WO2013083565A1 - Colophane protégeant des uv - Google Patents

Colophane protégeant des uv Download PDF

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Publication number
WO2013083565A1
WO2013083565A1 PCT/EP2012/074365 EP2012074365W WO2013083565A1 WO 2013083565 A1 WO2013083565 A1 WO 2013083565A1 EP 2012074365 W EP2012074365 W EP 2012074365W WO 2013083565 A1 WO2013083565 A1 WO 2013083565A1
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WO
WIPO (PCT)
Prior art keywords
rosin
mixture
compound
ester
absorbing
Prior art date
Application number
PCT/EP2012/074365
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English (en)
Inventor
Evert Smit
Erik Kelderman
Original Assignee
Arizona Chemical Company, Llc
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.)
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Publication date
Application filed by Arizona Chemical Company, Llc filed Critical Arizona Chemical Company, Llc
Publication of WO2013083565A1 publication Critical patent/WO2013083565A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04—Chemical modification, e.g. esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the instant invention relates to a rosin mixture comprising a modified rosin compound having a UV-absorbing moiety, to a method for preparing said rosin mixture, to compositions comprising said rosin mixture and to the use of said compositions as an adhesive formulation or a thermoplastic road marking formulation.
  • Rosin also called colophony or Greek pitch [Pix grasca)
  • Rosin comprises a mixture of resin acids such as abietic or pimaric acids, the type depending in part on the plant species.
  • the term "rosin" as used in this invention has this generally accepted meaning.
  • rosin compound as used herein means a resin acid, a rosin ester or a rosin derivative.
  • rosin derivative means a resin acid or a rosin ester which has been subjected to at least one reaction selected from a hydrogenation, a dehydrogenat ion, a
  • Rosin compounds are useful in numerous applications, and are included in formulations such as adhesives, inks, coatings, rubbers, sealants, asphalt, and thermoplastic road markings.
  • formulations such as adhesives, inks, coatings, rubbers, sealants, asphalt, and thermoplastic road markings.
  • the use of such formulations is limited in applications where they are exposed to direct sunlight because rosin compounds, and other components typically present in such formulations (e.g. polymers), can be sensitive to UV radiation.
  • materials containing rosin compounds may suffer from a deterioration of their properties over time.
  • adhesive compositions may suffer from yellowing, tend to crack and lose their adhesion properties when exposed to UV-radiation
  • ink compositions may suffer from color changes and rubbers, sealants, thermoplastic road markings and coatings may generally degrade.
  • UV-protecting additives such as UV filters, UV absorbers and/or UV stabilizers
  • UV filters such as UV filters, UV absorbers and/or UV stabilizers
  • UV stabilizers a problem associated with some of such additives is that they tend to migrate, and may present a health and/or environmental hazard. For instance, an additive may migrate to the surface of a packaging polymer, putting the additive in contact with consumable food or drink products.
  • UV-protecting additives are not satisfactorily used can be that the addition of separate UV- protecting additives can add complexity to the preparation of the polymer formulations. The additives can be difficult to mix, alter the properties of the final formulation or be
  • rosin compounds that are more stable in polymer-containing formulations, such as adhesives, inks, rubbers, sealants, coatings, asphalt and thermoplastic road markings, in particular when exposed to UV light.
  • One aspect of this invention is a rosin mixture comprising at least one of a modified rosin compound optionally in admixture with unmodified rosin compounds; the modified rosin compound is a rosin compound that is modified to have a UV- absorbing moiety. It has now been discovered that modifying a rosin compound by attaching a UV-absorbing moiety thereto results in a compound having increased UV-resistance .
  • rosin mixture that increases the stability of formulations (e.g. adhesives, coatings, inks, rubbers, sealants, asphalt and thermoplastic road markings), in particular formulations exposed to UV- radiation. It has now been discovered that such rosin mixtures containing a modified rosin compound can function in
  • formulations such as adhesives, inks, coatings, rubbers, sealants, asphalt or thermoplastic road markings
  • common rosin mixtures e.g. as tackifier and as a binder
  • UV- protecting additives e.g. UV-protecting additives
  • Such rosin mixtures may therefore be used as multifunctional components in formulations exposed to sun light, avoiding the need for using a separate UV-absorber.
  • An advantage of using rosin mixtures comprising a modified rosin compound having UV-absorbing moiety, is that the formulation wherein it is used advantageously may have a reduced migration of the UV- absorber.
  • modified rosin compound having a UV moiety means a rosin compound that is modified so that it contains a UV-absorbing moiety.
