WO2021007847A1 - Acrylic adhesive composition - Google Patents
Acrylic adhesive composition Download PDFInfo
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- WO2021007847A1 WO2021007847A1 PCT/CN2019/096517 CN2019096517W WO2021007847A1 WO 2021007847 A1 WO2021007847 A1 WO 2021007847A1 CN 2019096517 W CN2019096517 W CN 2019096517W WO 2021007847 A1 WO2021007847 A1 WO 2021007847A1
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- acrylate
- adhesive composition
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- sensitive adhesive
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- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- 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
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
Definitions
- the present disclosure relates to an acrylic adhesive composition, in particular an acrylic pressure sensitive adhesive composition.
- PES polyethylene terephthalate
- HDPE high density polyethylene
- PVC polyvinyl chloride
- PP polypropylene
- PSA pressure sensitive adhesive
- the present disclosure provides a novel pressure sensitive adhesive composition that has desirable performances, such as improved adhesion and/or cohesion or balanced adhesion and cohesion.
- the present disclosure provides a pressure sensitive adhesive composition comprising:
- the present disclosure provides a self-adhesive article comprising a backing material and a pressure sensitive adhesive composition comprising:
- composition As disclosed herein, the term “composition” , “formulation” or “mixture” refers to a physical blend of different components, which is obtained by mixing simply different components by a physical means.
- Glass transition temperature (T g ) can be measured by various techniques including, for example, differential scanning calorimetry (DSC) or calculation by using a Fox equation.
- (meth) acryl refers to both “methacryl” and “acryl” .
- (meth) acrylic acid refers to both methacrylic acid and acrylic acid
- methyl (meth) acrylate refers to both methyl methacrylate and methyl acrylate
- (meth) acryamide refers to both methacryamide and acryamide.
- aqueous composition or dispersion herein means that particles dispersed in an aqueous medium.
- aqueous medium herein is meant water and from 0 to 30%, by weight based on the weight of the medium, of water-miscible compound (s) such as, for example, alcohols, glycols, glycol ethers, glycol esters, and the like.
- the present disclosure provides a pressure sensitive adhesive composition
- a pressure sensitive adhesive composition comprising:
- the C 6 -C 10 alkyl acrylate is selected from 2-ethylhexyl acrylate and 2-propylheptyl acrylate. More preferably, the C 6 -C 10 alkyl acrylate is 2-ethylhexyl acrylate.
- the amount of C 6 -C 10 alkyl acrylate (a) in the monomer mixture can be not less than 50%by weight, not less than 60%by weight, not less than 65%by weight, not less than 70%by weight, but not greater than 90%by weight, preferably but not greater than 85%by weight, more preferably but not greater than 80%by weight. More preferably, the amount of C 6 -C 10 alkyl acrylate is 65 to 90%by weight of the monomer mixture.
- the monomer methyl (meth) acrylate (b) can be methyl acrylate, and/or methyl methacrylate.
- the amount of methyl (meth) acrylate (b) in the monomer mixture can be not less than 3%by weight, preferably not less than 4%by weight, more preferably not less than 5%by weight, even more preferably not less than 6%by weight, still more preferably not less than 8%by weight; but not greater than 15%by weight, preferably not greater than 13%by weight, more preferably not greater than 12%by weight, even more preferably not greater than 11%by weight, still more preferably not greater than 10%by weight.
- the ethylenically unsaturated compound having at least one keto or aldehyde group (c) are, for example, acrolein, methacrolein, vinyl alkyl ketones having 1 to 20, preferably 1 to 10, carbon atoms in the alkyl radical, formylstyrene, (meth) acrylic acid alkyl esters having one or two keto or aldehyde or one aldehyde and one keto group in the alkyl radical, said alkyl radical comprising preferably, in total, 3 to 10 carbon atoms, examples being (meth) acryloyloxyalkylpropanals, as described in DE-A 2 722 097.
- N-oxoalkyl (meth) acrylamides such as are known, for example, from U.S. Pat. No. 4,228,007, DE-A 2 061 213 or DE-A 2 207 209.
- acetoacetyl (meth) acrylate acetoacetoxyethyl (meth) acrylate and, in particular, diacetone acrylamide (DAAM) .
