Adhesive composition comprising modified tackifier

Abstract

The invention relates to an adhesive composition comprising:-a polymer (A); -a tackifying resin (B) comprising a modified resin (B1); and a use of the adhesive composition.

Description

TECHNICAL FIELD

[0001] The present invention relates to an adhesive composition comprising a polymer (A) and a tackifying resin comprising a modified rosin (B1) and the use thereof. BACKGROUND

[0002] There are different types of adhesives which can be hot melt adhesives, pressure sensitive adhesives, water based adhesives, reactive adhesives, etc.

[0003] These adhesives usually comprise a tackifier based on rosin resins, terpene resins, hydrocarbon resins and mixtures thereof. Hydrocarbon resins are based on petroleum feedstocks, rosin resins are usually based on natural feedstocks obtained from pine trees and terpene resins are produced from natural sources (wood turpentine) or kraft sulfate pulping processes.

[0004] In some applications, rosin ester resins have much better performance than hydrocarbon resins due to their wide compatibility with polymers and better wetting properties on low energy surfaces, and indeed have some advantages over hydrocarbon resins. However, it is well known that rosin esters have a high price fluctuation and the supply is therefore not stable. The high price and price fluctuation, supply instability of rosin resins have a negative impact on adhesive producers.

[0005] There have been some attempts to use acid modified petroleum resins in adhesive compositions. However, the change of tackifier can affect the light stability, heat stability, odor, Gardner color, compatibility with base polymer, adhesion properties, etc. of the adhesive composition, which are not desirable by the users.

[0006] Therefore, there is a need to provide new adhesive compositions to at least partially overcome the above-mentioned drawbacks.

[0007] More preferably, there is a need for an adhesive composition which is less costly than the current adhesive compositions containing rosin ester resins and which exhibits good adhesion properties (e.g. high fiber tear percentage and / or good tack and peel properties over a wider temperature range). SUMMARY

[0008] The present invention will be described in more detail in the following description, but not limited thereto.

[0009] Unless otherwise indicated, percentages in this application are by weight.

[0010] In this document, a number indicated for a given species can apply to that species according to all its definitions (as described herein), including narrower definitions.

[0011] A. Adhesive composition

[0012] This invention relates to adhesive compositions comprising:

[0013] Polymer (A);

[0014] Tackifying resin (B) containing modified resin (B1).

[0015] Polymer (A)

[0016] The polymer (A) may be selected from the group consisting of: polyolefin polymers, styrene block copolymers, polyurethanes, polyamides, acrylic copolymers and mixtures thereof.

[0017] Any polyolefin-based polymer known in the art can be used in this invention.

[0018] Polyolefin-based polymers include both homopolymers and copolymers.

[0019] The polyolefin-based polymer is preferably selected from the group consisting of: vinyl copolymers, amorphous poly-α-olefins (APAO), metallocene-catalyzed polyolefins, and olefin block copolymers.

[0020] The vinyl copolymer is preferably selected from the group consisting of ethylene-vinyl acetate copolymer (EVA) and ethylene-alkyl acrylate copolymer.

[0021] Ethylene-vinyl acetate copolymers (EVA) can be classified by the percentage of vinyl acetate (VA) content and melt flow rate (MFR) or melt index (MI). The most commonly used EVAs contain between approximately 19% and 30% VA by weight. MI values ​​range from approximately 3 to approximately 2500. EVA polymers are marketed under the following trade names: Elvax® from Dow Chemical (formerly DuPont), Ateva® from Celanese, Nipoflex® from Tosoh, and Greenflex® from Distrupol, or EVATHENE® UE653-04 from USI.

[0022] Preferably, the ethylene-vinyl acetate copolymer contains 20% or more vinyl acetate by weight.

[0023] Vinyl acetate content typically refers to the weight percentage of vinyl acetate-derived units in an ethylene-vinyl acetate copolymer.

[0024] The melt index of the ethylene-vinyl acetate copolymer is preferably greater than about 100 g / 10 min, more preferably greater than 150 g / 10 min, and even more preferably greater than 300 g / 10 min.

[0025] The melt index of ethylene-vinyl acetate copolymers was determined according to ASTM D1238 using a weight load of 2.16 kg and a test temperature of 190°C.

[0026] The terms “melt index” or “melt flow rate (MFR)” used in this article are used interchangeably.

[0027] Ethylene-alkyl acrylate copolymers typically include ethylene-methacrylate, ethylene-ethyl acrylate, or ethylene-butyl acrylate copolymers.

[0028] Amorphous polyalphaolefins (APAO) are typically produced using Ziegler-Natta catalysts and can be made from a variety of monomers, including but not limited to propylene, ethylene, butene, hexene, and octene.

[0029] Examples of APAO include, but are not limited to: amorphous (random) propylene (APP), amorphous propylene / ethylene (APE), amorphous propylene / butene (APB), amorphous propylene / hexene (APH), and amorphous propylene / ethylene / butene. Many manufacturers produce a variety of homopolymers, copolymers, and terpolymers. These include Evonik Industries, which produces Vestoplast® polymers; REXtac, LLC, which produces the Rextac® RT series of materials; and Eastman Chemical, a manufacturer of the Eastoflex® series of polymers. All are characterized by low crystallinity, as measured by DSC.

[0030] Metallocene-catalyzed polyolefins, also known as polyolefin elastomers, are produced using metallocene catalysis. Examples of these metallocene polymers include Dow Chemical's Affinity® and Engage® polymers, and Idemitsu's (Japan) L-MODU®. Metallocene polyolefin polymers are also supplied by several other companies, such as ExxonMobil (USA), LyondellBasel Industrial Holdings (Netherlands), Chevron Phillips Chemical Company (USA), Total SA (France), SABIC (Saudi Arabia), Nippon Polymer Co., Ltd., Braskem AG (Brazil), LG Chem Co., Ltd. (South Korea), and others.

[0031] Olefin block copolymers (OBCs) can be produced using chain shuttling catalysis technology, which produces linear block structures of monomers rather than random polymers produced by Ziegler-Natta or traditional metallocene technology. OBCs are produced by Dow Chemical Company under the trademark Infuse®. OBCs can be crystallizable ethylene-octene blocks (hard) and amorphous ethylene-octene blocks (soft). The block structure imparts much better high temperature resistance and elasticity to the polymer compared to typical metallocene random polymers of similar density. While certain grades of Infuse® have lower heat of fusion (about 20 Joules / gram), they are not considered amorphous polyalphaolefins because of the complete difference in polymer structure (i.e. block vs. random) and are specifically produced to have crystalline regions. They not only differ in structure, but also differ greatly in physical properties, with OBCs having better elastic recovery, resistance to compression set, and resistance to high temperatures.

[0032] Polyurethanes can be prepared according to methods known in the art, for example, one-step or two-step processes. The reaction can be carried out in the presence of a catalyst. Typical catalysts include organotin, tertiary amine or zinc salts. Polyurethanes are generally prepared by the reaction of polyisocyanates with polyols. Polyurethanes can be prepared as disclosed in US5866656 or US6465104.

[0033] There are also some commercial thermoplastic polyurethanes. For example, mention can be made of the « ELASTOLLAN® » series sold by BASF, the « Estane® » series sold by LUBRIZOL, the « DESMOPAN® » series sold by COVESTRO or the « Pellethane® » series sold by DOW. For example, there is Pellethane® 2103-70A (obtained more than 98% from methylene diphenyl diisocyanate, 1,4-butanediol and polytetramethylene glycol), or Elastollan® 1170 A10, 1175A10W by BASF, FJ-146P by FWU JI RESINS CHEMICALS (polyester-based aromatic thermoplastic polyurethane), and Pearlbond 5717 NT2 (polyester-based thermoplastic polyurethane) sold by LUBRIZOL. TM 5717 NT2 (polyester-based thermoplastic polyurethane).

[0034] Acrylic-based copolymers can be derived from monomers comprising alkyl methacrylate; alkyl acrylate; hydroxyalkyl acrylate or hydroxyalkyl methacrylate; or vinyl ester or an acidic monomer.

[0035] Alkyl methacrylates can include alkyl methacrylates having from 1 to about 20 carbon atoms in the alkyl group. For example, alkyl methacrylates can include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, and dodecyl methacrylate.