  • rosin compound is as defined hereinabove. Accordingly, a modified rosin compound having a UV- absorbing moiety of the rosin mixture as described herein, can be derived from a rosin ester, a resin acid or a rosin
  • rosin derivative is as defined
  • Rosin mixtures comprising modified rosin derived from a rosin ester and/or a resin acid are particularly useful because rosin esters and resin acids are used in numerous applications .
  • the rosin mixture as described herein is obtained from mixtures of rosin compounds.
  • the mixtures of rosin compounds comprise at least one of a rosin ester, a resin acid and a rosin derivative, as defined above.
  • Resin acids generally include C20 fused-ring monocarboxylic acids with a nucleus of three fused six-carbon rings and double bonds that vary in number and location.
  • resin acids examples include abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, levopimaric acid,
  • sandaracopimaric acid isopimaric acid and palustrxc acid.
  • Rosin can be used as a source of resin acid. Rosin is a hydrocarbon secretion of many plants, particularly coniferous trees such as Pinus palustris and Pinus caribaea . Natural rosin typically consists of a mixture of seven or eight resin acids, and in minor quantities other components. Rosin is commercially available and can be obtained from pine trees by distillation of oleoresin (gum rosin being the residue of distillation) , by extraction of pine stumps (wood rosin) or by fractionation of tall oil (tall oil rosin) . Any type of rosin can be used as a source of resin acid, including tall oil rosin, gum rosin and wood rosin. Examples of commercially available rosins include rosins from Arizona Chemical (e.g. SYLVAROSTM 85, SYLVAROSTM 90, and SYLVAROSTM 95) .
  • Arizona Chemical e.g. SYLVAROSTM 85, SYLVAROSTM 90, and SYLV
  • Mixtures of rosin compounds comprising a rosin ester can be obtained from resin acids and alcohols by methods known in the art. For example, reference is made to the processes described in the patent document US 5,504,152, which is
  • resin acids can be esterified by a thermal reaction of the resin acid with an alcohol.
  • esterification reaction can be driven to completion water, by methods, such as distillation, application of vacuum, and other techniques known to the skilled person.
  • any type of rosin as described above, can be used to provide a mixture of rosin compounds comprising a rosin ester.
  • the rosin ester may be obtained from fortified rosin.
  • fortified rosin is a rosin compound which is the result of an addition reaction of a resin acid with a dienophile such as an a, ⁇ -unsaturated organic acid or the anhydride of such an acid resulting in a rosin compound with an increased number of carboxylic acid groups.
  • dienophiles are those acids and anhydrides which comprise from 3 to 10 and preferably from 3 to 6 carbon atoms, the most preferred
  • dienophiles being maleic acid, maleic anhydride and fumaric acid.
  • alcohols such as glycols and other polyalcohols and monoalcohols
  • a resin acid mixture including, for instance, at least one of glycerol, pentaerythritol , ethylene glycol, diethylene glycol, triethylene glycol, sorbitol, neopentylglycol ,
  • a rosin ester- containing mixture may comprise at least one of a glycerol rosin ester, a pentaerythritol rosin ester, diethylene glycol rosin ester and triethylene glycol rosin ester.
  • the rosin ester-containing mixtures of rosin compounds may comprise some residual, unreacted resin acid and/or alcohol.
  • the acid number of rosin ester-containing mixtures can be measured and gives an indication of the amount of acid present in the mixtures.
  • mixtures comprising a rosin ester may have an acid number below 20 mg KOH/g, in particular below 15 mg KOH/g.
  • the acid number can be determined by methods known to the skilled person, such as the standard method ASTM D974 which uses a color-indicator titration.
  • rosin esters may also be used, as for example SYLVALITETM RE100, SYLVALITETM RE88, SYLVATACTM RE103, SYLVATACTM RE55, SYLVATACTM RE85, SYLVATACTM RE12 and
  • SYLVATACTM RE5 all obtained from Arizona Chemical; Eastman ® ester Gum 15 D- , Permalyn ® 3100, Permalyn ® 5110-C and StaybeliteTM ester 3-E all obtained from EASTMAN; Dertoline ® G2L, Dertoline ® SG2, Dertoline ® P105, Dertoline ® P110, Dertoline ® P2L, Dertoline ® PL5, Dertopoline P125, Granolite SG, Granolite P, Granolite P118 and Granolite TEG all obtained from DRT (les Derives Resiniques & Terpeniques ) ; and NovaRes ® 1100 obtained from Georgia Pacific.
  • mixtures of rosin compounds comprising rosin derivatives can be obtained by, for instance, subjecting mixtures comprising a resin acid and/or a rosin ester to at least one reaction selected from a hydrogenation, a
  • the rosin mixtures of this invention may comprise the rosin compounds as described herein above.
