventional manner using well-known additives and ingredients, such as emulsif ⁇ ers, free radical polymerization initiators, and the like, and mixtures thereof. Either thermal or redox initiation processes may be used.
  • the reaction temperature typically is maintained at a temperature lower than about 100 0 C throughout the course of the reaction. In one embodiment, a reaction temperature between about 25 0 C and 95 0 C is used.
  • pH control agents and buffers typically are added.
  • the initial reactor pH will normally be within the range of about 3 to about 10.
  • suitable pH control agents include but are not limited to ammonium and alkali metal hydroxides (such as sodium hydroxide and potassium hydroxide), and mixtures thereof, and the like.
  • suitable buffers include ammonium carbonate, sodium carbonate, sodium bicarbonate, and mixtures thereof, and the like. pH may be adjusted if desired at the end of the polymerization process according to the desired application.
  • any chain-transfer agent may be used to control molecular weight.
  • Suitable chain transfer agents include, for example, Ci to C12 alkyl or functional alkyl mercaptans, alkyl or functional alkyl mercaptoalkanoates, or halogenated hydrocarbons, and the like, and mixtures thereof. Chain transfer agents typically are employed at levels of about 0.1 weight percent to about 5 weight percent, based on total monomer weight of monomers used in the hard second acrylate copolymer.
  • the copolymers typically are prepared in the presence of water-soluble or organic solvent-soluble initiators (such as persulfates, peroxides, hydroperoxides, percarbonates, peracetates, perbenzoates, azo-functional compounds, and other free- radical generating species, and mixtures thereof, as is well known to those skilled in the art.
  • water-soluble or organic solvent-soluble initiators such as persulfates, peroxides, hydroperoxides, percarbonates, peracetates, perbenzoates, azo-functional compounds, and other free- radical generating species, and mixtures thereof, as is well known to those skilled in the art.
  • the latex formed by the multi-stage emulsion polymerization can optionally be diluted with additional water to any concentration (solids content) that is desired.
  • Multi-stage polymerization is used to indicate that two or more stages can be present.
  • the desirable feature from the multi-stage polymerization is that two or more different copolymer compositions are made such that a) a softer copolymer is present that provides wetting at the heat seal temperature and tack and b) a harder copolymer is present that helps prevent films the latex from adhering to adjacent materials during storage before use.
  • This latex can then be used in the preparation of water based adhesive heat seal coatings employing techniques that are well-known to those skilled in the art.
  • Desired pigments, plasticizers, coalescing solvents, fillers, wetting agents, stabilizers, defoamers, dryers, antibacterial agents, fungicides, insecticides, antifouling agents, and anticorrosive agents can be mixed directly into the latex.
  • Pigments may be added to adhesive formulations to impart color.
  • Titanium dioxide is an example of a widely used pigment which imparts hiding and a white color.
  • Mineral pigments such as oxides of iron and chromium
  • organic pigments such as phthalocyanine
  • active anticorrosive pigments such as zinc phosphate
  • Some representative examples of widely utilized fillers include chalks, clays, micas, barites, talcs, and silica.
  • a film forming, water based composition can be prepared utilizing a mixture of the copolymer with suitable additives, including but not limited to coalescing solvent and plasticizer.
  • suitable additives including but not limited to coalescing solvent and plasticizer.
  • suitable additives including but not limited to coalescing solvent and plasticizer.
  • suitable additives including but not limited to coalescing solvent and plasticizer.
  • suitable additives including but not limited to coalescing solvent and plasticizer.
  • suitable additives including but not limited to coalescing solvent and plasticizer.
  • suitable additives including but not limited to coalescing solvent and plasticizer.
  • the water based heat sealable adhesive composition as an aqueous dispersion or solution, can then be applied as a coating onto a suitable substrate such as plastic, paper, foil, or combinations thereof.
  • a suitable substrate such as plastic, paper, foil, or combinations thereof.
  • the water based heat sealable adhesive compositions of this invention are a particular value for application to lidding or other surfaces of high moisture food or condiment packaging.