[0036] Alkyl acrylates can include alkyl acrylates having from 1 to about 20 carbon atoms in the alkyl group. For example, alkyl acrylates can be selected from the group consisting of n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, iso-bomyl acrylate, iso-bomyl methyl acrylate, ethyl acrylate, iso-octyl acrylate, decyl acrylate, and hexyl acrylate.

[0037] Hydroxyalkyl acrylates or hydroxyalkyl methacrylates can include, but are not limited to, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

[0038] Vinyl esters can include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, and versatile vinyl esters.

[0039] Acid monomers can include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, dimethacrylic acid, maleic acid, and fumaric acid.

[0040] For example, Arkema markets various series of acrylic-based copolymers under the trademark Flexcryl®.

[0041] Styrene block copolymers are copolymers that include at least one styrene block, including styrene triblock copolymers and styrene diblock copolymers.

[0042] The styrene block copolymers have at least one A block comprising styrene and at least one B block comprising, for example, an elastomeric conjugated diene (e.g., hydrogenated and non-hydrogenated conjugated dienes), a hemi-terpene (e.g., hydrogenated and non-hydrogenated hemi-terpenes), and combinations thereof. The A blocks and B blocks are combined with one another in any combination such that the resulting copolymers exhibit a variety of structures, including, for example, random, linear, branched, radial, star, comb, tapered, and combinations thereof. The block copolymers can exhibit any form, including, for example, linear A-B blocks, linear A-B-A blocks, linear A-(B-A)n-B multi-blocks, and radial (A-B)n-Y blocks (where Y is a polyvalent compound and n is an integer of at least 3), tetra-block copolymers (e.g., A-B-A-B), and penta-block copolymers having an A-B-A-B-A structure.

[0043] Suitable styrene A blocks include, for example, styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, and combinations thereof.

[0044] Suitable blocky elastomeric conjugated diene B blocks include, for example, butadiene (e.g., polybutadiene), isoprene (e.g., polyisoprene), 2,3-dimethyl- 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and combinations thereof, as well as hydrogenated versions thereof, such as, for example, ethylene, propylene, butylene, and combinations thereof.

[0045] Suitable B blocks hemiterpenes include, for example, β-farnesene.

[0046] The average styrene content of the styrene block copolymer is preferably from 15 wt% to 45 wt%, more preferably from 15 wt% to 25 wt%.

[0047] The styrene block copolymer preferably comprises from 10 wt% to 80 wt%, more preferably from 30 wt% to 70 wt%, and even more preferably from 40 wt% to 60 wt% diblock.

[0048] "Diblock content" refers to the weight proportion of diblock copolymer in the styrene block copolymer.

[0049] The styrene block copolymer is preferably selected from the group consisting of SB, SI, SEB, SEP, SBBS, SBS, SEBS, SEPS, SEEPS, SIBS, SIS, random block SBR, random block SIR, and mixtures thereof.

[0050] Preferably, the styrene block copolymer is SIS, SI, or mixtures thereof.

[0051] “SBBS” refers to a styrene-butadiene-butene-styrene triblock copolymer. “SBS” refers to a styrene-butadiene-styrene triblock copolymer. “SEBS” refers to a styrene-ethylene-butene-styrene triblock copolymer. “SEPS” refers to a styrene-ethylene-propylene-styrene triblock copolymer. “SEEPS” refers to a styrene-ethylene-ethylene-propylene-styrene triblock copolymer. “SIBS refers to a styrene-isoprene-butadiene-styrene triblock copolymer. “SIS” refers to a styrene-isoprene-styrene triblock copolymer. “Random block SBR” refers to a random block styrene butadiene copolymer (part of the styrene is present as a polystyrene block). “Random block SIR” refers to a random block isoprene butadiene copolymer (part of the styrene is present as a polystyrene block). “SB” refers to a styrene-butadiene diblock copolymer. “SI” refers to a styrene-isoprene diblock copolymer. “SEB” refers to a styrene-ethylene-butene diblock copolymer. “SEP” refers to a styrene-ethylene-propylene diblock copolymer.

[0052] Useful commercial styrene block copolymers include the KRATON D and G series by Kraton Polymers, the EUROPRENE Sol T series by Versalis (Eni Group), the SOLPRENE series by Dynasol Elastomers, the SINOPEC series by SINOPEC, and the Taipol and Vector series by TSRC Corporation. Other useful examples include:

[0053] - Sinopec® YH-1126, a linear SIS triblock copolymer with a styrene content of 16% and a diblock content of 50%;

[0054] - Sinopec® YH-1209, a linear SIS triblock copolymer with a styrene content of 30% and a diblock content lower than 1%;

[0055] - Kraton® D1152, a mixture of a linear SBS triblock copolymer and a SB diblock copolymer, with a styrene content of 29.5 wt% relative to the total weight of the mixture, an average molecular weight of about 122000 g / mol, a melt flow index or MFI (measured according to ISO 1133) of 8.5 g / 10 min at 200°C and 5 kg load, and a SB diblock content of about 17 wt% relative to the total weight of the mixture.

[0056] - Kraton® D1161, a mixture of a linear SIS triblock copolymer and a SI diblock copolymer, having a styrene content of 15 wt% relative to the total weight of the mixture, an MFI (measured according to ISO 1133) of 9 g / 10 min at 200°C and a load of 5 kg, an average molecular weight of about 220000 g / mol, and a SI diblock content of about 19 wt% relative to the total weight of the mixture.

[0057] - Taipol® SBS 4202 by TSRC, a linear SBS triblock copolymer having a styrene content of 40 wt% relative to the total weight of the triblock copolymer, an MFI (measured according to ASTM D1238) of 3 to 10 g / 10 min at 190°C and a load of 5 kg, an average molecular weight of about 102400 g / mol.

[0058] - Vector® 4411 by TSRC, a linear SIS triblock copolymer having a styrene content of 44 wt% relative to the total weight of the triblock copolymer, an MFI (measured according to ASTM D1238) of 40 g / 10 min at 200°C and a load of 5 kg, an average molecular weight of about 106000 g / mol.

[0059] - Europrene® SOL TE9326 by Versalis, a linear SIS triblock copolymer having a styrene block content of about 30%, a diblock content of about 15%.

[0060] Preferably, the weight average molecular weight of the polymer (A) is greater than 5000 g / mol, more preferably greater than or equal to 10000 g / mol. More preferably, its molecular weight is greater than or equal to 15000 g / mol.

[0061] Preferably, the melt flow index (MI, measured according to ISO 1133) of the polymer (A) is greater than 6 g / 10 min, more preferably greater than 25 g / 10 min, and even more preferably greater than 150 g / 10 min.

[0062] The polymer (A) is preferably selected from the group consisting of ethylene-vinyl acetate copolymers (EVA), styrene block copolymers, and mixtures thereof. More preferably, the polymer (A) is a styrene block copolymer. Even more preferably, it is a SIS, SI, or a mixture thereof.

[0063] The adhesive composition can comprise 10 to 70% by weight of the total weight of the adhesive composition of the polymer (A) (or mixture of polymers (A)), preferably 15 to 50% by weight, and more preferably 20 to 40% by weight of the polymer (A) (or mixture of polymers (A)).

[0064] Tackifying resin (B)

[0065] The adhesive composition comprises a tackifying resin (B) comprising a modified resin (B1).

[0066] The terms "tackifier" and "tackifying resin" can be used interchangeably.

[0067] Modified resin (B1)

[0068] According to the present application, the modified resin (B1) is a rosin or rosin ester modified with a petroleum resin.

[0069] The modified resin (B1) is preferably not hydrogenated.

[0070] The acid value of the modified resin (B1) preferably ranges from 5 to 32 mg KOH / g, more preferably from 10 to 30 mg KOH / g, and even more preferably from 12 to 20 mg KOH / g. The acid value is measured according to the GB / T 2895-2008 standard.

[0071] The softening point of the modified resin (B1) preferably ranges from 80°C to 120°C, more preferably from 90°C to 100°C. The softening point is measured according to the GB / T 15332-1994 standard.

[0072] The melt viscosity of the modified resin (B1) at 150°C is preferably less than or equal to 5000 mPas, more preferably less than or equal to 2000 mPas, and even more preferably in the range of 500 to 1500 mPas. The melt viscosity is measured according to the GB / T 2794-2013 standard.

[0073] The average molecular weight (Mw) of the modified resin (B1) is preferably less than or equal to 10000 g / mol, more preferably less than or equal to 5000 g / mol, and even more preferably less than or equal to 2000 g / mol.