- DAAM diacetone acrylamide
- the amount of monomers (c) in the monomer mixture is 0.1 to 5%by weight, preferably 0.1 to 2%by weight and more preferably 0.2 to 1%by weight.
- the ethylenically unsaturated acid (d) can be a sulfonic acid, phosphoric acid or, preferably, carboxylic acid. Suitable examples include maleic acid, fumaric acid and itaconic acid or, preferably, acrylic and/or methacrylic acid. Preferably, the ethylenically unsaturated acid (d) is acrylic acid.
- the amount of ethylenically unsaturated acid (d) in the monomer mixture can be not less than 0.1%by weight, preferably not less than 0.15%by weight, more preferably not less than 0.20%by weight, even more preferably not less than 0.25%by weight, but not greater than 5%by weight, preferably not greater than 4%by weight, more preferably not greater than 3%by weight, even more preferably not greater than 2%by weight, still more preferably not greater than 1%by weight.
- the other ethylenically unsaturated monomers (e) can be of any kind. Suitable examples include C 1 to C 18 alkyl (meth) acrylate other than monomer (a) or monomer (b) , (meth) acryamide, vinyl aromatic compounds or a phosphorous functional monomer. Preferred examples of C 1 to C 18 alkyl (meth) acrylate other than monomer (a) or monomer (b) include ethyl acrylate, n-butyl acrylate and n-butyl methacrylate. Preferred examples of vinyl aromatic compounds include styrene and alpha-methylstyrene.
- the amount of ethyl acrylate can be 10 to 30%by weight.
- the amount of ethyl acrylate in the monomer mixture can be not less than 10%by weight, not less than 12%by weight, not less than 15%by weight, not less than 16 %by weight, but not greater than 30%by weight, preferably but not greater than 25%by weight, more preferably but not greater than 20%by weight. More preferably, the amount of ethyl acrylate is 15 to 20%by weight.
- the amount of the phosphorous functional monomer can be 0.01 to 2%by weight.
- the amount of phosphorous functional monomer in the monomer mixture can be not less than 0.02%by weight, not less than 0.04%by weight, not less than 0.06%by weight, not less than 0.08 %by weight, but not greater than 2%by weight, preferably but not greater than 1%by weight, more preferably but not greater than 0.5%by weight, more preferably but not greater than 0.3%by weight. More preferably, the amount of phosphorous functional monomer is 0.06 to 0.3%by weight.
- the amount of (meth) acryamide can be not less than 0.01%by weight, preferably not less than 0.05%by weight, more preferably not less than 0.10%by weight, even more preferably not less than 0.15%by weight, but not greater than 4%by weight, preferably not greater than 3%by weight, more preferably not greater than 2%by weight, even more preferably not greater than 1%by weight, still more preferably not greater than 0.5%by weight.
- the polymer A) is prepared by emulsion polymerization, and is therefore an emulsion polymer.
- a suitable surfactant system and/or protective colloids, or stabilizer is used.
- Suitable surfactant systems are those known in the art and include anionic, nonionic, cationic, or amphoteric emulsifiers and mixtures thereof.
- anionic surfactants include, but are not limited to, alkyl sulfates, sulfates of ethoxylate alcohols, aryl sulfonates, phosphates of ethoxylated alcohols, sulfosuccinates, sulfates and sulfonates of ethoxylated alkylphenols, and mixtures thereof.
- nonionic surfactants include, but are not limited to, ethoxylated alcohols, ethoxylated alkylphenols, and mixtures thereof.
- cationic surfactants include, but are not limited to, ethoxylated fatty amines.
- the typical weight of surfactant is 0.1 to 5.0 wt. %and more preferably 0.3 to 5.0 wt. %and most preferably 0.5 to 3.0 wt. %based on total weight of monomers.
- the surfactants are utilized by conventional methods that are well known in art.
- the process to prepare the PSA includes the emulsification of the monomer mix with the surfactant system prior to the polymerization reaction.
- surfactant trade names are A-102, FES 77, Dowfax TM 2A1, 2535 and DS-4.
- Water-soluble initiators for the emulsion polymerization are, for example, ammonium salts and alkali metal salts of peroxodisulfuric acid, e.g., sodium peroxodisulfate, ammonium persulfate, hydrogen peroxide, or organic peroxides, e.g., tert-butyl hydroperoxide.
