EP1716213A1 - Resines donnant du collant a base de monomere acrylate et de monomere aromatique - Google Patents

Resines donnant du collant a base de monomere acrylate et de monomere aromatique

Info

Publication number
EP1716213A1
EP1716213A1 EP05713421A EP05713421A EP1716213A1 EP 1716213 A1 EP1716213 A1 EP 1716213A1 EP 05713421 A EP05713421 A EP 05713421A EP 05713421 A EP05713421 A EP 05713421A EP 1716213 A1 EP1716213 A1 EP 1716213A1
Authority
EP
European Patent Office
Prior art keywords
tackifier resin
acrylate
monomer
methacrylate
tackifier
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05713421A
Other languages
German (de)
English (en)
Inventor
Michel Hendrikus Theelen
Derek William Bamborough
Elisabeth Eduarda Catharina Geertruida Gielens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
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
Priority claimed from US10/780,989 external-priority patent/US7262242B2/en
Priority claimed from US10/780,987 external-priority patent/US7332540B2/en
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP1716213A1 publication Critical patent/EP1716213A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/38—Steam distillation
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C09J125/14—Copolymers of styrene with unsaturated esters
    • 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
    • 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
    • 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

Definitions

  • This invention is related to the field of tackifier resins. More specifically, this invention is related to the field of tackifier resins having repeating units from at least one aromatic monomer and at least one acrylate monomer. The invention is also related to the field of processes to produce these tackifier resins.
  • BACKGROUND OF THE INVENTION Tackifying resins are used to modify various types of adhesive compositions.
  • Traditional tackifier resins include, for example, rosins, rosin esters, colophonium-based resins, C5 and C 9 based hydrocarbon resins, terpene based resins, coumarone and indene-based resins, and phenolic resins.
  • tackifiers are used to produce, for example, pressure- sensitive adhesives and hot-melt adhesives. Many of these commercial tackifier resins cannot be used in certain applications. For example, in medical applications, some tackifiers cannot be utilized due to skin sensitivity concerns. The medical adhesive industry has a perception that rosins and rosin esters can cause skin sensitivity, therefore, rosins and rosins esters may not be used in this application. In addition, tackifier resins used in many adhesive applications need to be clear and to not cause fogging. Also, tackifier resins may also need to not inhibit the breathability of an adhesive composition as indicated by the moisture vapor transport rate of the adhesive composition after the tackifier resin is added.
  • tackifier resin that can provide needed properties for an adhesive manufacturer including at least one of the following: low residual monomer concentration, low residual solvent concentration, low skin sensitivity, clarity, low fogging, and improved moisture vapor transport rate of the adhesive composition.
  • a tackifier resin comprising monomer units from at least one aromatic monomer and at least one acrylate monomer; wherein the tackifier resin has a styrene-acrylate tackifier resin.
  • a tackifier resin comprising repeating units of at least one aromatic monomer and at least one acrylate monomer; wherein the tackifier resin does not significantly decrease the moisture vapor transport rate of an adhesive composition comprising the tackifier resin.
  • a tackifier resin is provided comprising repeating units of at least one aromatic monomer and at least one acrylate monomer; wherein the tackifier resin does not significantly increase fogging of an adhesive composition comprising the tackifier resin.
  • a tackifier resin comprising repeating units of at least one aromatic monomer and at least one acrylate monomer; wherein the tackifier resin does not significantly exhibit skin sensitivity properties.
  • a process to produce the tackifier resin is provided. The process comprises: contacting a tackifier resin product stream with at least one carrier at a temperature sufficient to remove a portion of at least one residual monomer from the tackifier resin product stream to produce the tackifier resin. ln accordance with another embodiment of this invention, a process to produce a tackifier resin is provided.
  • the process comprises: a) providing at least one aromatic monomer, at least one acrylate monomer, and optionally, at least one solvent to a reactor zone to produce a reaction mixture; b) polymerizing the reaction mixture in the presence of at least one initiator to produce a tackifier resin product stream; and c) contacting the tackifier resin product stream with a carrier to remove a portion of at least one residual monomer from the tackifier resin product stream to yield the tackifier resin.
  • a process to produce a tackifier resin is provided.
  • the process comprises: a) providing at least one aromatic monomer, at least one acrylate monomer, and optionally at least one solvent to a reactor zone to produce a reaction mixture; b) polymerizing the reaction mixture in the presence of at least one initiator to produce a tackifier resin product stream; c) heating the tackifier resin product stream at a temperature sufficient to remove a portion of at least one residual monomer from the tackifier resin product stream; and d) contacting the tackifier resin product stream with at least one carrier to further remove a portion the residual monomers to produce the tackifier resin.
  • an adhesive composition comprising the tackifier resin is also provided.
  • a tackifier resin comprising repeating units of at least one aromatic monomer and at least one acrylate monomer; wherein the tackifier resin has a styrene-acrylate tackifier resin.
  • the aromatic monomer can be any aromatic monomer known in the art capable of polymerizing with at least one acrylate monomer.
  • aromatic monomer means a monomer containing at least one group of unsaturated cyclic hydrocarbons containing one or more rings.
  • aromatic monomers include, but are not limited to, olefinic substituted aromatics, such as, styrene, alpha-methyl styrene, vinyl toluene, indene, methylindenes, divinylbenzene, dicyclopentadiene, and methyl-dicyclopentadiene. Most preferably, the aromatic monomer is styrene.