[0074] Mw is determined by GPC using polystyrene as standard. More specifically, the measurement is performed on a Waters e2695 GPC instrument equipped with IR and UV detectors, using polystyrene of different molecular weights to build the calibration curve (calibration range 600-300000 g / mol), under the following conditions: 0.1 g of sample is dissolved in 10 ml of THF and 0.01 ml of toluene, the solution is filtered with a 0.45 pm filter and injected in 2 ml vials to be sent to the instrument for analysis.

[0075] Preferably, the modified resin (B1 ) has a Gardner color less than 6, more preferably ranging from 1 to 5. The Gardner color is measured according to the ASTM D1544-04 standard.

[0076] The modified resin (B1 ) is preferably prepared by reaction (or preferably derived from) by:

[0077] i) a rosin resin, a polyol and a petroleum resin; or

[0078] ii) a rosin ester resin and a petroleum resin.

[0079] The reactions i) and ii) can be performed in the presence of a catalyst.

[0080] The reactions i) and ii) can be performed at a temperature ranging from 220°C to 270°C, preferably from 250°C to 270°C.

[0081] The reactions i) and ii) can be performed for 1 to 12 hours, preferably from 5 to 8 hours.

[0082] In reaction i), the weight ratio of rosin resin to petroleum resin preferably ranges from 99:1 to 55:45.

[0083] In reaction ii), the weight ratio of rosin ester resin to petroleum resin preferably ranges from 99:1 to 55:45.

[0084] The rosin resin can be any rosin resin known by the person skilled in the art. The rosin can be any natural or modified rosin. Preferably, the rosin resin is selected from the group consisting of gum rosin, wood rosin, tall oil rosin, distilled rosin, dimeric rosin, polymeric rosin and mixtures thereof.

[0085] The rosin resin comprises non-hydrogenated resins, fully hydrogenated resins and partially hydrogenated resins.

[0086] More preferably, the rosin resin is a fatty rosin.

[0087] The polyol comprises 2 or more hydroxyl groups.

[0088] The polyol is preferably selected from the group consisting of diols, triols, tetraols, pentaols, hexaols and mixtures thereof.

[0089] For mixtures, if diols are present in the mixture, they are present in a weight content of less than 20 wt%, even more preferably less than 10 wt%, based on the sum of the weight content of all polyols.

[0090] The diols can be selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol and mixtures thereof.

[0091] The triols can be selected from the group consisting of glycerol, trimethylolpropane and mixtures thereof.

[0092] The tetraols can be selected from the group consisting of pentaerythritol, tetraethylene glycol and mixtures thereof.

[0093] Preferably, the polyol is selected from triols, tetraols and mixtures thereof, such as glycerol, pentaerythritol, and more preferably the polyol is a tetraol, such as pentaerythritol.

[0094] The petroleum resin is preferably selected from the group consisting of:

[0095] C5 resins;

[0096] C9 resins;

[0097] C5 / C9 resins;

[0098] DCPD resins;

[0099] mixtures thereof.

[0100] As used herein, the term "C5 resin" refers to aliphatic C5 hydrocarbon resin produced from the polymerization of monomers comprising C5 and / or C6 olefin species (boiling point range of about 20 °C to about 200 °C at atmospheric pressure). These monomers are typically produced in petroleum processing processes, such as cracking. Aliphatic C5 hydrocarbon resins can be produced by any method known in the art. Aliphatic C5 hydrocarbon thermoplastic resins can be prepared by cationic polymerization of cracked petroleum feedstocks containing C5 and C6 paraffins, olefins, and dienes, also known as "C5 monomers." These monomer streams are composed of cationically polymerizable monomers such as, for example, 1,3-pentadiene (the primary reaction component), as well as cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene. Polymerization is typically catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (A1C13), and alkyl aluminum chlorides). In addition to the reactive components, non-polymerizable components in the feedstock can include saturated hydrocarbons such as pentane, cyclopentane, or 2-methylpentane, which in some cases co-distill with the unsaturated components. Solid acid catalysts can also be used to produce aliphatic C5 hydrocarbon resins. Aliphatic C5 hydrocarbon resins include non-hydrogenated, partially hydrogenated, or fully hydrogenated resins. Aliphatic C5 thermoplastic resins are available from Eastman Chemical Company (Kingsport, Tenn., USA) as Piccotac® C5 and Eastotac® C5 H2 thermoplastic resins.

[0101] As used herein, the term "C5 / C9 resin" refers to an aliphatic / aromatic C5 / C9 hydrocarbon resin that is polymerized from monomers comprising at least one unsaturated aromatic C8, C9, and / or C10 species (boiling point range at atmospheric pressure from about 100 °C to about 300 °C) and at least one monomer comprising a C5 and / or C6 olefin species (boiling point range at atmospheric pressure from about 20 °C to about 200 °C). The C5 and / or C6 species generally include alkanes, alkenes, and dienes, also known as "C5 monomers." These monomer streams generally consist of cationically polymerizable monomers such as 1,3-pentadiene (the primary reaction component) as well as cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene. The unsaturated aromatic C8, C9, and / or C10 monomers are derived from petroleum distillates resulting from naphtha cracking and are known as "C9 monomers." These monomer streams consist of cationically polymerizable monomers such as styrene, a-methylstyrene, β-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. Cationic polymerization can be catalyzed using Friedel-Crafts polymerization catalysts, for example, Lewis acids such as boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkyl aluminum chlorides. Solid acid catalysts can also be used to produce aliphatic / aromatic C5 / C9 hydrocarbon resins. In addition to the reactive components, non-polymerizable components can include aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, indane, methylindane, naphthalene, and other similar materials. In some embodiments, the non-polymerizable components in the feed stream are incorporated into the thermoplastic resin through alkylation reactions. Aliphatic / aromatic C5 / C9 hydrocarbon resins include non-hydrogenated, partially hydrogenated resins, and hydrogenated resins. Aliphatic / aromatic C5 / C9 resins are available from Eastman Chemical Company as Piccotac® thermoplastic resins. The ratio of C5 to C9 is not limited. In other words, the amount of C5 monomers in a C5 / C9 thermoplastic resin can vary from 0.1% to 100%, and vice versa, the amount of C9 monomers in a C5 / C9 thermoplastic resin can vary from 0.1% to 100%.

[0102] As used herein, the term "C9 resin" refers to aromatic C9 hydrocarbon thermoplastic resins, which are produced by polymerization of monomers (boiling point range of about 100 °C to about 300 °C at atmospheric pressure) comprising unsaturated aromatic C8, C9, and / or C10 species. These monomers are typically produced in petroleum processing, such as cracking. Aromatic C9 hydrocarbon resins can be produced by any method known in the art. Aromatic C9 hydrocarbon resins can be prepared by cationic polymerization of aromatic C8, C9, and / or C10 unsaturated monomers derived from petroleum fractions produced by naphtha cracking, known as "C9 monomers." These monomer streams are typically composed of cationically polymerizable monomers such as styrene, alpha-methylstyrene (AMS), beta-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. In some embodiments of C9 resins, aliphatic olefin monomers containing four to six carbon atoms are also present during polymerization. Polymerization can be catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids, e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (A1C13), and alkyl aluminum chlorides. In addition to the reactive components, non-polymerizable components include, but are not limited to, aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, indane, methylindane, naphthalene, and other similar chemicals. In some embodiments, non-polymerizable components in the feed stream are incorporated into the thermoplastic resin through alkylation reactions. C9 hydrocarbon resins include non-hydrogenated, partially hydrogenated, or fully hydrogenated resins. Aromatic C9 hydrocarbon resins are available as Picco® C9 thermoplastic resins, and aliphatic hydrogenated and aliphatic / aromatic partially hydrogenated C9H2 hydrocarbon thermoplastic resins are available from Eastman Chemical Company as Regalite® thermoplastic resins.