- peroxodisulfuric acid e.g., sodium peroxodisulfate, ammonium persulfate, hydrogen peroxide, or organic peroxides, e.g., tert-butyl hydroperoxide.
- redox reduction-oxidation
- the redox initiator systems are composed of at least one, usually inorganic reducing agent and one organic or inorganic oxidizing agent.
- the oxidizing component comprises, for example, the emulsion polymerization initiators already mentioned above.
- the reducing component comprises, for example, alkali metal salts of sulfurous acid, such as sodium sulfite, sodium hydrogen sulfite, alkali metal salts of disulfurous acid such as sodium disulfite, bisulfite addition compounds with aliphatic aldehydes and ketones, such as acetone bisulfite, or reducing agents such as hydroxymethanesulfinic acid and its salts, or ascorbic acid.
- the redox initiator systems may be used together with soluble metal compounds whose metallic component is able to exist in a plurality of valence states.
- customary redox initiator systems include ascorbic acid/iron (II) sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium disulfite, and tert-butyl hydroperoxide/Na hydroxymethanesulfinate.
- the individual components, the reducing component for example, may also be mixtures: for example, a mixture of the sodium salt of hydroxymethanesulfinic acid with sodium disulfite.
- concentration is generally from 0.1 to 30%by weight, preferably from 0.5 to 20%by weight, with particular preference from 1.0 to 10%by weight, based on the solution.
- the amount of the initiators is generally from 0.1 to 10%by weight, preferably from 0.3 to 5%by weight, based on the monomers to be polymerized. It is also possible for two or more different initiators to be used for the emulsion polymerization.
- the emulsion polymerization takes place in general at from 30 to 130°C., preferably from 60 to 95°C.
- the polymerization medium may be composed either of water alone or of mixtures of water and water-miscible liquids such as methanol. Preferably, only water is used.
- the emulsion polymerization may be conducted either as a batch operation or in the form of a feed process, including staged or gradient procedures.
- the manner in which the initiator is added to the polymerization vessel in the course of the free-radical aqueous emulsion polymerization is known to the skilled worker. It may either be included in its entirety in the initial charge to the polymerization vessel or else introduced, continuously or in stages, at the rate at which it is consumed in the course of the free-radical aqueous emulsion polymerization. In each specific case this will depend both on the chemical nature of the initiator system and on the polymerization temperature. It is preferred to include one portion in the initial charge and to supply the remainder to the polymerization zone at the rate at which it is consumed.
- initiator In order to remove the residual monomers, it is common to add initiator after the end of the actual emulsion polymerization as well, i.e., after a monomer conversion of at least 95%.
- the individual components can be added to the reactor from the top, through the side, or from below, through the reactor floor.
- aqueous polymer dispersions with solids contents of generally from 15 to 75%by weight, preferably from 40 to 75%by weight, are obtained.
- dispersions with as high as possible a solids content are preferred.
- a bimodal or polymodal particle size ought to be set, since otherwise the viscosity becomes too high and the dispersion can no longer be handled.
- Producing a new generation of particles can be done, for example, by adding seed (EP 81083) , by adding excess quantities of emulsifier, or by adding miniemulsions.
- Another advantage associated with the low viscosity at high solids content is the improved coating behavior at high solids contents.
- One or more new generations of particles can be produced at any point in time. It is guided by the particle size distribution which is targeted for a low viscosity.
- the polymer thus prepared is used preferably in the form of its aqueous dispersion.
- the pH of the polymer dispersion is preferably adjusted to a pH of more than 4.5, and in particular to a pH of between 5 and 9.
- the glass transition temperature of the polymer, or of the polymer is preferably from -60 to -30°C, with particular preference from -55 to -30°C, and with very particular preference from -50 to -35°C.
- the glass transition temperature can be determined by customary methods such as differential thermoanalysis or differential scanning calorimetry (see, for example, ASTM 3418/82, midpoint temperature) .
- Compound B) is a polyhydrazide compound having at least two hydrazide functional groups.