  • High moisture food and/or high moisture condiments are particularly taught as many of the heat sealable adhesives for conventional paper, plastic and cardboard packaging is useful for packaging low moisture items such as nuts, cereal, candy, sugar, flour, etc.
  • the water based heat sealable adhesive is desirably applied to at least one surface of the packaging material (e.g. lidding) and allowed to dry to a film.
  • Desirable film thicknesses range from 2 to 50 g/m 2 , more desirably from 3 to 30 g/m 2 , and preferably from about 4 to 15 g/m 2 based on the dried weight of the adhesive per meter squared of surface.
  • the estimated interfacial activation temperature It would be desirable to characterize the interfacial activation temperature that the adhesive experiences at the moment that the two surfaces are adhered together.
  • the estimated interfacial activation temperature It is believed to be between 100 and 200 0 C, more desirably between 120 and 175 0 C, and preferably between 135 and 15O 0 C.
  • the platen temperature useful with the adhesives in the examples below was 163 0 C for 0.75 second of contact with an outer surface of the lidding material. Attempts to measure the adhesive temperature after contact with the heated platen resulted in the estimated temperatures.
  • n-BA n-Butyl acrylate
  • a monomer premix was made by mixing 230 grams of water, 16.67 grams of Dowfax 2Al, 3.33 grams of sodium lauryl sulfate, 1.0 grams of ammonium carbonate, 15 grams of methacrylic acid, 55 grams of methyl methacrylate, 250 grams of styrene, and 380 grams of 2-ethylhexyl acrylate.
  • Initiator A was made by dissolving 2 grams of ammonium persulfate in 23 grams of water.
  • Initiator B was made by dissolving 3 grams of ammonium persulfate in 100 grams of water.
  • a 3- liter reaction vessel was charged as follows: 600 grams of water and 2.22 grams of Dowfax 2Al, and then was heated to 82 0 C under nitrogen.
  • Initiator A was then added to the reaction vessel, followed by proportioning (metered in over a specified time) the monomer premix to the reaction vessel over a period of about 3 hours (a monomer premix feed rate of about 6.95 g/min).
  • the reaction temperature was kept at 86 0 C during polymerization.
  • initiator B was proportioned into the reaction vessel over a period of about 3 hours and 30 minutes.
  • 300 grams of methyl methacrylate was added to the remaining monomer premix. After completion of initiator B feed, the temperature of the reaction vessel was maintained at 86 0 C for 60 minutes.
  • the reaction vessel then was cooled to 57 0 C, and then 5.88 grams of 17% t-butyl hydroperoxide solution was added to the reaction vessel. After about 5 minutes, 35.3 grams of 3.68 % erythorbic acid solution was added to the reaction vessel. After 30 minutes, the addition of 40 wt.% more of t-butyl hydroperoxide solution and erythorbic acid solution was repeated based on the weight of the previous dose. After 30 minutes, the above the reaction vessel was cooled to room temperature and filtered through 100-micron cloth. Table 1 Recipe for Example 1
  • the emulsion copolymer was made exactly same as Example #1, except monomer composition in the monomer premix was 15 grams of methacrylic acid, 55 grams of methyl methacrylate, 150 grams of styrene, and 480 grams of 2-ethylhexyl acrylate. At 110 minutes after premix proportioning started, 300 grams of styrene was added to the remaining monomer premix not methyl methacrylate as shown in Example #1.
  • the emulsion copolymer was made exactly same as Example #1, except monomer composition in the monomer premix was 15 grams of methacrylic acid, 150 grams of methyl methacrylate, 305 grams of styrene, and 180 grams of n-butyl acrylate. At 110 minutes after premix proportioning started, 350 grams of n-butyl acrylate was added to the remaining monomer premix not methyl methacrylate as shown in Example #1.
  • the emulsion copolymer was made exactly same as Example #1, except monomer composition in the monomer premix was 15 grams of methacrylic acid, 150 grams of styrene, and 430 grams of 2-ethylhexyl acrylate. At 90 minutes after premix proportioning started, 250 grams of styrene and 155 grams of methyl methacrylate were added to the remaining monomer premix not methyl methacrylate at 110 minutes as shown in Example #1.
  • a surfactant mixture was made by mixing 230 grams of water, 8.89 grams of Dowfax 2Al, 3.33 grams of sodium lauryl sulfate and 1.0 grams of ammonium carbonate. Then, it was split into two parts, surfactant Part A and B. Surfactant Part A was 173.22 grams, and surfactant Part B was 70 grams. Premix I was made by mixing surfactant Part A, 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 75 grams of styrene, and 550 grams of 2-ethylhexyl acrylate.
  • Premix II was made by mixing surfactant Part B, 5 grams of methacrylic acid, 255 grams of styrene, and 90 grams of 2-ethylhexyl acrylate.