[0103] As used herein, the term "DCPD resin" refers to dicyclopentadiene (DCPD) resins, most commonly formed by ring-opening metathesis polymerization (ROMP) of dicyclopentadiene in the presence of a strong acid catalyst such as, for example, aqueous maleic acid or sulfuric acid, or by thermal polymerization. Dicyclopentadiene is also formed in some embodiments from two cyclopentadiene molecules through a Diels-Alder reaction, and exists in two stereoisomers: endo-DCPD and exo-DCPD. Typically, more than 90% of the DCPD molecules present in commercial grade DCPD are endo. DCPD resins include aromatic modified DCPD resins as well as hydrogenated, partially hydrogenated, and non-hydrogenated resins, but herein H2 DCPD is described in most cases only because H2 DCPD is the most readily available form of DCPD on the market. Aromatically modified DCPD is also considered a DCPD thermoplastic resin. Aromatic modification is performed, for example, by C9 resin oil, styrene, or alpha-methylstyrene (AMS), etc. Hydrogenated and partially hydrogenated DCPD, as well as hydrogenated and partially hydrogenated aromatic modified DCPD resins are commercially available as Escorez® 5000 series resins (ExxonMobil Chemical Company, TX, USA).

[0104] Preferably, the petroleum resin is not a DCPD resin.

[0105] Preferably, the petroleum resin is not hydrogenated.

[0106] Preferably, the petroleum resin is not acid modified, such as, for example, not maleic anhydride modified.

[0107] More preferably, the petroleum resin is selected from the group consisting of C5 resins, C9 resins, and C5 / C9 resins.

[0108] Commercial examples of petroleum resins are: Escorez® 5400, which is a hydrogenated dicyclopentadiene resin provided by ExxonMobil Chemical Company, having a softening temperature of 100 °C; Quintone® DX390N, which is a non-hydrogenated aliphatic / aromatic petroleum hydrocarbon resin sold by Zeon Corporation, having a softening point of 90 °C; Sukorez® SU400, which is a hydrogenated aliphatic / aromatic petroleum hydrocarbon resin sold by Kolon, HH2-1003 (C5 / C9 petroleum hydrocarbon resin) sold by Henghe Material Technology Co., Ltd.; M-90Z, which is a C5 / C9 petroleum hydrocarbon resin sold by Luha; Escorez® 2203LC (C5 / C9 resin) sold by ExxonMobil Chemical; and Sukorez® SU 120 (fully hydrogenated DCPD resin) sold by ExxonMobil Chemical.

[0109] The rosin ester resin can be glycol, glycerol and / or pentaerythritol esters of natural rosin and modified rosins (typically as described above). This includes their hydrogenated forms.

[0110] Preferably, the rosin ester is a glycerol ester of light wood rosin, a glycerol ester of hydrogenated rosin, a glycerol ester of polymerized rosin, a pentaerythritol ester of light wood rosin, a pentaerythritol ester of hydrogenated rosin, a pentaerythritol ester of tall oil rosin, a tall oil rosin ester obtained from a mixture of glycerol and pentaerythritol, a light wood rosin ester obtained from a mixture of glycerol and pentaerythritol, a hydrogenated rosin ester obtained from a mixture of glycerol and pentaerythritol, a polymerized rosin ester obtained from a mixture of glycerol and pentaerythritol, and a phenolic modified pentaerythritol ester of rosin.

[0111] More preferably, the rosin ester is a pentaerythritol ester or glycerol ester of gum rosin.

[0112] Commercial examples of rosin esters are Sylvalite® RE 100L or RE 100S (pentaerythritol based tall oil rosin ester), Sylvalite® RE 85L (glycerol ester of tall oil rosin) from Kraton; Sylvalite® 9000 (fully hydrogenated tall oil rosin ester) from Kraton.

[0113] The modified resin (B1 ) can also be purchased from some suppliers on the market, such as KOMOTAC® KE100H provided by Guangdong KOMO Co. Ltd.

[0114] More preferably, the modified resin (B1 ) is prepared (or derived) by reacting:

[0115] - i) gum rosin, a polyol selected from glycerol or pentaerythritol, and a petroleum resin selected from C5 resin, C9 resin and C5 / C9 resin, the petroleum resin being preferably unhydrogenated; or

[0116] - ii) a rosin ester resin based on glycerol or pentaerythritol, and a petroleum resin selected from C5 resin, C9 resin and C5 / C9 resin, the petroleum resin being preferably unhydrogenated.

[0117] Preferably, the modified resin (B1 ) does not comprise groups derived from maleic anhydride, maleic acid.

[0118] Preferably, the modified resin (B1 ) is not acid modified, and more preferably, is not maleic acid modified or not maleic anhydride modified.

[0119] Other tackifiers

[0120] The tackifying resin (B) can further comprise (in addition to the tackifier (B1 )):

[0121] - petroleum resins (B2); or

[0122] - rosin resins (B3); or

[0123] - rosin ester resins (B4); or

[0124] - mixtures thereof.

[0125] The above description of rosin resins, rosin ester resins and petroleum resins also applies herein to tackifiers (B2), (B3) and (B4).

[0126] The tackifier resin (B) can comprise from 40% to 100%, preferably from 60% to 100%, more preferably from 80% to 100% by weight of modified resin (B1), relative to the total weight of the tackifier resin (B).

[0127] The adhesive composition preferably comprises from 1% to 70% by weight, more preferably from 10% to 60% by weight, and even more preferably from 20% to 60% by weight of tackifier resin (B), based on the total weight of the adhesive composition.

[0128] Plasticizer (C1)

[0129] The adhesive composition can further comprise a plasticizer (C1).

[0130] Any plasticizer known to the person skilled in the art can be used.

[0131] The plasticizer (C1) can be selected from the group consisting of olefin oligomers, low molecular weight polyolefins (such as liquid polybutenes), low molecular weight non-aromatic polymers, phthalates, mineral oils, waxes, vegetable oils and animal oils and derivatives thereof.

[0132] The plasticizer (C1) comprises polyethylene, polypropylene, polybutene, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene or the like, having an average molecular weight between about 350 g / mol and about 10000 g / mol.

[0133] The mineral oil is preferably selected from the group consisting of naphthenic oils, paraffinic oils or any mixture thereof.

[0134] Naphthenic oils and paraffinic oils are petroleum-based oils comprising a mixture of naphthenic hydrocarbons (aliphatic, saturated or unsaturated C4 to C7-membered rings, and preferably aliphatic, saturated or unsaturated C4 to C6-membered rings; for example, naphthenic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane can be mentioned), paraffinic hydrocarbons (saturated, linear or branched alkanes) and aromatic hydrocarbons (aromatic rings, which can be monocyclic or polycyclic, and preferably C6-membered aromatic rings).

[0135] The classification of naphthenic and paraffinic oils is determined based on the content of each type of hydrocarbon in the oil. Typically, paraffinic oils have a paraffinic hydrocarbon content of at least 50% by weight; naphthenic oils have a naphthenic hydrocarbon content of between 30% and 40% by weight, relative to the total weight of the mineral oil.

[0136] Examples of commercial mineral oils are: naphthenic oils sold under the trade name NYFLEX® 223 and NYFLEX® 222B by NYNAS or naphthenic oil sold under the trade name KN4010 by Karamay.

[0137] Suitable vegetable and animal oils include glycerol esters of common fatty acids and their derivatives.

[0138] The wax can be selected from the group consisting of petroleum waxes, such as paraffin wax, Fischer-Tropsch wax, ethylene-vinyl acetate (EVA) wax, polyolefin wax, and any mixture thereof.

[0139] “Paraffin wax” means a wax derived from crude oil. It typically consists of a complex mixture of hydrocarbons having the following general properties: non-reactive; non-toxic; good water resistance; clean burning fuel; colorless. Paraffin wax is characterized by having a well-defined crystal structure. Paraffin wax generally has a melting point of between about 43 °C and about 71 °C. Paraffin wax typically contains a large amount of straight-chain hydrocarbons, and can also contain branched-chain hydrocarbons, such as isoparaffins and other branched-chain species, as well as cycloalkanes, such as cycloparaffins and other ring-containing species.

[0140] “Fischer-Tropsch wax” means a wax obtained by the so-called Fischer-Tropsch process. The Fischer-Tropsch process comprises the conversion of synthesis gas, which mainly comprises hydrogen and carbon monoxide, into hydrocarbons. The conversion is achieved by contacting the synthesis gas with a Fischer-Tropsch catalyst, typically an iron- or cobalt-based catalyst, in a fixed bed or slurry bed reactor under low- or high-temperature Fischer-Tropsch operating conditions. In this way, a mixture of hydrocarbons having different boiling point ranges is obtained. The Fischer-Tropsch wax is then recovered from the mixture of hydrocarbons, e.g. by distillation. Fischer-Tropsch wax typically has a composition in which about 80% by volume thereof has a boiling point higher than 550 °C atmospheric equivalent temperature (“AET”).