  • the aromatic monomer can be added to a reactor zone in the polymerization process as a single type of monomer or a mixture and can be added in varying amounts and at varying addition times during the polymerization.
  • the acrylate monomer is any acrylate monomer known in the art capable of polymerizing with the aromatic monomer.
  • the acrylate monomer can be added to a reactor zone in the polymerization process as a single type of monomer or as a mixture and can be added in varying amounts and at varying addition times during the polymerization.
  • the acrylate monomer has the general formula:
  • Ri is selected from the group consisting of hydrogen, aliphatic groups, and aromatic groups
  • R 2 is selected from the group consisting of hydrogen, aliphatic groups, and aromatic groups
  • R 3 is selected from the group consisting of hydrogen, aliphatic groups, aromatic groups.
  • aliphatic is defined as a straight or branched chain arrangement of constituent carbon atoms and includes, but is not limited to, alkanes, alkenes, alkadienes, and alkynes.
  • the aliphatic groups can contain functional groups, such as, but not limited to, hydroxyl, cycloaliphatic, acid, epoxide, amide, acrylonitril and acrylate.
  • the aliphatic group has 1 to about 20 carbon atoms, more preferably, from 1 to 12.
  • aromatic group means at least one group of unsaturated cyclic hydrocarbons containing one or more rings.
  • Aromatic groups can be selected from the group consisting of both unsubstituted and substituted aromatic groups having constituents with up to about 6 carbon atoms.
  • the aromatic group has about 6 to about 20 carbon atoms.
  • the aromatic groups can contain functional groups, such as, but not limited to, hydroxyl, cycloaliphatic, acid, epoxide, amide, acrylonitril and acrylate.
  • these functional groups can lead to an acrylate monomer that has more than one reactive site for polymerization or other reactions.
  • both Ri and R 2 of the acrylate monomer are -hydrogen.
  • R is a CH 3 group.
  • R 3 is often hydrogen, such as, acrylic acid and methacrylic acid.
  • the acid functionality monomers can also be difunctional components such as, for example, maleic acid, fumaric acid or can be the anhydride forms of these components.
  • the functional group is often found in the R 3 group.
  • Suitable examples are hydroxyethylacrylate, glycidylmethacrylate, and 1 ,3-butanediol dimethylacrylate.
  • acrylate monomers include, but are not limited to, methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, 2-methylheptyl (meth)acrylate, octyl acrylate, octyl methacrylate, isooctyl (meth)acrylate,
  • the acrylate monomer has up to about 20 carbon atoms, such as, but not limited to, acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n- hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, 2-methylh
  • the acrylate monomers are acrylic acid and 2-ethylhexyl acrylate.
  • Functionality can be built in to the tackifier resin by choosing an acrylate monomer containing at least one functional group.
  • the functional group can be selected from hydroxy, cycloaliphatic, acid, epoxide, amide, acrylonitril and acrylate groups.
  • the acrylate monomer contains acid groups or hydroxyl groups. This functionality can lead to even better cohesion in the adhesive composition as determined by the Shear Adhesion Failure Test (SAFT), however, the tackifier resin can be less heat stable due to trans- esterfication reactions.
  • SAFT Shear Adhesion Failure Test
  • Other specific functional groups can be chosen to improve MVTR, fogging, and adhesion.
  • the tackifier resin can be produced by any process known in the art. In one embodiment, the tackifier resin can be produced by a radical catalyzed polymerization mechanism:
  • I represents an initiator
  • R « represents a radical
  • M represents a monomer.
  • Any polymerization initiator known in the art for radical catalyzed polymerization can be utilized.
  • Initiators are typically chosen based on the desired molecular weight of the tackifier resin and the polymerization temperature. The effect of decomposition products of the initiator on the odor of the tackifier resin can also be a factor.
  • Suitable initiators can be chosen from all kinds of commercially available organic peroxides, such as, but not limited to, diacyl peroxides, dialkylperoxidicarbonaf.es, tert- alkyl peroxyesters, di-tert-alkyl peroxides, tert-alkyl hydroperoxides, ketone peroxides, and mixtures thereof.
  • the initiator is selected from the group consisting of di-tert-butyl peroxide, dicumyl peroxide, and di-amyl peroxide.
  • the radical catalyzed polymerization can occur in a reactor, zone in the presence of at least one solvent. Processes may also be used without the use of solvents.
  • the reactor zone comprises at least one reactor.
  • the solvent can be any solvent that is known in the art to be utilized in radical catalyzed polymerizations.
  • solvents include, but are not limited to, xylene, toluene, ethylbenzene, trimethylbenzene, and mixtures thereof.
  • the solvent is xylene or a mixture of the isomers of methyethylbenzene, trimethylbenzene, ethyl-dimethylbenzene, propylmethylbenzene and tetramethylbenzene.
  • the solvent is xylene. Radical catalyzed polymerization to produce the tackifier resins can be batch, fed batch or continuous.
  • Reaction temperatures for the radical catalyzed polymerization can be from 0 to about 250°C, preferably from about 100°C to about 200°C, and most preferably from 150°C to 160°C.