- polyhydrazide compounds include, but are not limited to, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide; adipic acid dihydrazide, sebacic acid dihydrazide; monoolefin unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; carbonic acid 10 polyhydrazide such as carbonic acid dihydrazide; aromatic dihydrazides such as phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide; trihydrazides such as 1, 2, 4-butanetricarbohydrazide, 1, 1, 4-butanetricarbohydrazide, 1, 2,
- the polyhydrazide includes adipic dihydrazide, isophthalic dihydrazide, sebacic dihydrazide, bis-semicarbizides, and mixtures thereof. In another embodiment, the polyhydrazide is adipic acid dihydrazide.
- the effective amount of the polyhydrazide crosslinker is such that the ratio of hydrazine functionality is between about 0.02 and about 5 equivalents per 1 equivalent of the ketone or aldehyde functionality of the ethylenically unsaturated compound having at least one keto or aldehyde group, or between about 0.1 and about 3 equivalents per 1 equivalent of the ketone or aldehyde functionality of the ethylenically unsaturated compound having at least one keto or aldehyde group or between about 0.2 and about 1 equivalents per 1 equivalent of the ketone or aldehyde functionality of the ethylenically unsaturated compound having at least one keto or aldehyde group.
- the polyhydrazide compound B) can be added at any point in the process. In one embodiment, it is added after the emulsion reaction.
- the weight fraction of B) is preferably 0.05 to 2, in particular 0.05 to 1, and very preferably 0.1 to 0.7 part by weight per 100 parts by weight of polymer A) , more preferably 0.1 to 0.3 part by weight per 100 parts by weight of polymer A) .
- Polymer A) or the aqueous dispersion of the polymer, can be mixed in a simple way with compound B) .
- the resulting mixture is stable on storage.
- PSAs pressure sensitive adhesives
- the pressure sensitive adhesives may be composed solely of the polymer or of the aqueous dispersion of the polymer A) and compound B) .
- the PSAs may comprise further additives: a thickener, a defoamer, a wetting agent, a mechanical stabilizer, a pigment, a filler, a freeze-thaw agent, a neutralizing agent, a plasticizer, a tackifier (tackifying resin) , an adhesion promoter, and combinations thereof.
- tackifiers are natural resins, such as rosins and their derivatives formed by disproportionation or isomerization, polymerization, dimerization and/or hydrogenation. They 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.
- hydrocarbon resins e.g. non-hydrogenated aliphatic C5 resins, hydrogenated aliphatic C5 resins, aromatic modified C5 resins, terpene resins, hydrogenated C9 resins, and combinations thereof.
- polyacrylates which have a low molar weight. These polyacrylates preferably have a weight-average molecular weight MW of less than 30,000. With preference the polyacrylates are composed of at least 60%by weight, in particular 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 its derivatives.
- the amount by weight of tackifiers is preferably from 5 to 100 parts by weight, with particular preference from 10 to 50 parts by weight, per 100 parts by weight of polymer (solids/solids) .
- the PSAs may comprise 0 to 5 percent by weight of a thickener, based on the total weight of the adhesive composition. All individual values and subranges from 0 to 5 percent by weight are included herein and disclosed herein.
- the wt%of the neutralizing agent can be from a lower limit of 0, 0.5, or 1 percent by weight to an upper limit of 1, 3, or 5 percent by weight.
- Example thickeners include, but are not limited to, ACRYSOL TM , UCAR TM and CELOSIZE TM which are commercially available from The Dow Chemical Company, Midland, Michigan.
- the PSAs may comprise 0 to 2 percent by weight of a neutralizing agent, based on the total weight of the adhesive composition. All individual values and subranges from 0 to 2 percent by weight are included herein and disclosed herein.
- the wt%of the neutralizing agent can be from a lower limit of 0, 0.3, or 0.5 percent by weight to an upper limit of 0.5, 1, or 2 percent by weight.
- Neutralizing agents are typically used to control pH to provide stability to the formulated pressure sensitive adhesive composition. Examples of the neutralizing agent include, but are not limited to, aqueous ammonia, aqueous amines, and other aqueous inorganic salts.
- the PSAs are used for producing self-adhesive articles, such as labels, adhesive tapes or adhesive sheets, e.g., protective films.
- the self-adhesive articles are generally composed of a backing with a layer of the adhesive applied to one or both sides, preferably to one side.
- the backing material may comprise, for example, paper, metal foils, polymer films preferably made of polyolefins including polyethylene and polypropylene which can be biaxially or monoaxially oriented, polyethylene terephthalate (PET) , polyvinyl chloride (PVC) , polystyrene or polyamide.