  • Initiator A was made by dissolving 2 grams of ammonium persulfate in 23 grams of water.
  • Initiator B was made by dissolving 3 grams of ammonium persulfate in 100 grams of water.
  • a 3 -liter reaction vessel was charged as follows: 620 grams of water and 1.33 grams of Dowfax 2Al, and then was heated to 82 0 C under nitrogen. Initiator A was then added to the reaction vessel, followed by proportioning the Premix I to the reaction vessel. The reaction temperature was kept at 86 0 C during polymerization.
  • Premix II About 15 minutes after Premix I proportioning was finished, started the proportion of Premix II. Total proportion time for Premix I (66% of time) and Premix II (34% of time) was about 3 hours. At 30 minutes after Premix I proportioning started, initiator B was proportioned into the reaction vessel over a period of about 3 hours and 30 minutes. After completion of initiator B feed, the temperature of the reaction vessel was maintained at 86 0 C for 60 minutes. The reaction vessel then was cooled to 57 0 C, and then 5.88 grams of 17% t-butyl hydroperoxide solution was added to the reaction vessel. After about 5 minutes, 35.3 grams of 3.68% erythorbic acid solution was added to the reaction vessel.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 65 grams of styrene, and 470 grams of 2-ethylhexyl acrylate. Premix II was 5 grams of methacrylic acid, 330 grams of styrene, and 115 grams of 2-ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 65 grams of styrene, and 470 grams of 2-ethylhexyl acrylate. Premix II was 5 grams of methacrylic acid, 330 grams of styrene, 115 grams of 2-ethylhexyl acrylate and 5 grams of n-dodecyl mercaptan.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 130 grams of styrene, and 495 grams of 2-ethylhexyl acrylate.
  • Premix II was 5 grams of methacrylic acid, 255 grams of styrene, 90 grams of 2- ethylhexyl acrylate and 5 grams of n-dodecyl mercaptan.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 58 grams of styrene, and 467 grams of 2-ethylhexyl acrylate. Premix II was 5 grams of methacrylic acid, 330 grams of styrene, and 115 grams of 2-ethylhexyl acrylate.
  • Example #11 The emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 160 grams of styrene, and 465 grams of 2-ethylhexyl acrylate. [0046]
  • monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 160 grams of styrene, and 465 grams of 2-ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 25 grams of methacrylic acid, 10 grams of allyl methacrylate, 65 grams of styrene, and 550 grams of 2-ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that Premix
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 38 grams of styrene, and 587 grams of 2-ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 38 grams of styrene, and 587 grams of 2-ethylhexyl acrylate. Premix II was 5 grams of methacrylic acid, 275 grams of styrene, and 70 grams of 2- ethylhexyl acrylate. [0050]
  • monomer composition in Premix I was 15 grams of methacrylic acid, 10 grams of allyl methacrylate, 38 grams of styrene, and 587 grams of 2-ethylhexyl acrylate.
  • Premix II was 5 grams of methacrylic acid, 275 grams of styrene, and 70 grams of 2- ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 10 grams of methacrylic acid, 10 grams of allyl methacrylate, 80 grams of styrene, and 550 grams of 2-ethylhexyl acrylate.
  • Premix II was 3 grams of methacrylic acid, 258 grams of styrene, and 90 grams of 2- ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix I was 15 grams of acrylic acid, 10 grams of allyl methacrylate, 75 grams of styrene, and 550 grams of 2-ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that
  • Premix I and Premix II were combined together first and then proportioned.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix II was 5 grams of methacrylic acid, 238 grams of styrene, and 110 grams of 2-ethylhexyl acrylate.
  • the emulsion copolymer was made exactly same as Example #5, except that monomer composition in Premix II was 5 grams of methacrylic acid, 174 grams of styrene, 81 grams of methyl methacrylate, and 90 grams of 2-ethylhexyl acrylate.
  • Table 6 Recipes for Monomer Premix for Examples 14-19
  • the following tests were used to evaluate the heat seal adhesive.
  • the water based copolymer dispersion was applied as a film with a dry coating weight of 4.5 to 5.5 g/m 2 and dried at 20-25 0 C (air temperature) on a foiled polyester film for 24 hours/days or in a forced air oven at 75 0 C for 5 minutes.
  • the specimen was mounted face to face or face to back and the specified pressure was applied for the specified time at the specified temperature.
  • the specimen comprise the above heat seal adhesive dried onto a foiled polyester film in contact with sheets of high impact polystyrene (HIPS) that are meant to simulate the sealing surface of HIPS based containers.
  • HIPS high impact polystyrene