  • Initiator levels can be from about 0.1% by weight to about 6% by weight based on the weight of the monomer feed, preferably the amount of initiator can range from 0.1 % to 3%.
  • a process to produce a tackifier resin comprising contacting a tackifier resin product stream with at least one carrier at a temperature sufficient to remove a portion of at least one residual monomer to produce the tackifier resin. Residual monomer is defined as unreacted monomer or monomers contained in the tackifier resin.
  • the tackifier resin product stream comprises tackifier resin and optionally, solvent. A portion of the residual solvent can also be removed from the tackifier resin product stream.
  • the tackifier resin and solvent were previously discussed in this disclosure.
  • the tackifier resiri concentration is particularly useful in adhesives for medical applications since it can have a clear color.
  • the low residual monomer concentration in the inventive tackifier resin can also reduce or eliminate skin sensitivity properties. It can also give much better fogging behavior of the adhesive composition over adhesive compositions containing tackifier resins without low residual monomer concentrations.
  • the amount of the residual monomer in the tackifier resin depends on the use of the adhesive composition.
  • the inventive tackifier resin can have a low residual monomer concentration such that the tackifier resin does not significantly decrease the MVTR of the adhesive composition.
  • a tackifier resin does not significantly decrease the MVTR of the adhesive composition if the MVTR is not decreased by more than 25%, preferably 10% over the adhesive composition without the tackifier resin.
  • the MVTR of the adhesive composition is the same or increased over the adhesive composition without the tackifier resin.
  • the MVTR of the adhesive composition can range from about 200 to about 3000, preferably from 500 to 1500.
  • the contacting of the tackifier resin product stream with the carrier to remove a ⁇ portion of the. residual monomers can be conducted by any means known in the art.
  • Examples of carriers include, but are not limited to, steam, nitrogen and ethane.
  • the carrier is stream.
  • the temperature and pressure of the carrier is that which is sufficient to remove a portion of the residual monomers to obtain the desired residual monomer concentration of the tackifier resin or desired MVTR of the adhesive composition.
  • the residual monomer concentration of the tackifier resin is such that it does not increase fogging of the adhesive composition or cause any significant level of skin sensitivity.
  • the residual monomer concentration of the tackifier resin is less than about 600 ppm by weight based on the weight of the tackifier resin, more preferably less than about 300 ppm by weight, and most preferably,, less than 250 ppm by weight.
  • the residual monomer level of the tackifier resin is less than about 200 ppm aromatic monomer based on the weight of the tackifier resin and less than about 400 ppm acrylic monomer, preferably less than about 100 ppm by weight aromatic monomer and less than about 200 ppm by weight acrylic monomer, and most preferably, less than 100 ppm by weight aromatic monomer and less than 150 ppm by weight acrylic monomer.
  • the residual solvent level in the tackifier resin is less than about 500 ppm by weight based on the weight of the tackifier resin, preferably less than about 200 ppm by weight, and most preferably, less than 50 ppm by weight.
  • the contacting of the tackifier resin product stream with the carrier can occur at any temperature and pressure sufficient to obtain the desired residual monomer concentration in the tackifier resin.
  • the contacting can occur at a temperature in the range of about 150°C to about 250 ⁇ 0, more preferably, from 160°C to 220°C.
  • the contacting of the tackifier resin product stream with the carrier occurs at a pressure in the range. of about 10 mbar to about 1000 mbar, preferably from 20 mbar to 200 mbar.
  • a process to produce the tackifier resin is provided.
  • the process comprises: a) providing at least one aromatic monomer, at least one acrylate monomer, and optionally at least one solvent to a reactor zone to produce a reaction mixture; b) polymerizing the reaction mixture in the presence of at least one initiator to produce a tackifier resin product stream; and c) contacting the tackifier resin product stream with a carrier to remove a portion of at least one residual monomer from the tackifier resin product stream to yield the tackifier resin.
  • the process of contacting the tackifier resin product stream with the carrier has been previously discussed in this disclosure.
  • a process to produce the tackifier resin is provided.
  • the process comprises: a) providing at least one aromatic monomer, at least one acrylate monomer, and optionally at least one solvent to a reactor zone to produce a reaction mixture; b) polymerizing the reaction mixture in the presence of at least one initiator to produce a tackifier resin product stream; c) heating the tackifier resin product stream at a temperature sufficient to remove a portion of at least one residual monomer from the tackifier resin product stream; and d) contacting the tackifier resin product stream with at least one carrier to further remove a portion of the residual monomers to produce the tackifier resin.
  • the residual monomer concentration of the tackifier resin is less than about 600 ppm by weight based on the weight of the tackifier resin.
  • the residual monomer concentration and residual solvent concentration can vary and were discussed previously in this disclosure.
  • the heating of the tackifier resin product stream can be conducted by any method known in the art.
  • the tackifier resin product stream can be heated while in the reactor vessel or it can be removed to other processing equipment.
  • the heating is conducted at a temperature and pressure sufficient to remove a portion of at least one residual monomer.
  • the temperature however should not be too high to cause color deterioration of the tackifier resin.
  • the residual monomer can be removed by heating the tackifier resin product stream to a temperature ranging from about 150°C to about 250°C, preferably 160°C to 220°C.
  • the pressure can vary from about 10 mbar to about 1000 mbar, preferably from 20 mbar to 200 mbar.