- PET polyethylene terephthalate
- PVC polyvinyl chloride
- polystyrene or polyamide polystyrene or polyamide.
- the present disclosure provides a self-adhesive article comprising a backing material and a pressure sensitive adhesive composition disclosed herein.
- the backing material can be coated conventionally.
- Customary application rates are, for example, 5 to 50 g/m 2 (solids, without water) .
- coated substrates comprised are used, for example, as self-adhesive articles, such as labels, adhesive tapes or sheets, e.g., protective films.
- the PSA-coated side of the substrate for example the labels, can be covered with a release paper, such as with a siliconized paper.
- the self-adhesive articles of the invention have good performance properties, in particular, improved adhesion and cohesion and/or an improved adhesion/cohesion balance.
- the emulsion mixture according to the disclosure is prepared as follows.
- a four liter, five-neck reactor equipped with a condenser, a mechanical stirrer, a temperature-controlled thermal couple and inlets for initiators and monomers, is fed with 675 g of deionized ( “DI” ) water and heated to 88 °C under a gentle N 2 flow.
- DI deionized
- a monomer emulsion is prepared by mixing 275 g of DI water, 10 g of RHODACAL DS-4, 12 g of AEROSOL A-102, 2.5 g of Na 2 CO 3 , and 1,672 g of a monomer mixture comprising at least one of 2-ethylhexyl acrylate ( “2-EHA” ) , butyl acrylate ( “BA” ) , ethyl acrylate ( “EA” ) , methyl methacrylate ( “MMA” ) , acrylic acid ( “AA” ) , AM, PEM, and DAAM.
- a solution of a mixture of Na 2 CO 3 and ammonium persulfate ( “APS” ) in 40 g DI water is added into the reactor.
- the monomer emulsion is fed into the reactor. The feeding proceeds for 80 minutes.
- the reaction mixture Upon completion of the monomer emulsion addition, the reaction mixture is cooled to 60°C before gradual addition of a solution of tert-butyl hydroperoxide (70%) ( “t-BHP” ) (9.2 g in 32 g DI water) and 6.8 g of a reducing agent, such as BRUGGOLITE FF6 M from Brüggemann Chemical US Company, Chadds Ford, Pennsylvania ( “FF6” ) , in 34.5 g DI water, via two separate pipes over 30 minutes.
- a solution of tert-butyl hydroperoxide (70%) 9.2 g in 32 g DI water
- 6.8 g of a reducing agent such as BRUGGOLITE FF6 M from Brüggemann Chemical US Company, Chadds Ford, Pennsylvania ( “FF6” )
- a wetting agent such as 0.3% (wet/wet) Surfynol 420 wetting agent obtained from Evonik Industries ( “420” ) , based on total emulsion, to improve wet-out for lab drawdowns unless otherwise specified. ADH was also added. The viscosity is then adjusted to about 600 cps (Brookfield, RVDV, 30 rpm, 63#) using a thickener, such as ACRYSOL RM-2020 from The Dow Chemical Company, Midland, Michigan ( “RM-2020” ) , and final pH is adjusted to 7.0 ⁇ 7.5 using ammonia.
- a wetting agent such as 0.3% (wet/wet) Surfynol 420 wetting agent obtained from Evonik Industries ( “420” ) , based on total emulsion, to improve wet-out for lab drawdowns unless otherwise specified. ADH was also added. The viscosity is then adjusted to about 600 cps (Brookfield, RVDV, 30 rpm
- Polypropylene ( “PP” ) film (60micrometer in thickness) is pre-treated by corona treatment before lamination.
- the formulated adhesive is coated to a release liner in an amount of 17 g/m 2 on dry weight basis and dried at 105 °C for 2 minutes.
- the PE film is laminated with the pressure sensitive adhesive coated release liner at 40°C under 40 psi pressure.
- Performance testing can be conducted after the adhesive laminate is conditioned in a controlled environment (22–24 °C, 50–60%relative humidity) testing laboratory for 5 days.
- Peel Strength Test FINAT Test Method No. 1 was followed for peel strength test at 90° on both glass and high density polyethylene (HDPE) test plates. Before testing, the sample strip (formulated without wax) was applied to test plate for dwell time of 20 minutes and one day.