Abstract

Cette invention concerne une composition d'adhésif thermoscellable pour des récipients en plastique et en métal pour produits alimentaires à teneur en humidité modérée à élevée. L'adhésif comprend un latex dans de l'eau avec une température minimale de formation de film proche de ou inférieure à 25 °C, une résistance de l'adhérence allant jusqu'à 50 °C, une aptitude à l'adhésion thermique dans des conditions raisonnables, de bonnes propriétés d'adhésion et une homologation pour le contact avec les aliments.
PCT/US2010/044333 2009-08-07 2010-08-04 Copolymères en émulsion pour adhésif de joint thermique WO2011017388A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23205709P 2009-08-07 2009-08-07
US61/232,057 2009-08-07

Publications (2)

Publication Number Publication Date
WO2011017388A2 true WO2011017388A2 (fr) 2011-02-10
WO2011017388A3 WO2011017388A3 (fr) 2011-05-19

Family

ID=43544914

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/044333 WO2011017388A2 (fr) 2009-08-07 2010-08-04 Copolymères en émulsion pour adhésif de joint thermique

Country Status (1)

Country Link
WO (1) WO2011017388A2 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011086372A1 (de) 2011-11-15 2013-05-16 Constantia Hueck Folien Gmbh & Co. Kg Heißsiegellack
DE102012218108A1 (de) 2012-10-04 2014-04-10 Evonik Industries Ag Wässrige Bindemittel für Heißsiegelanwendungen
WO2015119873A1 (fr) * 2014-02-06 2015-08-13 Lubrizol Advanced Materials, Inc. Polymères à base aqueuse pour adhésif thermoscellable
CN105732905A (zh) * 2016-04-12 2016-07-06 华南理工大学 一种树莓状有机/有机复合乳胶粒子及其制备方法
WO2016160249A1 (fr) * 2015-03-31 2016-10-06 Rohm And Haas Company Procédé de fabrication des compositions adhésives sensibles à la pression
WO2019190615A1 (fr) * 2018-03-29 2019-10-03 Dow Global Technologies Llc Compositions de revêtement de thermoscellage antimicrobien
US10620570B2 (en) 2017-04-05 2020-04-14 Hp Indigo B.V. Heat transfer printing
WO2020173876A1 (fr) * 2019-02-28 2020-09-03 Topchim Nv Formulation de revêtement polymère à chaînes latérales hydrophobes
CN112280043A (zh) * 2020-10-30 2021-01-29 三棵树(上海)新材料研究有限公司 一种二氧化硅/聚丙烯酸酯/聚硅氧烷复合乳液、制备方法及其应用
CN114008152A (zh) * 2019-02-28 2022-02-01 索理思比利时有限公司 具有疏水性侧链的聚合物涂料制剂
EP4063412A1 (fr) * 2021-03-24 2022-09-28 FUJIFILM Business Innovation Corp. Procédé de production d'une dispersion de particules de résine composite, procédé de production d'un adhésif sensible à la pression, procédé de production d'une résine sensible à la pression, procédé de production de toner pour le développement d'images à charge électrostatique et dispersion de particules de résine composite
EP4092058A1 (fr) 2021-05-18 2022-11-23 Evonik Operations GmbH Dispersion aqueuse comprenant des particules polymères utiles dans des applications de thermoscellage