  • the rosin mixtures obligatory contain at least one modified rosin compound.
  • the modified rosin compound in the rosin mixtures as described herein has a UV-absorbing moiety.
  • a UV-absorbing moiety is a group which absorbs and dissipates the light energy from UV radiation, typically by reversible intra-molecular proton transfer.
  • the UV-absorbing moieties as described herein have a protecting effect against UV-radiation due to their ability of dissipating the light energy from UV radiation.
  • UV- absorbing moieties have aromatic systems which are conjugated to double bonds and/or lone pairs of electrons.
  • the modified rosin compound has at least one UV-absorbing moiety derived from a UV absorbing compound selected from a hydroxybenzophenone , an oxybenzone, a dioxybenzone , an oxanilide, a benzotriazole , a hydroxyphenylbenzotriazole , and a hydroxyphenyltriazine .
  • UV-absorbing compounds are compounds which have the named structure (i.e.
  • hydroxybenzophenone, oxybenzone, dioxybenzone, oxanilide, benzotriazole, hydroxyphenylbenzotriazole, and hydroxyphenyltriazine as the core structure and which, as elucidated in more detail below, are provided with at least one group which is susceptible of reacting with the rosin compounds.
  • Rosin mixtures as described herein comprise at least 0.01 wt . % of a modified rosin compound having a UV-absorbing moiety.
  • the rosin mixtures may comprise at least 0.1 wt.%, at least 0.5 wt.%, at least 1 wt.%, or at least 2 wt.% of the modified rosin compound.
  • Maximum amounts of modified rosin compounds in the rosin mixtures can be 99 wt.%, 90 wt.%, 75 wt.%, 50 wt.%, 30 wt.%, 20 wt.% or 10 wt.%.
  • the rosin mixtures can have an amount of modified rosin compound varying from any of the minimum weight percentage amounts to any of the maximum weight percentage amounts.
  • the rosin mixture may comprise 100 wt.% of modified rosin compounds having a UV-absorbing moiety. The percentages by weight are based on the total weight of the rosin mixture.
  • the amount of modified rosin compound having a UV-absorbing moiety can be determined by, for instance, Gel Permeation
  • the rosin mixture may also comprise at least one rosin compound selected from a rosin ester, a resin acid and a rosin
  • the rosin mixture may comprise mixtures of different modified rosin compounds, e.g. with different number of rosin moieties and/or different UV-absorbing moieties, with different type of rosin moieties and/or different UV-absorbing moieties or both with different type and number of rosin moieties and/or different UV-absorbing moieties. Since rosin is a mixture of rosin compounds (resin acids) most embodiments of this invention will comprise such mixtures.
  • a modified rosin compound derived from a pentaerythritol rosin ester may have 1 to 4 rosin moieties and 1 to 4 UV-absorbing moieties, the number of UV-absorbing moieties being the same or lower than the number of rosin moieties.
  • the rosin mixture comprising the modified rosin compound is generally obtained by reacting a mixture of rosin compounds with a UV-absorbing compound under mixing at a
  • the reaction can be stopped (e.g. by cooling) once the reaction is completed or earlier, if desired.
  • the reaction can be monitored by, for instance, Gel Permeation Chromatography (GPC) , and the reaction can be stopped when, for instance, changes in the peak size of the products are no longer observed.
  • GPC Gel Permeation Chromatography
  • reaction times can be of at least 1 minute, 15 minutes, 0.5 h, 1 h, 2 h, 4 h, 6 h, 8 h, 12 h, 16 h or 24 h.
  • the reaction can be performed in the presence of a solvent.
  • Suitable solvents include, for example,
  • DMSO dimethylsulfoxide
  • DMAC dimethylacetamide
  • reaction can be performed in the absence of a solvent. This advantageously avoids having to remove the solvent at a later stage, reduces the waste
  • reaction may also be performed in the presence of a suitable catalyst.
  • the reaction product can be used as such as a UV- protecting rosin mixture or can be subjected to purification steps (e.g. to remove unreacted starting materials or side products) .
  • the rosin compounds and the UV-absorbing compound can be mixed in any order.
  • the rosin mixture comprising the modified rosin compound is obtained by first heating a mixture of rosin compounds to a temperature of at most 400 °C, in particular from 30 to 400°C, more in particular from 50 to 350 °C, even more in particular from 80 to 300 °C, even more in particular from 160 to 250 °C, and yet more in particular from 190 to 225 °C, and then adding the UV-absorber to the mixture of rosin compounds.