- HDPE high density polyethylene
- Cohesion/Shear Test FINAT Test Method No. 8 is used for the shear resistance test on glass test plates.
- Tg will be too high. If the MMA content in the monomer mixture is too high, the Tg will be very high. An increase in Tg will lead to a stiffer polymer, decreased wettability, and most likely a decline in adhesive properties. Too high Tg polymer doesn’ t possess sufficient conformability to exhibit adequate pressure-sensitive adhesion, especially on low surface energy surface.
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Abstract
Description
Claims (11)
- A pressure sensitive adhesive composition comprising:A) a polymer polymerized from a monomer mixture comprising(a) 40-90 wt%of C 6-C 10 alkyl acrylate;(b) 3-15 wt%of methyl (meth) acrylate;(c) 0.1-5 wt%of an ethylenically unsaturated compound having at least one keto or aldehyde group;(d) 0-2 wt%of an ethylenically unsaturated acid;(e) 0-30wt%of other ethylenically unsaturated monomers;wherein the percentages are based on the total weight of the monomer mixture;and B) a polyhydrazide compound having at least two hydrazide functional groups which react with the keto or aldehyde groups by a crosslinking reaction.
- The pressure sensitive adhesive composition of claim 1, wherein the amount of C 6-C 10 alkyl acrylate in the monomer mixture is 65 to 90%by weight.
- The pressure sensitive adhesive composition of claim 1, wherein the C 6-C 10 alkyl acrylate is selected from the group consisting of 2-ethylhexyl acrylate and 2-propylheptyl acrylate.
- The pressure sensitive adhesive composition of claim 1, wherein the ethylenically unsaturated compound having at least one keto or aldehyde group is selected from the group consisting of acetoacetyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate and diacetone acrylamide.
- The pressure sensitive adhesive composition of claim 1, wherein the amount of ethylenically unsaturated compound having at least one keto or aldehyde group in the monomer mixture is 0.1 to 2%by weight.
- The pressure sensitive adhesive composition of claim 1, wherein the other ethylenically unsaturated monomers (e) is selected from the group consisting of ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, (meth) acryamide, vinyl aromatic compounds and a phosphorous functional monomer.
- The pressure sensitive adhesive composition of claim 1, wherein the ethylenically unsaturated acid is selected from the group consisting of a sulfonic acid, phosphoric acid and carboxylic acid.
- The pressure sensitive adhesive composition of claim 1, wherein the polyhydrazide compound having at least two hydrazide functional groups which react with the keto or aldehyde groups by a crosslinking reaction is oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide; adipic acid dihydrazide, sebacic acid dihydrazide; monoolefin unsaturated dicarboxylic acid dihydrazide; carbonic acid 10 polyhydrazide; aromatic dihydrazides; trihydrazides, and mixtures or any subsets thereof.
- The pressure sensitive adhesive composition of claim 1, wherein the amount of the polyhydrazide crosslinker is such that the ratio of hydrazine functionality is between about 0.02 and about 5 equivalents per 1 equivalent of the ketone or aldehyde functionality of the ethylenically unsaturated compound having at least one keto or aldehyde group.
- A self-adhesive article comprising a backing material and a pressure sensitive adhesive composition according to any one of claims 1-9.