  • the portion removed can range from about 1% by weight to about 200% by weight based on the weight of the tackifier resin. Preferably, the portion removed can range from 50% by weight to 150% by weight.
  • the duration of the heating varies depending on the amount of tackifier resin product stream to be handled. For example, the duration can range from about 0.5 hours to about 8 hours. The contacting of the tackifier resin product stream with a carrier was previously described in this disclosure.
  • a tackifier resin is produced by a process comprising: a) providing at least one aromatic monomer, at least one acrylate monomer, and optionally at least one solvent to a reactor zone to produce a reaction mixture; b) polymerizing the reaction mixture in the presence of at least one initiator to produce a tackifier resin product stream; c) heating the tackifier resin product stream at a temperature in a range of about 150°C to about 250°C to remove a portion of the residual monomers from the tackifier resin product stream; and d) contacting the tackifier resin product stream with a carrier to further remove a portion of the residual monomers to yield the tackifier resin having residual monomer concentrations of less than about 200 ppm of aromatic monomer and 400 ppm of acrylate monomer.
  • the tackifer resin is produced by a processs comprising: a) contacting at least one aromatic monomer, at least one acrylate monomer, and at least one initiator to produce a monomer- initiator stream; b) routing the monomer-initiator stream to a reaction zone containing solvent at a temperature in the range of about 100°C to about 250°C; c) polymerizing the monomer-initiator feed stream at polymerization conditions to produce a tackifier resin product stream; d) optionally, providing an additional amount of initiator to the reaction zone; e) heating the tackifier resin product stream at a temperature in a range of about 150°C to about 250°C and at a pressure of about 10 mbar to about 1000 mbar to remove a portion of the residual monomer from the tackifier resin product stream; and f) contacting the tackifier resin product stream with steam at
  • the tackifier resin can also have a residual solvent concentration of less than about 500 ppm.
  • the tackifier resin polymerization process are aromatic monomer type, acrylate monomer type, functionality in the form of acid or hydroxyl groups in the acrylate monomer, different process conditions, which all result in different softening points and molecular weights of the tackifier resin.
  • the amount of aromatic monomer repeating units in the tackifier resin can range from about 0.1% to 99.9% based on the total amount of monomer repeating units in the tackifier resin, preferably from about
  • the amount of acrylate monomer repeating units in the tackifier resin can range from 0.1% to 99.9%, preferably from about 30% to about 80%, and most preferably, from 35% to 75% based on the total amount of monomer repeating units in the tackifier resin.
  • the tackifier resin can have a R&B softening point ranging from being a liquid at room temperature to about 180°C , preferably from about 50°C to about 150°C, and most preferably, from 75°C to 120°C.
  • the acid number of the tackifier resin can range from about 0 to about 300 mg KOH/g resin, preferably from about 0 mg KOH/g resin to about 200 mg KOH/g resin, and most preferably from 5 to 150 mg KOH/g resin.
  • the hydroxyl number can vary from about 0 to about 300, preferably from 0 to 200.
  • the MMAP cloud point of the tackifier resin is typically less than 50°C, preferably the MMAP ranges from about -20°C to about 30°C, and most preferably from ⁇ 10°C to 20°C.
  • the number average molecular weight (Mn) of the tackifier resin can range from about 1 ,500 to about 7,000 daltons, preferably from about 1 ,600 to about 4,500, and most preferably from 2,000 to 4,000.
  • the weight average molecular weight (Mw) of the tackifier resin can range from about 2,000 to about 25,000 daltons, preferably from about 2,500 to about 12,000 and most preferably from 3,000 to 10,000.
  • the z-average molecular weight (Mz) of the tackifier resin can range from about 3,000 to about 75,000 daltons, preferably from about 4,500 to about 30,000, and most preferably 5,000 to 20,000.
  • the Gardner color of the tackifier resin generally is lower than 5, preferably is lower than 2, and most preferably is lower than 1.
  • the Gardner color of the tackifier resin is generally lower than 2, and preferably is lower than 1.
  • Light colored tackifier resins are often required for certain applications, especially in the medical adhesive field.
  • the residual monomer concentrations in the tackifier resin is typically less than about 200 ppm by weight aromatic monomer based on the weight of the tackifier resin and less than about 400 ppm by weight acrylic monomer based on the weight of the tackifier resin.
  • the amount of residual aromatic monomer is less than about 100 ppm by weight, and the amount of residual acrylic monomer is less than about 200 ppm by weight based on the weight of the tackifier resin.
  • the amount of residual aromatic monomer is less than 100 ppm by weight based on the weight of the tackifier resin, and the amount of residual acrylic monomer is less than 150 ppm based on the weight of the tackifier resin.
  • the residual solvent in the tackifier resin is less than about 500 ppm based on the weight of the tackifier resin, preferably less than about 200 ppm, and most preferably, less than 50 ppm.
  • the tackifier resin comprises monomer repeating units from at least one aromatic monomer and monomer repeating units from at least one acrylate monomer, wherein the monomer repeating units is at least one selected from styrene, acrylic acid, and 2-ethylhexyl acrylate.
  • the amount of styrene repeating units can range from 0.1 to 99.9% based on the total amount of monomer repeating units in the tackifier resin.