[0141] “EVA wax” means an oligomeric polymeric compound prepared by a process comprising the copolymerization of ethylene monomers and vinyl acetate monomers, and having the following properties: (a) solid at room temperature; (b) low melting point; (c) insoluble in water. The EVA copolymer of the EVA wax can be functionalized or modified in any possible way.

[0142] As used herein, the term "polyolefin wax" refers to those polymeric or long chain entities composed of olefin monomer units. Such materials can be purchased from Westlake Chemical Corporation (Houston, TX) under the trade name "Epolene" and from Honeywell Corporation (Morristown, NJ) under the trade name "A-C".

[0143] The wax can be a commercially available wax. Examples of commercially available waxes suitable for use in the present application include the Fischer-Tropsch waxes sold by Shell under the trade name SX60S (freezing point 58-62°C), SX70S (freezing point 67-72°C), SX80S (freezing point 78-85°C) and SX105 (freezing point 101-108°C), and the Fischer-Tropsch wax sold by Sasol under the trade name C-80M (freezing point 80-85°C). Other examples are the 64# paraffin wax (melting point 64-66°C) from Sinopec, and the EVA wax (vinyl acetate content 13 wt%, drop point 92°C, viscosity at 140°C 595 mPa.s) sold by Honeywell under the trade name AC-400A.

[0144] Preferably, the plasticizer (C1) in the adhesive composition is selected from mineral oil or a wax.

[0145] The adhesive composition can comprise from 0% to 50% by weight of the total weight of the adhesive composition of the plasticizer (C1), preferably from 1% to 40% by weight, more preferably from 5% to 20% by weight.

[0146] Antioxidant (C2)

[0147] The adhesive composition can comprise an antioxidant (C2).

[0148] The adhesive composition comprises from about 0 to about 5%, preferably from 0 to about 3%, more preferably from about 0.1 to about 3%, more preferably from about 0.1 to about 2% by weight of the total weight of the adhesive composition of the antioxidant.

[0149] Suitable antioxidants are added to help protect the above-mentioned polymers, and thus the overall adhesive system, from the effects of heat and oxidative degradation normally occurring during the manufacture and application of the adhesive composition, and ultimately the product when normally exposed to ambient surroundings. Such degradation is typically manifested as a deterioration in the appearance, physical properties and performance characteristics of the hot melt adhesive composition.

[0150] Among the antioxidants that can be used, mention can be made of high-molecular-weight hindered phenols and multifunctional phenols, such as the sulphur-containing and phosphorus-containing phenols. Hindered phenols are well known to those skilled in the art, and their characteristic feature can be that they also contain, in the phenolic compound, a bulky group that is spatially close to the phenolic hydroxyl group. In particular, a tert-butyl group is generally substituted on the benzene ring in at least one ortho position relative to the phenolic hydroxyl group. The presence of these bulky substituents in the vicinity of the hydroxyl group serves to slow down its stretching frequency and to slow down its reactivity accordingly; this steric hindrance thus confers on the phenolic compound its stabilizing properties. Representative hindered phenols include: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene; pentaerythrityl tetra-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 4,4'-methylenebis(4- methyl-6-tert-butylphenol); 2,6-di-tert-butylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n- octylthio)-1,3,5-triazine; 2,3,6-tris(4-hydroxy-3,5-di-tert-butyl-phenoxy)-1,3,5-triazine; di-n- octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; 2-(n-octyl-thio)ethyl-3,5-di-tert- butyl-4-hydroxybenzoate; and sorbitol hexa-3(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate.

[0151] The performance of these antioxidants can be further enhanced by the use in combination with: (1 ) synergists such as thiodipropionic acid esters and phosphites; examples of which include dilaurylthiodipropionate (DLTDP); and (2) chelating agents and metal deactivators, for example ethylenediaminetetraacetic acid, its salts and disalicylidenepropylene diimine.

[0152] Suitable antioxidants include those commercially available under the trade names: BASF's Irganox® 1010 (Tetra(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane), Irgafos® 168 (Tris(2,4-di-tert-butylphenyl)phosphate) and Irganox® PS800 (3,3'-thiobis-1,1 '-propanoic acid dodecyl ester); Shuangjian's Chinox® 1010 (Pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)); Everspring Chemical's Evernox® 1010 and Everfos® 168; Songwon's Songnox® 10 and 1680, BASF's Irganox PS800.

[0153] Other additives (C3)

[0154] The adhesive composition can further comprise at least one other additive, preferably in an amount of 0 to 10% by weight, for example 0.1 to 10% by weight, based on the total weight of the adhesive composition.

[0155] The additive can be selected from the group consisting of inert colorants (such as titanium dioxide), fillers (such as talc, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, aluminum oxide, hydrated aluminum oxide, glass microbeads, ceramic microbeads, thermoplastic microspheres and mixtures thereof), surfactants, crosslinking agents, nucleating agents, reactive compounds, flame-retardant mineral or organic agents, UV or / and infrared (IR) light absorbers (such as HALS hindered amine light stabilizers), UV or / and IR fluorescent agents and mixtures thereof. These optional other additives are well known in the art.

[0156] The type of additive generally depends on the end use of the adhesive composition.

[0157] Preferably, the adhesive composition does not comprise polycaprolactone.

[0158] Adhesive composition

[0159] The adhesive composition can be a hot melt adhesive composition, a pressure sensitive adhesive composition (PSA), a hot melt pressure sensitive adhesive composition (HMPSA).

[0160] A pressure sensitive adhesive (PSA) is a substance that imparts tack to the carrier layer on which it is coated at ambient temperature (23°C). This tack enables the self-adhesive carrier to adhere instantaneously to all types of substrates under the action of light and brief pressure. PSAs are widely used in the manufacture of self-adhesive labels that adhere to articles (for example packaging) for the purpose of displaying information (such as bar codes, names, prices) and / or for decorative purposes. PSAs are also used in the manufacture of self-adhesive adhesive tapes for various uses. For example, in addition to the transparent adhesive tapes widely used in everyday life, mention can be made of the shaping and assembly of cardboard packaging; surface protection for paint jobs in the construction industry; maintenance of cables in the transport industry; and joining of carpeting with double-sided adhesive tape.

[0161] Hot-melt adhesives or hot-melt glues are substances which are solid at ambient temperature (23°C) and which do not contain either water or solvents. They are applied in the molten state and solidify on cooling, thus forming a joint which adheres the substrates to be assembled due to the adhesive strength of the joint. Certain hot-melt glues are formulated to give the carrier they coat the property of being relatively hard and tack-free. Other hot-melt glues give the carrier the property of being relatively soft and highly adhesive; these are the PSAs widely used to manufacture self-adhesive articles such as self-adhesive labels. The corresponding adhesives are designated by the name "hot-melt pressure-sensitive adhesives" (or HMPSA). HMPSA are thus in a different category from hot-melt glues HM. Due to their adhesive strength, they also make it possible to adhere labels or tapes firmly to the desired substrates, whether it be packaging which needs to be labelled or panels to be assembled, for example.

[0162] Preferably, the adhesive composition is a hot-melt pressure-sensitive adhesive composition or a hot-melt adhesive composition.

[0163] In one embodiment, if the adhesive composition is a hot-melt pressure-sensitive adhesive composition, it preferably comprises:

[0164] - from 10% to 70% by weight of a polymer (A) chosen from styrene block copolymers;

[0165] - from 1% to 70% by weight of a tackifying resin (B) comprising a modified resin (B1) and optionally a petroleum resin (B2);

[0166] - from 0% to 50% by weight of a plasticizer (C1); and

[0167] - from 0% to 5% by weight of an antioxidant (C2).

[0168] In another embodiment, if the adhesive composition is a hot-melt adhesive composition, it preferably comprises:

[0169] - from 10% to 70% by weight of a polymer (A) chosen from vinyl copolymers;

[0170] - from 1% to 70% by weight of a tackifying resin (B) comprising a modified resin (B1) and optionally a petroleum resin (B2);

[0171] - from 0% to 50% by weight of a plasticizer (C1); and

[0172] - from 0% to 5% by weight of an antioxidant (C2).

[0173] In another embodiment, the adhesive comprises:

[0174] - 10% to 70% by weight of polymer (A), said polymer (A) being selected from amorphous poly-α-olefins;

[0175] - 1% to 70% by weight of tackifying resin (B), said tackifying resin (B) comprising modified resin (B1) and optionally petroleum resin (B2).