  • the relative amount of UV-absorbing compound with respect to rosin compounds in the reaction may vary.
  • the total amount of the UV-absorbing compound can be from 0.01 wt . % to 75 wt . % based on the total weight of mixture of rosin compounds and UV-absorbing compound, in particular from 0.1 wt.% to 50 wt.%, 0.5 wt.% to 30 wt . % , 1 wt . % to 20 wt . % and from 2 wt.% of 10 wt.%.
  • the rosin source used to provide the modified rosin compound can be selected from, for example, a rosin ester, a resin acid or a rosin derivative, as described above.
  • rosin compounds generally have groups which may undergo a chemical reaction, e.g. an unsaturated group (such as carbon-carbon double bonds, in particular conjugated double bonds such as dienes), an ester group or a carboxylic acid group.
  • Rosin esters of polyalcohols e.g. glycols, glycerol and/or pentaerythritol
  • Rosin derivatives may have other groups.
  • resin acid or rosin ester compounds can be subjected to addition reactions or to
  • Suitable UV-absorbing compounds have a group susceptible of reacting with at least one of the groups present in the rosin compounds, referred hereinafter as a linking group.
  • the linking group may be selected from an unsaturated group (e.g. a double bond, a triple bond and conjugated double bonds), an ester, a carboxylic acid, an amine and an alcohol.
  • the unsaturated group may have carbon and/or heteroatoms (e.g. nitrogen, oxygen or sulfur) .
  • the unsaturated group can be a dienophile.
  • the dienophile may have a carbon-carbon double bond conjugated to at least one electron-withdrawing group.
  • UV-absorbing compounds include for instance compounds having a a, ⁇ -unsaturated carbonyl group (e.g. an acryloyl functionality) , an a, ⁇ -unsaturated nitrile group, and a nitroalkene group.
  • a ⁇ -unsaturated carbonyl group e.g. an acryloyl functionality
  • an a, ⁇ -unsaturated nitrile group e.g. an acryloyl functionality
  • a nitroalkene group e.g. 2- ( 4-benzoyl-3-hydroxy- phenoxy) ethyl acrylate and (2- [3- ( 2H-benzotriazol-2-yl ) -4- hydroxyphenyl ] ethyl methacrylate can be mentioned.
  • Suitable compounds are commercially available, such as 2- (4-benzoyl-3- hydroxyphenoxy) ethyl acrylate, (2- [3- ( 2H-benzotriazol-2-yl ) -4- hydroxyphenyl ] ethyl methacrylate, 4-allyloxy-2-hydroxybenzo- phenone, 2-hydroxy-4 -acryloylethoxy benzophenone , which is another name for 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, and 2- ( 2 ' -methacryloxy-5 ' methylphenyl ) benzotriazole .
  • Other suitable UV-absorbing compounds can be obtained by methods known to the skilled person.
  • UV-absorbing compounds comprising an acryloyl functionality
  • UV-absorbing oligomers or polymers comprising at least one group susceptible of reacting with rosin compounds as described above can also be used. More than one UV-absorbing compound can be used as an ingredient in the reaction.
  • the rosin mixture comprising modified rosin compound can be obtained by reacting a mixture of rosin compounds comprising a rosin ester with a UV-absorbing compound provided with an unsaturated group as the linking group, in particular the unsaturated group can be a dienophile.
  • the rosin mixture comprising a modified rosin compound can be obtained by reacting a mixture of rosin compounds comprising a resin acid with a UV-absorbing compound provided with an alcohol group as the linking group.
  • a rosin mixture comprising a modified rosin compound can be obtained by reacting a mixture of rosin compounds comprising a resin acid with a UV-absorbing compound provided with an unsaturated group as the linking group to provide a rosin mixture comprising a modified resin acid.
  • the rosin mixture obtained can be reacted with an alcohol selected from at least one of glycerol, pentaerythritol , diethylene glycol, triethylene glycol, sorbitol, neopentyl- glycol, trimethylolpropane, methanol, ethanol, butanol, 2-ethyl hexanol, Ce-Cn branched and unbranched alkyl alcohols to provide a rosin mixture comprising a modified rosin ester.
  • an alcohol selected from at least one of glycerol, pentaerythritol , diethylene glycol, triethylene glycol, sorbitol, neopentyl- glycol, trimethylolpropane, methanol, ethanol, butanol, 2-ethyl hexanol, Ce-Cn branched and unbranched alkyl alcohols to provide a rosin mixture comprising a modified rosin ester.
  • UV-absorbing compounds provided with an unsaturated group, and in particular a dienophile, as the linking group may react with the unsaturated groups generally present in rosin compounds, and in particular with conjugated double bonds.