  • the amount of acrylic acid and 2-ethylhexyl acrylate can range from 0.1% to 99.9% based on the total amount of monomer repeating units in the tackifier resin.
  • the amount of styrene repeating units can range from about 20% to about 70%, and the combined amount of acrylic acid repeating units and 2-ethylhexyl acrylate repeating units can range from about 30% to about 80%. Most preferably, the amount of styrene repeating units can range from 25% to 65%, and the combined amount of acrylic acid repeating units and 2-ethylhexyl acrylate repeating units can range from 35% to 75%.
  • the amount of acrylic acid in the tackifier resin can be less than about 30% in order to help prevent gelling of the tackifier resin.
  • the amount of acrylic acid in the tackifier resin can range from 0.1% to 99.9%.
  • a process is provided to produce the adhesive composition. The process comprises contacting at least one tackifier resin and at least one adhesive component to produce the adhesive composition.
  • the composition of the adhesive composition may be adjusted by adding a surfactant or by diluting with water or an aqueous medium.
  • various additives can be added to the adhesive composition to give the adhesive composition desired properties or for preventing degradation, or for any other purpose.
  • Such additives include, but are not limited to, reinforcing agents, fire retardants, foaming agents, conventional tackifiers, plasticizers, oils, antioxidants, polymers, curable/reactive monomers, crosslinking agents, fillers, and pigments. Because of the number of possible compounding ingredients, the properties of the tackifier resin prepared according to this invention can be varied to satisfy most foreseeable requirements for tack, peel, strength, shear strength, and solvent media resistant, on whatever combination of substrate utilized. Any adhesive component known in the art can be utilized.
  • Adhesive components include, but are not limited to, polyurethanes; poly ether amides block copolymers; polyethylene copolymers, including, but not limited to, polyethylene-vinyl acetate, polyethylene- butyl acrylate, polyethylene- 2-ethyl hexyl acrylate, polyethylene- methyl acrylate, polyethylene- acrylic acid, polyethylene oxide and its copolymers; amorphous poly-alpha olefins and the functionalized copolymers thereof; poly lactide and copolymers; polyamides; polyesters and co-polyesters; polyester block copolymers; functionalized polyesters and co-polyesters including, but not limited to, sulphonated polyesters; polyacrylic compositions; polyvinyl ethers; poly caprolactones and copolymers; epoxides and copolymers thereof including, but not limited to, urethane- epoxides; isoprene compositions; poly-is
  • Coating thickness varies depending on the application. Suitable coating thicknesses can range from about 0 g/m 2 to about 200 g/m 2 , preferably, from 10 g/m 2 to 100 g/m 2 .
  • the adhesive composition can be coated on a wide array of substrates. Suitable examples include, but are not limited to, polymer films such as polyethylene terephthalate (PET) and biaxially oriented polypropylene (BOPP); woven and non-woven fabrics; metals and metal foils, such as aluminum copper lead, gold and the like; paper; glass; ceramics; and composite materials comprising laminates of one or more of these materials.
  • the adhesive composition is used as a pressure-sensitive adhesive.
  • pressure-sensitive adhesives comprise at least one elastomeric polymer and at least one tackifier resin.
  • the pressure-sensitive adhesive can further comprise at least one additive.
  • additives for adhesive compositions were previously given in this disclosure.
  • Elastomeric polymers include, but are not limited to, natural rubber, butyl rubber, acrylic polymers, and block copolymers, such as styrene-butadiene-styrene block copolymers and styrene-isoprene-styrene block copolymers.
  • the tackifier resin is utilized to produce hot-melt adhesives.
  • Hot-melt adhesives are nonvolatile thermoplastic materials that can be heated to a melt and then applied as a liquid to a substrate.
  • Thermoplastic materials include, but are not limited to, ethylene-vinyl acetate polymers , paraffin waxes, polypropylene, phenoxy resins, styrene-butadiene copolymers, ethylene-ethyl acrylate copolymers, polyesters, polyamides, polyurethanes, and mixtures thereof.
  • Hot-melt adhesives can further comprise at least one additive. Examples of additives for adhesive compositions were previously given in this disclosure. . Possible adhesive applications in which the adhesive composition may be used are numerous.
  • Examples include, but are not limited to, skin-contact medical applications, surgical tapes, bandages, wound care, operation tapes and drapes, hygiene applications including feminine care products, box sealing tapes, masking applications, low fogging, automotive interior applications including foam gaskets, instrument displays, sound deadening, trim bonding, sealants, chaulks, general pressure sensitive adhesives, semi-pressure sensitive adhesives, building and hydroxyl ion adhesives, assembly adhesives, adhesive films and membranes, bottle labeling, water soluble adhesives, laminating adhesives, adhesives for flexible packaging, concrete curing compounds, mounting tapes, double sided tapes, electrical tapes, permanent and removable labels, filmic labels, pressure sensitive adhesives for the graphic industry, labels for laser printers, insulation tapes, primer compounds, tie layers, road marking adhesives, inks, mounting tapes, labels for chemicals including sea water resistant labels, and labeling for pharmaceuticals and cosmetics, etc.
  • Another embodiment of this invention comprises a laminated structure of at least a first and a second substrate, the substrates being joined by a layer of the adhesive composition.
  • mice were sacrificed by using euthasate.