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325856A (en) 1980-01-02 1982-04-20 The Dow Chemical Company Sequential emulsion polymerization process
US4654397A (en) 1984-12-01 1987-03-31 Basf Aktiengesellschaft Preparation of polymer dispersions which form block-resistant films
US4814373A (en) 1984-12-20 1989-03-21 Rohm And Haas Company Modified latex polymer composition
US5306743A (en) 1988-12-24 1994-04-26 Rohm Gmbh Multiple phase synthetic resin dispersion
US5385967A (en) 1992-06-16 1995-01-31 Basf Aktiengesellschaft Use of aqueous dispersions as heat-seal adhesives
US6258887B1 (en) 1998-12-08 2001-07-10 Rohm And Haas Company Dirt pickup resistant coating binder and coatings
US6368707B1 (en) 1996-07-19 2002-04-09 Toagosei Co., Ltd. Heat-sensitive adhesive sheet
US7189461B2 (en) 2003-03-04 2007-03-13 Air Products Polymers, L.P. Semi-crystalline ethylene vinyl acetate emulsion polymers for heat seal applications

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4439459A1 (de) * 1994-11-04 1995-05-04 Basf Ag Wäßrige Polymerisatdispersion

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325856A (en) 1980-01-02 1982-04-20 The Dow Chemical Company Sequential emulsion polymerization process
US4654397A (en) 1984-12-01 1987-03-31 Basf Aktiengesellschaft Preparation of polymer dispersions which form block-resistant films
US4814373A (en) 1984-12-20 1989-03-21 Rohm And Haas Company Modified latex polymer composition
US5306743A (en) 1988-12-24 1994-04-26 Rohm Gmbh Multiple phase synthetic resin dispersion
US5385967A (en) 1992-06-16 1995-01-31 Basf Aktiengesellschaft Use of aqueous dispersions as heat-seal adhesives
US6368707B1 (en) 1996-07-19 2002-04-09 Toagosei Co., Ltd. Heat-sensitive adhesive sheet
US6258887B1 (en) 1998-12-08 2001-07-10 Rohm And Haas Company Dirt pickup resistant coating binder and coatings
US7189461B2 (en) 2003-03-04 2007-03-13 Air Products Polymers, L.P. Semi-crystalline ethylene vinyl acetate emulsion polymers for heat seal applications

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T. G. FOX, BULL. AM. PHYSICS SOC., vol. 1, no. 3, 1956, pages 123