  • the resulting modified rosin compound can be a Diels-Alder adduct formed between the rosin compound and the UV- absorbing compound.
  • the resulting modified rosin compound can also be an adduct resulting from other pericyclic reactions (e.g. an ene reaction) between the unsaturated group of the UV- absorbing compound and the unsaturated group of the rosin compound .
  • UV-absorbing compounds having an ester group or an alcohol group as the linking group may react with, for instance, the carboxylic functionality present in resin acid, e.g. by esterification and transesterification .
  • the rosin compound is linked to the UV-absorbing moiety via an ester bond.
  • UV-absorbing compounds having an amine group as the linking group may react with, for instance, the carboxylic functionality present in resin acid. Accordingly, the rosin compound is linked to the UV-absorbing moiety via an amide bond.
  • UV-absorbing compounds provided with a carboxylic acid as the linking group may react with a residual alcohol group present in a rosin ester of a polyalcohol such as glycerol, pentaerythritol , diethylene glycol, triethylene glycol or sorbitol, neopentylglycol , trimethylolpropane . Accordingly, the rosin compound is also linked to the UV-absorbing moiety via an ester bond.
  • a rosin ester of a polyalcohol such as glycerol, pentaerythritol , diethylene glycol, triethylene glycol or sorbitol, neopentylglycol , trimethylolpropane .
  • the rosin compound is covalently bonded to the UV-absorbing moiety.
  • the covalent bond between the rosin compound and UV- absorber moiety generally involves a linker and, optionally, a linking molecule.
  • a linker is generally present in the UV-absorbing compound, wherein the linker is attached to the UV-absorbing moiety.
  • the linker has a linking group which is able to from a covalent bond with the rosin compound. In one embodiment the linker consist of said linking group.
  • a separate linking molecule is able to form a covalent bond with both the rosin compound and with the UV-absorbing compound. Accordingly, the separate linking molecule has two linking groups.
  • linking group present in the UV-absorbing compound applies to the linking group described herein as part of the linker or the linking molecule. It is within the scope of the skilled person to select UV-absorbing compounds with appropriate linkers and, optionally, linking molecules to react with appropriate rosin compounds to provide
  • the rosin moiety and the UV-absorbing moiety in the modified rosin compound preferably have a short distance to each other. This is achieved by attaching the rosin compound to the UV-absorbing moiety by using linkers and, when applicable, separate linking molecules, of short length.
  • the sum of the main chain (or back-bone) atoms of the linker and, if present, of the separate linking molecule generally is from 1 to 12 atoms, in particular from 2 to 10 atoms, more in particular from 3 to 8 atoms.
  • the number of atoms include the main-chain atoms of the linking groups of the linker and, if present, also the main- chain atoms of the linking groups of the separate linking molecule.
  • Modified rosin compounds as described herein generally have an average molecular weight (MW) from 600 to 2000
  • grams/mol in particular from 700 to 1800, more in particular from 800 to 1600, more in particular from 900 to 1500 grams/mol.
  • the molecular weight can be measured by methods known in the art. For instance, the ASTM D5296-05 method for
  • GPC Gel Permeation Chromatography
  • the rosin mixture comprising the modified rosin compound as described herein, not only has an enhanced UV- resistance itself but also enhances the UV-resistance of
  • compositions comprising the same.
  • the invention relates to a composition
  • a composition comprising the rosin mixture as described herein.
  • This composition can be an intermediate which can be
  • compositions or formulations comprising the same.
  • the composition as described herein may comprise at least 0.01 wt . % of the rosin mixture, based on the total weight of the composition.
  • the composition may have at least 0.1 wt . % , at least 0.5 wt.%, or at least 1 wt . % of the rosin mixture.
  • the rosin mixture can perform the same function as rosin in a common formulation (e.g. may function as a tackifier and as a binder)
  • the composition may comprise higher amounts of the rosin mixture than necessary to prevent degradation by UV light, such as at least 5 wt.%, in particular at least 10 wt%, more in particular at least 20 wt.%, even more in particular at least 50 wt.%, or even more in particular at least 75 wt.%, depending on the requirements of the formulation.
  • a rosin mixture as described herein is particularly suited for use in formulations which can be exposed to UV- radiation (e.g. for outdoor applications).
  • the rosin mixture or compositions comprising the rosin mixture can be used in formulations together with components which can be UV-sensitive .
  • the UV-protecting mixture can be used to protect any formulation from UV-radiation.