[0176] - 0% to 50% by weight of plasticizer (C1); and

[0177] - 0% to 5% antioxidant (C2) by weight.

[0178] In another embodiment, if the adhesive composition is a hot melt adhesive composition, then the adhesive comprises:

[0179] - 10% to 70% by weight of polymer (A), wherein polymer (A) is selected from polyurethane;

[0180] - 1% to 70% by weight of tackifying resin (B), said tackifying resin (B) comprising modified resin (B1) and optionally petroleum resin (B2).

[0181] - 0% to 50% by weight of plasticizer (C1); and

[0182] - 0% to 5% antioxidant (C2) by weight.

[0183] The viscosity of the adhesive composition at 170°C is preferably in the range of 500 to 10,000 mPas, more preferably in the range of 600 to 8,000 mPas. The viscosity is measured according to standard GB / T 2794-2013.

[0184] The softening point of the adhesive composition is preferably in the range of 80°C to 120°C. The softening point is measured according to GB / T 15332-1994.

[0185] The adhesive compositions of the present invention advantageously exhibit good adhesive properties (such as, for example, a good balance between 180° peel and loop tack, or even high fiber tearing over a wide temperature range).

[0186] The adhesive composition of the present invention advantageously exhibits low odor, low cost, low color, and good adhesive properties (adhesion, fiber tearing, etc.).

[0187] B. Process for preparing an adhesive composition

[0188] The present invention also relates to a process for preparing the above-described adhesive composition.

[0189] The adhesive composition of the present application can be produced using any technique known in the art.

[0190] For example, the adhesive composition can be prepared by mixing the polymer (A) with the tackifying resin (B) in the molten state. As mentioned above, the optional other ingredients or additives of the composition, in particular the at least one antioxidant, can be mixed with the above components. Another method of preparing the adhesive composition is to add the tackifying resin (B) to the polymer (A), optionally in the presence of a plasticizer or other additives.

[0191] Preferably, the mixing step is carried out at a temperature of 140 to 180 °C. The ingredients are preferably mixed for at least 1 hour.

[0192] The adhesive composition according to the present application can be prepared in the presence of oxygen, such as under an air atmosphere, or preferably under an inert atmosphere, such as under a carbon dioxide or nitrogen environment, to limit potential degradation due to oxidation reactions.

[0193] C. Use

[0194] The present application relates to the use of the adhesive composition as defined herein for bonding two substrates together, or as a surface coating of a substrate.

[0195] The adhesive composition can be used for a variety of applications, including but not limited to disposable articles, packaging (such as boxes, cartons, trays, etc.), paper converting, laminates, pressure sensitive adhesives, tapes, labels, assembly, bookbinding, wood bonding (such as edge banding, profile wrapping, etc.), transportation, reflective coatings, road marking, etc.

[0196] The adhesive composition as defined above can be applied to any substrate. Preferred substrates include wood; paper; paperboard; plastic; thermoplastic; rubber; metal; metal foil (such as aluminum foil and tin foil); metallized surfaces; cloth; nonwoven (in particular polypropylene spunbond fibers or nonwovens); spunbond fibers; paperboard; stone; gypsum; glass (including silicon oxide coatings applied by evaporating silicon oxide (SiOx) on the surface of a film); foam; rock; ceramic; film; polymeric foam (such as polyurethane foam); substrates coated with inks, dyes, pigments, PVDC and the like; or combinations thereof.

[0197] In particular embodiments, the adhesive compositions of the present application can be used in packaging articles. The packaging articles can be used as, for example, cartons, containers, crates, boxes, corrugated boxes, or trays. More specifically, the packaging articles can be used as cereal products, cookie products, beer packaging, frozen food products, paper bags, beverage cups, milk cartons, juice cartons, beverage cups, or as containers for shipping produce, to name a few example uses.

[0198] The packaging articles are formed by applying the adhesive composition to at least a portion of one or more packaging elements. The packaging elements can be made from paper, paperboard, boxboard, label stock, corrugated board, flake board, kraft paper, hardboard, fiberboard, plastic resins, metals, metal alloys, foils, films, plastic films, laminates, sheets, or any combination thereof. In one aspect, the adhesive composition can be used to join or bond two or more packaging elements together, wherein the packaging elements are made from the same or different types of materials. Thus, the packaging elements can be made from paper, paperboard, boxboard, label stock, corrugated board, flake board, kraft paper, hardboard, fiberboard, plastic resins, metals, metal alloys, foils, films, plastic films, laminates, sheets, or any combination thereof, respectively. One or more of the packaging elements can also be coated individually with paper, foil, metal, metal alloy, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamide, homopolymers thereof, and combinations and copolymers thereof.

[0199] The adhesive compositions of the present application can be used to manufacture tape, or alternatively, to apply labels to various articles, such as containers, magazines, and the like. The labels / tape can be selected from a variety of materials, including paper, non-paper films (such as polypropylene (e.g., polypropylene (PP), oriented polypropylene (OP), and biaxially oriented polypropylene (BOPP)), polyethylene, and the like). The containers can be metal (e.g., aluminum or steel) or plastic (polyethylene terephthalate (PET), high density polyethylene (HDPE), and polypropylene). The labels can be spot labels, i.e., labels that do not extend completely around the container. Alternatively, the labels can be wraparound labels, i.e., labels that wrap completely around the entire container. If the labels are wraparound labels, they can be fed into the applicator on a spool. Alternatively, the labels are pre-cut and fed in a stack. In the wraparound label application method, the label stock is fed into a label station. Then, a pick-up adhesive and a lap glue are applied to the label, typically from the same glue pot. The pick-up adhesive adheres the leading end of the label to the container. Then, the lap glue wraps the adhered label around itself with an overlapping portion of the label overlapping itself.

[0200] The adhesive composition is also suitable for use in various applications and structures, including, for example, disposable absorbent articles, including, for example, disposable diapers, adult incontinence products, sanitary napkins, medical dressings (such as wound care products), bandages, surgical pads, pet training pads (such as puppy pads), and meat packaging products, as well as absorbent article components, including, for example, absorbent elements, absorbent cores, impermeable layers (such as backsheets), paper towels (such as packaging paper towels), acquisition layers, and woven and nonwoven web layers (such as top sheets, absorbent papers), and elastic materials. The adhesive composition is suitable for use on substrates made from various fibers, including, for example, natural cellulosic fibers (such as wood pulp, cotton, viscose, starch, and the like), silk, PLA (poly-lactic acid), PHA (poly-hydroxyalkanoate), PBS (polybutylene succinate), PBAT (polybutylene adipate terephthalate), and wool; synthetic fibers such as nylon, rayon, polyester, acrylic, polypropylene, polyethylene, polyvinyl chloride, polyurethane, and glass; recycled fibers, and various combinations thereof. The hot melt adhesive composition can be used on various films, including polyethylene, polypropylene, ethylene-vinyl acetate, ethylene copolymers, bio-based films (such as PLA, PHA, starch, and the like). The composition can be applied to the substrates using various application techniques, including, for example, slot coating, spraying (including, for example, spiral spraying and random spraying), screen printing, foaming, engraved rollers, extrusion, and meltblown application techniques.

[0201] In disposable articles, the adhesive composition can be used as an elastic attachment adhesive, a positioning adhesive, and / or a core stabilization adhesive.

[0202] The adhesive composition can be used in woodworking processes. Woodworking processes include forming a woodworking article by applying the adhesive composition to at least a portion of a structural element. The structural element can include a variety of materials, including but not limited to wood or plywood, or plastic or veneer. For example, the structural element can also include wood, lumber, fiberboard, gypsum board, gypsum, wallboard, plywood, PVC, melamine, polyester, impregnated paper, and gypsum plasterboard. The woodworking process can be used to make, for example, indoor furniture, outdoor furniture, decorative moldings, moldings, doors, sashes, windows, millwork, and cabinets, among others.

[0203] The present invention also relates to an article comprising the adhesive composition as defined herein.

[0204] The article can be selected from the group consisting of adhesive tapes, labels, boxes, cartons, bags, and disposable absorbent articles.

[0205] Aspects

[0206] Aspect 1 : An adhesive composition comprising:

[0207] - a polymer (A);

[0208] - tackifying resin (B) comprising a modified resin (B1).