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011086372A1 (de) 2011-11-15 2013-05-16 Constantia Hueck Folien Gmbh & Co. Kg Heißsiegellack
DE102012218108A1 (de) 2012-10-04 2014-04-10 Evonik Industries Ag Wässrige Bindemittel für Heißsiegelanwendungen
JP2015535874A (ja) * 2012-10-04 2015-12-17 エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ ヒートシール用途のための水性結合剤
RU2639157C2 (ru) * 2012-10-04 2017-12-20 Эвоник Рём ГмбХ Водное связующее средство для применения в термической сварке
US10227511B2 (en) 2014-02-06 2019-03-12 Lubrizol Advanced Materials, Inc. Waterborne polymers for heat seal adhesive
WO2015119873A1 (fr) * 2014-02-06 2015-08-13 Lubrizol Advanced Materials, Inc. Polymères à base aqueuse pour adhésif thermoscellable
WO2016160249A1 (fr) * 2015-03-31 2016-10-06 Rohm And Haas Company Procédé de fabrication des compositions adhésives sensibles à la pression
CN107429138A (zh) * 2015-03-31 2017-12-01 罗门哈斯公司 制备压敏粘着剂组合物的方法
CN105732905A (zh) * 2016-04-12 2016-07-06 华南理工大学 一种树莓状有机/有机复合乳胶粒子及其制备方法
US10620570B2 (en) 2017-04-05 2020-04-14 Hp Indigo B.V. Heat transfer printing
WO2019190615A1 (fr) * 2018-03-29 2019-10-03 Dow Global Technologies Llc Compositions de revêtement de thermoscellage antimicrobien
WO2020173876A1 (fr) * 2019-02-28 2020-09-03 Topchim Nv Formulation de revêtement polymère à chaînes latérales hydrophobes
CN114008152A (zh) * 2019-02-28 2022-02-01 索理思比利时有限公司 具有疏水性侧链的聚合物涂料制剂
CN112280043A (zh) * 2020-10-30 2021-01-29 三棵树(上海)新材料研究有限公司 一种二氧化硅/聚丙烯酸酯/聚硅氧烷复合乳液、制备方法及其应用
CN112280043B (zh) * 2020-10-30 2022-06-07 三棵树(上海)新材料研究有限公司 一种二氧化硅/聚丙烯酸酯/聚硅氧烷复合乳液、制备方法及其应用
EP4063412A1 (fr) * 2021-03-24 2022-09-28 FUJIFILM Business Innovation Corp. Procédé de production d'une dispersion de particules de résine composite, procédé de production d'un adhésif sensible à la pression, procédé de production d'une résine sensible à la pression, procédé de production de toner pour le développement d'images à charge électrostatique et dispersion de particules de résine composite
EP4092058A1 (fr) 2021-05-18 2022-11-23 Evonik Operations GmbH Dispersion aqueuse comprenant des particules polymères utiles dans des applications de thermoscellage
WO2022243103A1 (fr) 2021-05-18 2022-11-24 Evonik Operations Gmbh Dispersion aqueuse comprenant des particules polymères utiles dans des applications de thermoscellage

Also Published As

Publication number Publication date
WO2011017388A3 (fr) 2011-05-19

Similar Documents

Publication Publication Date Title
US10227511B2 (en) Waterborne polymers for heat seal adhesive
WO2011017388A2 (fr) Copolymères en émulsion pour adhésif de joint thermique
EP1317518B1 (fr) Compositions adhesives comportant des additifs polymeriques de faible poids moleculaire
JP4107618B2 (ja) 水性ポリマー分散液
JP4596546B2 (ja) 水性ポリマー分散物
AU674219B2 (en) Vinylidene chloride emulsion interpolymer composition
US10221343B2 (en) One part, fast-setting, aqueous adhesive emulsions
TWI225087B (en) Adhesive compositions containing graft copolymers
JP2006299260A (ja) 多段エマルジョンポリマーの水性分散物を製造する方法
JPH07507079A (ja) 優れた断裁性能を示す乳化感圧接着性重合体
AU776415B2 (en) Improved polymeric compositions
US20030235685A1 (en) Water-based adhesives
CA2123286C (fr) Acetoacetoxyalkyl(meth)acrylate dans des latex d'acrylique et de styrene et acrylique pour adhesifs de tuiles de ceramique
JPH06172732A (ja) 水性高凝集性感圧性接着剤
JP4683515B2 (ja) 複層塗膜の形成方法
CA2200890A1 (fr) Utilisation d'une dispersion aqueuse comme laque de thermoscellage
JP3794583B2 (ja) 水性樹脂組成物
JP5741838B2 (ja) プラスチック基材用の水性被覆材、これを含有する塗料及びプラスチック成形物
JPH02238078A (ja) 感圧接着済およびシート
US5089335A (en) Crosslinking primer for flexible packaging film
US11685800B2 (en) Multi-stage polymer with low MW shell and high Tg core for early block resistance
JPH08104858A (ja) 木質接着用アクリルエマルション組成物
JP4244733B2 (ja) 車輌カーペット用不織布バインダー用水性樹脂組成物
JPH01153777A (ja) 水性接着剤組成物
JPH07329007A (ja) 突板化粧合板の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10744630

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10744630

Country of ref document: EP

Kind code of ref document: A2