  • composition as described herein may comprise polymers, which may or may not suffer from long
  • suitable polymers include polymers commonly used or suitable for use in coating, sealing or adhesive applications.
  • suitable polymers can be selected from at least one of polyacrylate , polyacrylate co ⁇ polymer, butyl rubber, chlorinated rubber, ethylene vinyl acetate, polyamide, polyester, polyisobutylene , polyolefin, polyurethane , and styrene block copolymers.
  • compositions as described herein include, for instance, dyes, antioxidants (such as hindered amine light stabilizers (HALS)), oils,
  • UV-protecting additives including UV-absorbers , UV-filters and/or UV-stabilizers known in the art such as Ti0 2 and Zn0 2 .
  • the composition generally does not require the presence of further UV-protecting additives.
  • the UV-protecting rosin as described herein surprisingly retains the properties of the original rosin compounds, e.g. as a tackifier and as a binder
  • the UV- protecting mixture of rosin compounds can be suitably used in compositions which typically comprise rosin mixtures.
  • compositions typically comprise rosin mixtures.
  • the UV-absorbing moiety is part of the modified rosin compound present in the rosin mixture, migration of the UV-absorbing moiety is prevented, reducing a health and/or environmental hazard and reducing the chances of leaving parts of a formulation vulnerable to UV-radiation .
  • the rosin mixture comprising a modified rosin and the compositions as described herein can suitably be used in
  • UV-absorbing moiety in the modified rosin compound a good distribution of the UV-protection can be achieved.
  • one aspect of the invention relates to adhesive formulations and thermoplastic formulations comprising a rosin mixture as described herein.
  • a rosin mixture as described herein.
  • part or all of the rosin compound used as a tackifier in common adhesive formulations or as a binder in common thermoplastic road marking formulations can be
  • An adhesive formulation may generally comprise 30-70 wt . % of the rosin mixture as a tackifier (e.g. comprising a rosin ester), 20-60 wt . % of a polymer (e.g. styrene-isoprene- styrene (SIS) block copolymer), 0.1-2 wt . % of an antioxidant and the remaining to 100 wt . % of a mineral oil.
  • a tackifier e.g. comprising a rosin ester
  • SIS styrene-isoprene- styrene
  • thermoplastic road marking formulation may generally comprise 10-20 wt . % of the rosin mixture as a binder (e.g.
  • a rosin ester comprising a rosin ester), 1-5 wt . % of mineral oil, 0.5-1.5 wt . % of a wax (e.g. polyethylene wax), 0.5-1.5 wt . % of a
  • thermoplastic polymer e.g. an ethylene vinyl acetate resin (EVA)
  • EVA ethylene vinyl acetate resin
  • stabilizer e.g. stearic acid
  • pigment e.g. titanium dioxide
  • fillers e.g. calcium carbonate
  • An exemplary road marking formulation may be prepared as follows:
  • one aspect of the instant invention relates to the use of the rosin mixture as described herein as an antioxidant. Accordingly, the rosin mixture as described herein can be added to compositions as an antioxidant. In particular, the rosin mixture can be used as antioxidant in formulations where rosin mixtures are normally used .
  • the acid number was measured according to the ASTM D465 method. A sample of a known weight amount was dissolved in isopropyl alcohol. The solution was then titrated with an alcoholic solution of potassium hydroxide. The acid values obtained correspond to the amount of potassium hydroxide used to neutralize said measured amount of sample. This is generally expressed in milligrams of potassium hydroxide per gram of samp1e : mg KOH/g .
  • the softening point was measured according to the Ring and Ball method (ASTM E28-99) .
  • a sample of the rosin mixture A, prepared above, was poured, when still warm, into a metal ring and then cooled. The ring was cleaned in such a way that the material fitted the ring.
  • a steel ball was placed resting on top of the ring. The ring and ball were lowered into a beaker containing glycerol. The glycerol was heated at a rate of 5 °C per minute while stirring. When the ball dropped completely through the ring, the temperature of the glycerol was recorded. This temperature value is reported as the softening point of the rosin mixtures obtained.
  • the rosin mixture A was used as the tackifier in an adhesive composition prepared as follows.
  • Each adhesive composition was applied at 110 °C with a hotmelt coater (Laboratory Laminator LL-100 obtained from
  • PET terephtalate
  • the siliconized release liner paper was removed from the films.
  • the films were then kept in a QUV machine (obtained from the Q-panel Company, UK) whilst being irradiated with a UV- A radiation.
  • the films were irradiated on the side of the film which comprised the adhesive.
  • adhesive compositions comprising the rosin mixture A display better properties than the reference adhesive composition (without the rosin mixture A) after being subjected to the same conditions.