[0209] Aspect 2: The adhesive composition according to aspect 1, wherein the polymer (A) is selected from the group consisting of polyolefin-based polymers, styrene block copolymers, polyurethanes, polyamides, acrylic-based copolymers and mixtures thereof.

[0210] Aspect 3: The adhesive composition according to aspect 2, wherein the polyolefin-based polymer is selected from the group consisting of ethylene-based copolymers, amorphous polyalphaolefins (APAOs), metallocene-catalyzed polyolefins, olefin block copolymers.

[0211] Aspect 4: The adhesive composition according to aspect 2, wherein the styrene block copolymer is preferably selected from the group consisting of SB, SI, SEB, SEP, SBBS, SBS, SEBS, SEPS, SEEPS, SIBS, SIS, random-block SBR, random-block SIR and mixtures thereof.

[0212] Aspect 5: The adhesive composition according to aspect 4, wherein the styrene block copolymer is SIS, SI or a mixture thereof.

[0213] Aspect 6: The adhesive composition according to any one of aspects 1 to 5, wherein the weight average molecular weight of the polymer (A) is greater than or equal to 15000 g / mol.

[0214] Aspect 7: The adhesive composition according to any one of aspects 1 to 6, wherein the polymer (A) is selected from the group consisting of ethylene-vinyl acetate copolymers (EVA), styrene block copolymers and mixtures thereof.

[0215] Aspect 8: The adhesive composition according to any one of aspects 1 to 7, wherein the adhesive composition comprises from 10% to 70% by weight of the polymer (A) (or mixture of polymers (A)), preferably from 15% to 50% by weight, and more preferably from 20% to 40% by weight of the polymer (A) (or mixture of polymers (A)) based on the total weight of the adhesive composition.

[0216] Aspect 9: The adhesive composition according to any one of aspects 1 to 8, wherein the modified resin (B1) is not hydrogenated.

[0217] Aspect 10: The adhesive composition according to any one of aspects 1 to 9, wherein the acid value of the modified resin (B1) ranges from 5 to 32 mg KOH / g, preferably from 10 to 30 mg KOH / g, and more preferably from 12 to 20 mg KOH / g.

[0218] Aspect 11 : The adhesive composition according to any one of aspects 1 to 10, wherein the modified resin (B1 ) has a melt viscosity at 150°C of less than or equal to 5000 mPas, preferably less than or equal to 2000 mPas, and more preferably in the range of 500 to 1500 mPas.

[0219] Aspect 12: The adhesive composition according to any one of aspects 1 to 11, wherein the modified resin (B1 ) has an average molecular weight (Mw) of less than or equal to 10000 g / mol, preferably less than or equal to 5000 g / mol, and more preferably less than or equal to 2000 g / mol.

[0220] Aspect 13: The adhesive composition according to any one of aspects 1 to 12, wherein the modified resin (B1 ) has a Gardner color of less than 6, preferably in the range of 1 to 5.

[0221] Aspect 14: The adhesive composition according to any one of aspects 1 to 13, wherein the modified resin (B1 ) is prepared by reaction of:

[0222] iii) a rosin resin, a polyol and a petroleum resin; or

[0223] iv) a rosin ester resin and a petroleum resin.

[0224] Aspect 15: The adhesive composition according to aspect 14, wherein:

[0225] - in reaction i), the weight ratio of rosin resin to petroleum resin is in the range of 99:1 to 55:45;

[0226] - in reaction ii), the weight ratio of rosin ester resin to petroleum resin is in the range of 99:1 to 55:45.

[0227] Aspect 16: The adhesive composition according to any one of aspects 14 or 15, wherein the rosin resin is selected from the group consisting of a gum rosin, a wood rosin, a tall oil rosin, a distilled rosin, a dimeric rosin, a polymerized rosin, and mixtures thereof, the rosin resin being preferably a gum rosin.

[0228] Aspect 17: The adhesive composition according to any one of aspects 14 to 16, wherein the polyol is selected from the group consisting of a triol, a tetraol, and mixtures thereof, such as for example glycerol, pentaerythritol, and more preferably the polyol is a tetraol, such as pentaerythritol.

[0229] Aspect 18: The adhesive composition according to any one of aspects 14 to 17, wherein the petroleum resin is selected from the group consisting of:

[0230] - a C5 resin;

[0231] - C9 resin;

[0232] - C5 / C9 resin;

[0233] - DCPD resin;

[0234] - mixtures thereof.

[0235] Aspect 19: The adhesive composition according to any one of aspects 14 to 18, wherein the petroleum resin is not a DCPD resin.

[0236] Aspect 20: The adhesive composition according to any one of aspects 14 to 19, wherein the petroleum resin is not hydrogenated.

[0237] Aspect 21 : The adhesive composition according to any one of aspects 14 to 20, wherein the petroleum resin is selected from the group consisting of C5 resin, C9 resin and C5 / C9 resin.

[0238] Aspect 22: The adhesive composition according to any one of aspects 14 to 21, wherein the rosin ester is a glycerol ester of light wood rosin, a glycerol ester of hydrogenated rosin, a glycerol ester of polymerized rosin, a pentaerythritol ester of light wood rosin, a pentaerythritol ester of hydrogenated rosin, a pentaerythritol ester of tall oil rosin, a tall oil rosin ester obtained from a mixture of glycerol and pentaerythritol, a light wood rosin ester obtained from a mixture of glycerol and pentaerythritol, a hydrogenated rosin ester obtained from a mixture of glycerol and pentaerythritol, a polymerized rosin ester obtained from a mixture of glycerol and pentaerythritol, and a phenolic modified pentaerythritol ester of rosin.

[0239] Aspect 23: The adhesive composition according to any one of aspects 14 to 22, wherein the rosin ester is a pentaerythritol ester or a glycerol ester of gum rosin.

[0240] Aspect 24: The adhesive composition according to any one of aspects 1 to 23, wherein the modified resin (B1 ) is prepared (or derived) by reacting:

[0241] - i) a gum rosin, selected from a polyol of glycerol or pentaerythritol, and a petroleum resin selected from the group consisting of C5 resin, C9 resin and C5 / C9 resin, the petroleum resin being preferably not hydrogenated; or

[0242] - ii) a glycerol or pentaerythritol based rosin ester resin, and a petroleum resin selected from the group consisting of C5 resin, C9 resin and C5 / C9 resin, the petroleum resin being preferably not hydrogenated.

[0243] Aspect 25: The adhesive composition according to any one of aspects 1 to 24, the tackifying resin (B) comprises 40% to 100%, preferably 60% to 100%, more preferably 80% to 100% by weight of modified resin (B1) relative to the total weight of tackifying resin (B).

[0244] Aspect 26: The adhesive composition according to any one of aspects 1 to 25, wherein the adhesive composition comprises 1% to 70% by weight, more preferably 10% to 60% by weight, and even more preferably 20% to 60% by weight of tackifying resin (B) based on the total weight of the adhesive composition.

[0245] Aspect 27: The adhesive composition according to any one of aspects 1 to 26, wherein the adhesive composition further comprises a plasticizer (C1).

[0246] Aspect 28: The adhesive composition according to aspect 27, wherein the plasticizer (C1) is selected from the group consisting of an olefin oligomer, a low molecular weight polyolefin such as liquid polybutene, a low molecular weight non-aromatic polymer, a phthalate, a mineral oil, a wax, a vegetable oil, and an animal oil, and derivatives thereof.

[0247] Aspect 29: The adhesive composition according to aspect 27 or 28, wherein the plasticizer (C1) in the adhesive composition is selected from a mineral oil or a wax.

[0248] Aspect 30: The adhesive composition according to any one of aspects 1 to 29, wherein the adhesive composition comprises 0% to 50% by weight, preferably 1% to 40% by weight, more preferably 5% to 20% by weight of plasticizer (C1) based on the total weight of the adhesive composition.

[0249] Aspect 31 : The adhesive composition according to any one of aspects 1 to 30, wherein the adhesive composition does not comprise polycaprolactone.

[0250] Aspect 32: The adhesive composition according to any one of aspects 1 to 31, wherein the adhesive composition is a hot melt adhesive composition, a pressure sensitive adhesive composition (PSA), a hot melt pressure sensitive adhesive composition (HMPSA), preferably the adhesive composition is a hot melt pressure sensitive adhesive composition or a hot melt adhesive composition.