- The self-adhesive article of claim 10, wherein the backing material is paper, metal foil or polymer films.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19937423.2A EP3999606A4 (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
PCT/CN2019/096517 WO2021007847A1 (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
CN201980098187.4A CN114072477B (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
MX2022000241A MX2022000241A (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition. |
BR112022000084A BR112022000084A2 (en) | 2019-07-18 | 2019-07-18 | Pressure sensitive adhesive composition and self-adhesive article |
JP2022502164A JP2022546911A (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
US17/597,422 US20220282134A1 (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
TW109120085A TW202104502A (en) | 2019-07-18 | 2020-06-15 | Acrylic adhesive composition |
ARP200101851A AR119316A1 (en) | 2019-07-18 | 2020-06-30 | ACRYLIC ADHESIVE COMPOSITION |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2019/096517 WO2021007847A1 (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021007847A1 true WO2021007847A1 (en) | 2021-01-21 |
Family
ID=74209639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2019/096517 WO2021007847A1 (en) | 2019-07-18 | 2019-07-18 | Acrylic adhesive composition |
Country Status (9)
Country | Link |
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US (1) | US20220282134A1 (en) |
EP (1) | EP3999606A4 (en) |
JP (1) | JP2022546911A (en) |
CN (1) | CN114072477B (en) |
AR (1) | AR119316A1 (en) |
BR (1) | BR112022000084A2 (en) |
MX (1) | MX2022000241A (en) |
TW (1) | TW202104502A (en) |
WO (1) | WO2021007847A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023144446A1 (en) * | 2022-01-28 | 2023-08-03 | Upm Raflatac Oy | Wash-off label |
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CN105408437A (en) * | 2013-05-21 | 2016-03-16 | 巴斯夫欧洲公司 | Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films |
CN107043607A (en) * | 2016-02-08 | 2017-08-15 | 巴斯夫欧洲公司 | Adhesive dispersion is used for the laminated purposes of high gloss films |
WO2017216108A1 (en) * | 2016-06-17 | 2017-12-21 | Basf Se | Pressure sensitive adhesive and the removable articles |
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JPH06158010A (en) * | 1992-11-19 | 1994-06-07 | Mitsubishi Yuka Badische Co Ltd | Water-base hardenable pressure-sensitive adhesive composition |
EP1546280A1 (en) * | 2002-09-26 | 2005-06-29 | Surface Specialties, S.A. | Removable, water-whitening resistant pressure sensitive adhesives |
JP4507610B2 (en) * | 2003-02-28 | 2010-07-21 | Dic株式会社 | Re-peelable water-based pressure-sensitive adhesive composition and pressure-sensitive adhesive product |
JP5348875B2 (en) * | 2007-12-10 | 2013-11-20 | 日本合成化学工業株式会社 | Peelable aqueous pressure-sensitive adhesive composition, peelable pressure-sensitive adhesive, and curing pressure-sensitive adhesive sheet or tape using the same |
US9472126B2 (en) * | 2014-10-24 | 2016-10-18 | Synthomer Usa Llc | Pressure sensitive adhesive compositons |
-
2019
- 2019-07-18 BR BR112022000084A patent/BR112022000084A2/en unknown
- 2019-07-18 JP JP2022502164A patent/JP2022546911A/en active Pending
- 2019-07-18 EP EP19937423.2A patent/EP3999606A4/en active Pending
- 2019-07-18 CN CN201980098187.4A patent/CN114072477B/en active Active
- 2019-07-18 WO PCT/CN2019/096517 patent/WO2021007847A1/en unknown
- 2019-07-18 MX MX2022000241A patent/MX2022000241A/en unknown
- 2019-07-18 US US17/597,422 patent/US20220282134A1/en active Pending
-
2020
- 2020-06-15 TW TW109120085A patent/TW202104502A/en unknown
- 2020-06-30 AR ARP200101851A patent/AR119316A1/en active IP Right Grant
Patent Citations (4)
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CN101080472A (en) * | 2004-12-17 | 2007-11-28 | 巴斯福股份公司 | Cross-linkable pressure-sensitive adhesive for detachable soft PVC supports |
CN105408437A (en) * | 2013-05-21 | 2016-03-16 | 巴斯夫欧洲公司 | Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films |
CN107043607A (en) * | 2016-02-08 | 2017-08-15 | 巴斯夫欧洲公司 | Adhesive dispersion is used for the laminated purposes of high gloss films |
WO2017216108A1 (en) * | 2016-06-17 | 2017-12-21 | Basf Se | Pressure sensitive adhesive and the removable articles |
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WO2023144446A1 (en) * | 2022-01-28 | 2023-08-03 | Upm Raflatac Oy | Wash-off label |
Also Published As
Publication number | Publication date |
---|---|
AR119316A1 (en) | 2021-12-09 |
MX2022000241A (en) | 2022-01-31 |
JP2022546911A (en) | 2022-11-10 |
TW202104502A (en) | 2021-02-01 |
US20220282134A1 (en) | 2022-09-08 |
CN114072477A (en) | 2022-02-18 |
EP3999606A1 (en) | 2022-05-25 |
EP3999606A4 (en) | 2023-04-26 |
BR112022000084A2 (en) | 2022-02-22 |
CN114072477B (en) | 2024-04-16 |
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