  • the reference adhesive composition loses its adhesive properties after 1 day whereas the adhesive composition
  • both the appearance of cracks and yellowing are delayed when rosin mixture A is present in the adhesive composition. Both cracks and yellowing only start appearing on the third day for adhesive compositions comprising rosin mixture A, whereas in the absence of the rosin mixture A cracking starts on the first day and yellowing on the second day.
  • Adhesive composition Reference Adhesive
  • Adhesive Absence Absence Adhesive Absence Absence properties of of properties of of of
  • the reaction was monitored by Gel permeation chromatography (GPC) using a Waters HPLC system.
  • GPC Gel permeation chromatography
  • a chromatogram was taken for each starting rosin ester, for each starting UV absorbing compound and for each reaction mixture.
  • One sample was taken at the beginning of the reaction (i.e. after the UV absorber is mixed with the rosin ester, referred to in the tables as starting mixture) and another sample was taken at the end of the reaction.
  • the results are shown in Table 3.
  • the chromatogram was obtained by measuring the absorption of the samples at the region from 210 to 400 nm as explained in detail below .
  • the peaks for the rosin ester were generally broad indicating a mixture of species.
  • the starting rosin esters do not show significant absorbance in the 300-400 nm region, whereas the UV-absorbers absorb in the 300-400 nm region.
  • the evolution of the reaction was monitored at 300-400 nm, where the UV-absorber displays absorbance. As the reaction progressed it could be observed that the peak at the retention time of the UV-absorbing compound becomes smaller. A new peak with a retention time in the region of the rosin ester was observed to appear. The new peak was generally observed to become larger with time. This indicates that the UV-absorbing moiety is built onto the rosin ester.
  • the yield of the reaction was provided by the UV- chromatogram.
  • the percentage of unreacted product is based on the area of the peak observed in the 300-400 nm region, at the retention time of the UV-absorber, divided by the total area of peaks observed in the 300-400 nm region.
  • the percentage of reacted product is based on the area of the newly formed peak observed in the 300-400 nm region, close to the retention time of the rosin ester, divided by the total area of the peaks observed in the 300-400 nm region.
  • 100 ⁇ of the sample were automatically injected to a HPLC system fitted with a Waters 717 plus autosampler; a Waters 515 HPLC pump; a Waters Column Heater Module fitted with two mixed E columns (obtained from Polymer laboratories), i.e. a 50- Angstrom column (5 ⁇ ) and a 3 ⁇ guard column; a refractive index (RI) detector (Waters 2414) and a Photodiode Array (PDA) detector (Waters 996) ; and Empower software, all obtained from Waters.
  • the detector and the column heater were set at 40 °C.
  • the samples were run with an isocratic solvent system over 35 minutes with the flow set at 1 ml/min.
  • the chromatogram was registered with the PDA detector with a scanning range from 210 to 400 nm at 1.2 nm intervals.
  • the peaks observed were generally broad indicating the presence of a mixture of species.
  • the retention time as recorded in Table 3 is that of the peak at its highest.
  • acrylate-hydroxybenzophenone 4-benzoyl-3- hydroxyphenoxy ethyl acrylate
  • Table 4 the UV-absorber 2- ( 4-benzoyl-3- hydroxyphenoxy) ethyl acrylate
  • All of the acrylate-hydroxybenzophenone was added to the molten rosin ester in a single addition, with mixing under nitrogen.
  • the reaction mixture was kept at 190°C for 24 hours after which it was cooled down to room temperature.
  • the amount of reacted and unreacted UV-blocking agent was measured by Gel Permeation Chromatography as described above for Examples A-G. The GPC characterization data is not shown for rosin mixtures H-M.
  • the antioxidant properties of the rosin mixtures H-M were determined by measuring the oxidative induction time (OIT) of the rosin mixtures obtained.
  • the oxidative induction time of the starting materials i.e. acrylate-hydroxybenzophenone, SYLVALITETM RE88 and fortified rosin ester
  • the oxidative induction time of the starting materials i.e. acrylate-hydroxybenzophenone, SYLVALITETM RE88 and fortified rosin ester
  • the machine used was a DSC 2910 provided with high pressure cell (obtained from TA
  • Table 5 shows that rosin mixtures comprising a rosin compound modified with a UV-absorbing moiety as described herein have anti-oxidant properties.
  • Examples H-J and the starting rosin ester material (SYLVALITETM RE 88) display equivalent OIT values. They all are within error of the method (i.e. 5%) .
  • examples K and L show higher OIT numbers than the starting rosin ester, indicating improved oxidative stability over the starting material (SYLVALITETM RE88) .