  • statistical analyses were performed by means of the Welch-ANOVA (for 3 H- thymidine incorporation in the auricular lymph nodes (ARN)) because Levene's test for variances showed that variances occurred between the different groups.
  • Mettler Drop Softening Point MDSP was determined by a modified ASTM D6090-99 method. The method was modified in that the measurement was performed without a ball and using a cup with a 4.5 mm hole.
  • MMAP Cloud Point (methylcyclohexane and aniline) was determined by ASTM D-611. Molecular weight distribution parameters, Mn, Mw, Mz and Mp (weight at the top of the peak) were determined by Gel Permeation Chromatography (GPC) on a Waters GPC 2690 system equipped with Waters Styragel HR2 (7.8X300mm) columns and a Waters 410 RI detector. Polystyrene standards were used for calibration. Moisture Vapor Transport Rate (MVTR) was measured by ASTM 3-96. Peel was determined by AFERA 4001. The following definitions are utilized to interpret the data from this test.
  • Cohesive failure and slip- stick are defined in the Handbook of Pressure Sensitive Adhesive Technology, 2nd Edition, edited by Don Satas and Van Nostrand Reinhold.
  • Cohesive failure is a failure mode leaving adhesive residue on the test panel.
  • Slip-stick is a failure mode in which the peel force is not smooth but starts to fluctuate periodically from low to high force. Residual monomer levels were determined by a gas chromatograph (GC) for the styrene, 2-ethylhexyl acrylate and xylene and with a high performance liquid chromatograph (HPLC) for acrylic acid. The procedure followed when using the gas chromatograph is described below.
  • GC gas chromatograph
  • HPLC high performance liquid chromatograph
  • a Trace 2000 GC Thermo Quest was utilized having a CP-WAX 57 CB (Chrompack) column having a length of 25 meters, an inner diameter of 0.25 mm, and a film thickness of 0.2 urn.
  • the temperature was 50°C for 20 minutes with a change of temperature of 4°C per minute, and a maximum of 200°C was achieved for 5 minutes.
  • the detector was a FID at 230°C.
  • a split injector was utilized, and the carrier was hydrogen.
  • the internal standard utilized was 250 mg anisole, and 50 mg of the substance to be analyzed (e.g. xylene, acrylate) were dissolved in 10 ml of acetonitrite.
  • the procedure followed when using HPLC is described below. This method was used for the analysis of styrene-acrylate tackifier resins, to determine the residual acrylic acid content.
  • the samples were dissolved in tetrahydrofuran or carbon disulfide and then filtered prior to analysis by reverse phase HPLC.
  • An external standard of acrylic acid was used for calibration.
  • the acrylic acid standard and the styrene- acrylate tackifier resin samples were analyzed on a Zorbax® RX-C18 column (5 ⁇ m), using a two-part gradient.
  • This two-part gradient consisted of part (1) 2% methanol in 0.05 M phosphoric acid for the elution of the acrylic acid and part (2) 100% tetrahydrofuran for purging the column during the actual sample analysis.
  • the purge helped to minimize chromatographic problems for repetitive analysis. Peak detection was accomplished by monitoring the eluent with a UV detector. The primary UV wavelength monitored was 200 nm. The average response factor for acrylic acid was determined by several injections. The calibration curve of the acrylic acid standard was linear over the range of 0-1000 ppm with a lower limit of detection of about 5 ppm. The following is a summary of the apparatus and chromatographic conditions utilized for the HPLC.
  • Apparatus (1) Liquid chromatograph, Hewlett-Packard Model 1090, or equivalent. (2) Ultraviolet (UV) detector, Hewlett-Packard Model 1100, or equivalent. (3) Data system or integrator capable of measuring peak area. (4) Column, Zorbax® RX-C18 (5 ⁇ m), 150 mm x 4.6 mm - available from Agilent located in Palo Alto, California. (5) Guard column cartridge, Zorbax® RX-C18 (5 ⁇ m), 12.5 mm x 4.6 mm - available from Agilent, or equivalent. (6) Sample loop injection valve, 5 ⁇ L, Rheodyne Model 7125 - available from Supelco located in Bellefonte, PA.
  • SAFT Shear Adhesion Failure Test
  • UV-C is the effective wavelength for curing a UV-curable adhesive composition. UV-C was measured with a calibrated UVICURE PLUS 8788, a self-contained electro-optic radiometer obtained from Electronic Instrumentation and Technology, Inc, Sterling, VA. In some experiments, the total UV dose was measured. In others, the UV-C dose was measured. A relation between total UV dose and UV-C dose was determined for the equipment utilized in these examples. Testing was conducted by varying the UV dose for some UV-curable adhesive compositions. The results are given in Figure 1 and Table 2 Table 2. Relation Between Total UV Dose and UV-C Dose for the Equipment Used
  • Table 2 and Figure 1 can be used to compare the results when measuring total UV rather than UV-C.
  • Inventive Example 1 Synthesis of the Inventive Styrene-Acrylate Tackifier Resins Styrene-acrylate tackifier resins were produced in a high-pressure reactor using a fed batch method. Xylene was used as a solvent and was pumped into the reactor and heated with stirring under nitrogen atmosphere to 150°C. The monomers (styrene, acrylic acid, and 2-ethyl hexyl acrylate) and 2% by weight initiator based on the weight of the monomers were mixed to produce a monomer-initiator feed stream. The monomer-initiator feed stream was added gradually to the hot solvent over two hours to produce a reaction mixture.