  • the antioxidant effect is observed to a higher extent in Example M, where an increase of OIT of the 76 % with respect to the starting rosin ester.

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur un mélange de colophanes comprenant au moins un composé de colophane modifié ayant une fraction absorbant les UV, laquelle fraction absorbant les UV est dérivée d'un composé choisi parmi une hydroxybenzophénone, une oxybenzone, une dioxybenzone, un oxanilide, un benzotriazole et une hydroxyphényltriazine. L'invention porte également sur un procédé de préparation dudit mélange de colophanes, sur une composition comprenant ledit mélange de colophanes et sur l'utilisation d'une composition comprenant ledit mélange de colophanes comme formulation adhésive ou comme formulation thermoplastique pour la signalisation horizontale sur les routes. En particulier, la composition comprend au moins 0,01 % en poids du mélange de colophanes ; et le procédé comprend la réaction sous mélange à une température d'au maximum 400°C, pendant une durée de 1 minute à 24 h, d'un mélange de composés de colophane avec un composé absorbant les UV choisi parmi une hydroxybenzophénone, une oxybenzone, une dioxybenzone, un oxanilide, un benzotriazole et une hydroxyphényltriazine.
PCT/EP2012/074365 2011-12-05 2012-12-04 Colophane protégeant des uv WO2013083565A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017914A (zh) * 2015-07-21 2015-11-04 厦门双瑞船舶涂料有限公司 一种由松香改性丙烯酸酯制备连接涂料的方法
US10017600B2 (en) 2014-12-15 2018-07-10 Dow Global Technologies Llc Adhesive composition

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DE577691C (de) * 1928-02-17 1933-06-02 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von Harzestern
GB1310909A (en) * 1970-04-09 1973-03-21 Cataphote Corp Hot melt highway marking composition
US4612358A (en) 1984-10-27 1986-09-16 Rohm Gmbh UV-absorbing monomer and polymers thereof
US4985559A (en) 1987-10-15 1991-01-15 University Of Florida UV Absorbing vinyl monomers
US5504152A (en) 1995-01-10 1996-04-02 Arizona Chemical Company Esterification of rosin
GB2293823A (en) * 1994-10-04 1996-04-10 Ciba Geigy Ag 2-Hydroxyphenyltriazines
WO2000006657A2 (fr) * 1998-07-27 2000-02-10 International Paper Company Esters de resine de couleur claire et compositions adhesives
WO2001053376A1 (fr) * 2000-01-18 2001-07-26 Arizona Chemical Company Polymeres prepares a partir de melanges d'amidoamine/polyethylenanine de colophane
CN100358959C (zh) * 2005-10-28 2008-01-02 中国林业科学研究院林产化学工业研究所 高稳定性无色松香季戊四醇酯及其制备方法
US20110054062A1 (en) * 2009-08-26 2011-03-03 Desanto Jr Ronald F UV Pressure-Sensitive Adhesive for Stickers and Labels

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE577691C (de) * 1928-02-17 1933-06-02 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von Harzestern
GB1310909A (en) * 1970-04-09 1973-03-21 Cataphote Corp Hot melt highway marking composition
US4612358A (en) 1984-10-27 1986-09-16 Rohm Gmbh UV-absorbing monomer and polymers thereof
US4985559A (en) 1987-10-15 1991-01-15 University Of Florida UV Absorbing vinyl monomers
GB2293823A (en) * 1994-10-04 1996-04-10 Ciba Geigy Ag 2-Hydroxyphenyltriazines
US5504152A (en) 1995-01-10 1996-04-02 Arizona Chemical Company Esterification of rosin
WO2000006657A2 (fr) * 1998-07-27 2000-02-10 International Paper Company Esters de resine de couleur claire et compositions adhesives
WO2001053376A1 (fr) * 2000-01-18 2001-07-26 Arizona Chemical Company Polymeres prepares a partir de melanges d'amidoamine/polyethylenanine de colophane
CN100358959C (zh) * 2005-10-28 2008-01-02 中国林业科学研究院林产化学工业研究所 高稳定性无色松香季戊四醇酯及其制备方法
US20110054062A1 (en) * 2009-08-26 2011-03-03 Desanto Jr Ronald F UV Pressure-Sensitive Adhesive for Stickers and Labels

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10017600B2 (en) 2014-12-15 2018-07-10 Dow Global Technologies Llc Adhesive composition
CN105017914A (zh) * 2015-07-21 2015-11-04 厦门双瑞船舶涂料有限公司 一种由松香改性丙烯酸酯制备连接涂料的方法

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