  • the reaction temperature was maintained at 150°C.
  • the reaction mixture was stirred for another 30 minutes at this temperature and at a pressure of about 3 bar.
  • a small amount of initiator was post-added, and the process was maintained for another 30 minutes at 150°C to produce a tackifier resin product stream.
  • the styrene-acrylate tackifier resin was isolated from the tackifier resin product stream by distilling off the solvent.
  • the temperature was slowly increased to 170°C, and vacuum was applied up to 25 mbar. After about 30 minutes, 90% of the solvent was evaporated. After 2.5 hours, the temperature reached 170°C and vacuum reached 25 mbar, and about
  • 2-ethylhexyl acrylate levels were less than 40 ppm. Residual acrylic acid was less than 134 ppm, and residual solvent was less than 24 ppm. These levels were significantly less than the residual monomer and solvent levels of the styrene-acrylate tackifier resins prior to steaming and to other commercial tackifiers as shown in Comparative Example 2. It should also be noted that the other properties of the styrene-acrylate tackifier resins were hardly effected by removing a substantial portion of the residual monomers. Low levels of residual monomers are extremely important for the end application, since the residual monomers can cause skin sensitivity. Low residual monomer and solvent levels in the tackifier resins can also positively influence the fogging behavior of an UV-curable adhesive composition.
  • Example 3 Variation of Monomer Repeating Unit Amounts in Styrene-Acrylate Tackifier Resins -Effect on Properties
  • the amount of the monomer repeating units in the styrene- acrylate tackifier resins were varied using the same process as described in Example 1 , and the resulting properties of the styrene- acrylate tackifier resins were monitored. The results of these experiments are given in Table 5. Table 5. Variation of Monomer Amounts in Styrene-Acrylate Tackifier Resins -Effect on Properties
  • styrene-acrylate tackifier resins were obtained with a MDSP from about 44.9°C to about 171.2°C, with acid numbers from 35 mg KOH/g to 187 mg KOH/g, a MMAP from 4°C to 32°C, and a Mzfrom 15921 to 51019 Dalton. More styrene instead of acrylic acid or 2-ethylhexylacrylate made the styrene-acrylate tackifier resin more aromatic resulting in a higher MDSP and a higher Mz. More acrylic acid increased the acid number and the functionality. It also increased the softening point and the MDSP.
  • Example 4 Skin Sensitivity of the Tackifier Resin A local lymph node assay test (LLNA) in. mice was performed to determine if the styrene-acrylate tackifier of Formulation II in Example 1 has skin sensitivity properties. Under the experimental conditions, there were no indications that the styrene-acrylate tackifier resin of Formulation II (see Example 1 ) had sensitizing properties.
  • the basic principle underlying the LLNA is that sensitizers induce a primary proliferation of lymphocytes in the lymph node draining the site of chemical application. This proliferation only occurs with allergens and is proportional to the dose applied. Therefore, the LLNA provides a simple means of obtaining an objective, quantitative measurement of sensitization.
  • Hexyl cinnamic aldehyde was used as a positive control.
  • the hexyl cinnamic aldehyde was mixed in acetone/olive oil to a concentration of 25% by volume.
  • a mixture of acetone and olive oil in a 4:1 ratio was used as a negative control.
  • the tackifier resin was diluted in acetone/olive oil (4:1 v/v) to the desired concentration.
  • Twenty mice were divided into 5 groups of 4 animals each. Three groups of 4 mice each were treated with different doses of the tackifier resin (Group B: 10%; Group C: 25%; and Group D: 50%).
  • Group E was treated with the positive control substance, and Group A was treated with the negative control.
  • the test substance was administered with 25 ⁇ l on each ear of the mouse. The data collected showed that there were no indications that the tackifier resin had skin sensitizing properties.
  • Example 5 Thermal Stability of Styrene-Acrylate Tackifier Resins
  • the thermal stability of the styrene-acrylate tackifier resins produced in Example 1 has been studied. The results are given in Table 6. The styrene-acrylate tackifier resins were heated as specified in Table 6.
  • the R&B softening point of the styrene-acrylate tackifier resin increased slightly upon heating. All other tackifier resin properties were not influenced by heating under the given circumstances. Therefore, it can be concluded that the styrene-acrylate tackifier resins do not only have good gelling stability but also a good heat stability, despite the fact that no antioxidants were used.
  • the Reactol® AC 11 and AC 18 tackifier resins were also aged upon heating, and both products showed an unstable performance. Initially, Reactol® AC11 and AC18 tackifier resins were liquid, after 24 hours at 175°C, the products were gels. This can be due to trans- esterification reactions. However, at temperatures below about 175°C, Reactor® AC11 and AC 18 tackifier resins function well in UV-curable adhesive compositions and do not gel.
  • Example 6 Moisture Vapor Transfer Rate and Fogging Tests
  • styrene-acrylate tackifier resins compared to conventional tackifiers, such as, Foral® 85-E rosin esters and Kristalex® F100 aromatic resin are that styrene-acrylate tackifiers can give better results in fogging tests and does not significantly reduce the MVTR of the adhesive composition.
  • Films prepared with an 18:85 ratio of tackifier resin to UV-curable acrylic composition were evaluated. In case of MVTR, the films were transferred to a highly breathable kimwipe structure, and the values was corrected by assuming that the resistances (1/MVTR) were additive. Results are given in Table 7.
  • Styrene acrylate tackifiers can be used to tackify solvent-based acrylic polymers. These styrene-acrylic tackifier can be used in radiation- curable, heat curable, and non-cured adhesive compositions.
  • two styrene-acrylate tackifier resins, Formulation I and II from Example 1 were compared with two conventional tackifiers in two solvent- based acrylic polymers, Solucryl 300 and Solucryl 303, produced by UCB in Brussels, Belgium.
  • the tackifier resins were mixed in a 5:85 ratio with the solvent-based acrylic polymer and coated at a coating weight of 30 g/m 2 .
  • the coatings were dried and cross linked for 10 minutes at 110°C.
  • the results were also compared with hot-melt adhesives produced from the styrene-acrylate tackifier resins of Formulation I and II and acResin® acrylic copolymer produced by BASF.
  • the following procedure was used in the hotmelt coating method.
  • the acResin® acrylic copolymer and tackifier resin were mixed together in an aluminium tray on a hot-plate at 150°C to produce a UV-curable acrylic adhesive composition.
  • the UV-curable acrylic adhesive composition was poured in a LC 200 pilot-plant-scale Lab-coater and coated onto 200 mm wide bi-axially. oriented polypropylene (BOPP) film at about an average 7 m/minute coating speed at 140°C.
  • the coating speed depended on the viscosity of the
  • UV-curable adhesive composition therefore, 7m/minute was the average.
  • Example 8 Water-Based Adhesive Compositions
  • Styrene-acrylate tackifiers also can be used in water-based acrylic polymer systems.
  • the tackifier resins were dispersed in water to a 50% dispersion, using a surfactant for stabilization.
  • the final dispersion was mixed in a 1 :3 ratio with Acronal® V215, a water based acrylic polymer from BASF.
  • the adhesives were coated and dried to 21 gsm.
  • Table 9 Application Results of Various Tackifier Resins in a Water-Based Adhesive Compositions Containing Acronal® V215 as an Adhesive Component
  • Tacolyn® 3179H is a rosin ester dispersion produced by Eastman Chemical company.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une résine donnant du collant, contenant des unités monomères issues d'au moins un monomère aromatique et d'au moins un monomère acrylate, cette résine présentant une faible concentration de monomères résiduels. Dans d'autres modes de réalisation, ladite résine ne réduit sensiblement pas la vitesse de transport de vapeur d'eau d'une composition adhésive la contenant, n'augmente sensiblement pas la formation de buée d'une composition adhésive la contenant, et ne présente sensiblement pas de propriétés de sensibilité cutanée. L'invention concerne également un procédé de production de cette résine donnant du collant. Ce procédé consiste à mettre en contact un flux de produit de résine donnant du collant avec au moins un support, à une température suffisante pour éliminer au moins une partie d'au moins un monomère résiduel du flux de produit afin de produire la résine donnant du collant.
EP05713421A 2004-02-18 2005-02-14 Resines donnant du collant a base de monomere acrylate et de monomere aromatique Withdrawn EP1716213A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/780,989 US7262242B2 (en) 2004-02-18 2004-02-18 Aromatic/acrylate tackifier resin and acrylic polymer blends
US10/780,987 US7332540B2 (en) 2004-02-18 2004-02-18 Aromatic-acrylate tackifier resins
PCT/US2005/004470 WO2005080520A1 (fr) 2004-02-18 2005-02-14 Resines donnant du collant a base de monomere acrylate et de monomere aromatique

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EP05713418A Withdrawn EP1716214A1 (fr) 2004-02-18 2005-02-14 Melanges de resine poissante aromatique ou acrylate et de polymere acrylique

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JP2007523250A (ja) * 2004-02-18 2007-08-16 イーストマン ケミカル カンパニー 芳香族−アクリレート粘着付与樹脂
US20060110596A1 (en) * 2004-11-24 2006-05-25 National Starch And Chemical Investment Holding Company Hot melt adhesives for medical application
KR101396749B1 (ko) * 2006-11-07 2014-05-21 헨켈 아게 운트 코. 카게아아 아크릴 핫멜트 접착제
DE102008023758A1 (de) 2008-05-09 2009-11-12 Tesa Se Haftklebebänder zur Verklebung von Druckplatten
US8361633B2 (en) 2008-10-03 2013-01-29 3M Innovative Properties Company Cloud point-resistant adhesives and laminates
US8361632B2 (en) * 2008-10-03 2013-01-29 3M Innovative Properties Company Cloud point-resistant adhesives and laminates
JP5426700B2 (ja) * 2011-03-31 2014-02-26 日本エイアンドエル株式会社 共重合体ラテックス及び該共重合体ラテックスを含有する組成物
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JP2007523250A (ja) 2007-08-16
CA2555094A1 (fr) 2005-09-01
CA2555094C (fr) 2009-09-15
JP2007523978A (ja) 2007-08-23
CA2555090C (fr) 2009-09-22
WO2005080520A1 (fr) 2005-09-01
CA2555090A1 (fr) 2005-09-01
EP1716214A1 (fr) 2006-11-02

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