[0251] Aspect 33: The adhesive composition according to any one of aspects 1 to 32, wherein the adhesive composition is a hot melt pressure sensitive adhesive composition comprising:

[0252] - 10% to 70% by weight of a polymer (A) selected from a styrene block copolymer;

[0253] - 1 to 70 % by weight of tackifying resins (B) including modified resins (B1 ) and optionally petroleum resins (B2);

[0254] - 0 to 50 % by weight of plasticizers (C1 ); and

[0255] - 0 to 5 % by weight of antioxidants (C2).

[0256] Aspect 34: The adhesive composition according to any one of aspects 1 to 32, wherein the adhesive composition is a hot melt adhesive composition comprising:

[0257] - 10 to 70 % by weight of polymers (A) selected from ethylene copolymers;

[0258] - 1 to 70 % by weight of tackifying resins (B) including modified resins (B1 ) and optionally petroleum resins (B2);

[0259] - 0 to 50 % by weight of plasticizers (C1 ); and

[0260] - 0 to 5 % by weight of antioxidants (C2).

[0261] Aspect 35: The adhesive composition according to any one of aspects 1 to 34, having a viscosity in the range of 500 to 10000 mPas at 170 °C, more preferably in the range of 600 to 8000 mPas.

[0262] Aspect 36: Use of the adhesive composition as defined in any one of aspects 1 to 34 for bonding two substrates together or as a coating on a substrate surface.

[0263] Aspect 37: The use according to aspect 36 for various applications including but not limited to disposable articles, packaging (such as boxes, cartons, trays, etc.), paper products processing, laminates, pressure sensitive adhesives, tapes, labels, assembly, bookbinding, wood bonding (such as edge banding, profile wrapping, etc.), transportation, reflective coatings, road marking, and similar applications.

[0264] Aspect 38: An article comprising the adhesive composition according to any one of aspects 1 to 36.

[0265] Aspect 39: The article according to aspect 38 selected from the group consisting of tapes, labels, boxes, cartons, bags, and disposable absorbent articles.

[0266] The ranges disclosed herein include the lower and upper limits. For example, the expression "from x to y" or "between x and y" includes the limits x and y.

[0267] The following examples are intended to illustrate the application and are not intended to limit the application.

[0268] Experimental part

[0269] The raw materials shown in the table were used.

[0270] Table 1. Raw materials

[0271]

[0272] Test methods:

[0273] Gardner color was measured according to standard ASTM D1544-04

[0274] Acid value was measured according to standard GB / T 2895-2008

[0275] Softening point was measured according to standard GB / T 15332-1994

[0276] Viscosity was measured according to standard GB / T 2794-2013

[0277] Rheology was used to analyze the viscoelastic properties of the materials.

[0278] Temperature sweep for adhesive composition: a temperature sweep was performed on a TA DHR-2 instrument from 140 °C to -10 °C at 10 rad / s on a 25 mm parallel plate. The cooling rate from 140 °C to 40 °C was set to 5 °C / min and the cooling rate from 40 °C to -10 °C was set to 2 °C / min.

[0279] Adhesion strength 180° peel test

[0280] The adhesive strength of the adhesive compositions was evaluated by a 180° peel test performed on a specific substrate panel as described in FINAT test method No. 1 (FTM 1), FTM 1 is disclosed in FINAT Technical Handbook 6thEdition 2001. FINAT is the International Federation of Self-Adhesive Label Manufacturers and Converters.

[0281] The principle of this test is as follows: a carrier layer consisting of a 50 pm thick PET film is pre-coated with the adhesive composition in an amount of 18 g / m 2 .

[0282] A test specimen in the form of a rectangular strip (25.4 mm x 175 mm) is cut from the self-adhesive carrier thus obtained. This test specimen is fixed to a plate consisting of a specific substrate. The resulting assembly is left to stand for 20 minutes at room temperature. It is then introduced into a tensile testing apparatus that is capable of performing strip peeling or separation at an angle of 180° and at a separation speed of 300 mm / min. This apparatus measures the force required to separate the strip under these conditions.

[0283] The results are expressed in N / 2.54 cm and are indicated together with the nature of the substrate of the plate.

[0284] Instantaneous tack : Loop tack test

[0285] The instant tack of the composition is evaluated by the loop tack test described in FINAT test method No. 9 (FTM9).

[0286] A carrier layer consisting of a 50 pm thick PET film is pre-coated with the HMPSA in an amount of 18 g / m2, thus obtaining a rectangular strip of 25.4 mm x 175 mm. The two ends of this strip are joined together to form a loop, with the adhesive layer facing outwards. The joined ends are placed in the moving grips of a tensile testing apparatus, which is capable of applying a displacement rate of 300 millimetres / minute along a vertical axis and can perform a reciprocating motion. First, the lower part of the loop, placed in a vertical position, is brought into contact with a horizontal specific substrate plate of 25 mm x 30 mm on a square area of approximately 25 mm measured on each side. Once contact is established, the displacement direction of the grips is reversed. The instant tack is the maximum value of the force required to completely disengage the loop from the substrate plate.

[0287] The results are expressed in N / 2.54 cm and are indicated together with the nature of the substrate of the horizontal plate.

[0288] Experiments were performed on each HMPSA composition in the 180° peel strength test, the loop tack test. The coating conditions used in each of these experiments are as follows:

[0289]

[0290] “Temperature” is the temperature of the tank containing the adhesive composition to be applied.

[0291] “Width” is the width of the coating of the HMPSA on the primary substrate.

[0292] “Addition amount” is the amount of HMPSA coated on the primary substrate.

[0293] "O.T." stands for Open Time, which is the time required for the HMPSA to reach the compression zone (where the secondary substrate is applied onto the HMPSA) from the nozzle to the primary substrate, coated.

[0294] Fiber tear percentage test:

[0295] Carton substrates were cut to standard size 45 mm x 75 mm. The adhesive was melted and then applied as a small drop through a glue gun nozzle (1 mm - 1.5 mm, melted for 30 minutes) onto the standard piece, outside of the carton. The drop was about 3 grams per linear meter, with a length of about 40 mm. The secondary substrate was applied on the other side and pressed with a weight of 1 kg for about 3 seconds. The bonded samples were left to rest for 2 hours at 23 °C and then placed at 5 °C, 20 °C and 50 °C (refrigerator or oven) for 24 hours. After 24 hours, the substrates of the construction were separated from each other by hand at the test temperature (e.g. immediately after the sample was removed from the conditioned room). The surface of the adhesive composition was observed and the percentage of the surface area of the adhesive composition covered by fibers was determined and recorded. At least three samples were prepared and tested for each adhesive composition. The results were reported in units of percentage of fiber tear.

[0296] Example 1 Preparation of SBC-based HMPSA E1 and E2 (present invention) and comparative compositions CE1 and CE2

[0297] The adhesive compositions in Table 1 were prepared as follows: Polymer Al was added to the mixture of plasticizer and antioxidant mixture already heated at a temperature of 165 °C. After obtaining a homogeneous mixture (90 minutes), the resin was added in two to three times and the mixture was stirred for 1 hour.

[0298] In the table, % is the weight percentage based on the total weight of the hot melt adhesive composition.

[0299] Table 2: HMPSA

[0300]

[0301] CP*: clean panel - no visible stain on the panel

[0302] *CF: cohesive failure - during the test, the adhesive film broke, resulting in adhesive residue on the panel and front material.

[0303] **PS: panel stain - the test area discolored, but there was no adhesive residue.

[0304] Example 2 Preparation of EVA-based HMA E3 for rigid packaging applications

[0305] Adhesive composition E3 was prepared by mixing the raw materials at 165 °C for 2 hours.

[0306] Table 3: EVA based adhesives

[0307]

[0308] Adhesive composition E3 comprising modified rosin (B1 ) advantageously exhibits a high percentage of fibre tear in the temperature range from 20 °C to 50 °C.

Claims

1. An adhesive composition comprising: - Polymer (A); - Tackifying resin (B) containing modified resin (B1).

2. The adhesive composition according to claim 1, wherein the polymer (A) is selected from the group consisting of polyolefin-based polymers, styrene block copolymers, polyurethanes, polyamides, acrylic copolymers, and mixtures thereof, more preferably from the group consisting of ethylene-vinyl acetate copolymers (EVA), styrene block copolymers, and mixtures thereof.

3. The adhesive composition according to any one of claims 1 to 2, wherein the weight-average molecular weight of polymer (A) is greater than or equal to 15,000 g / mol.

4. The adhesive composition according to any one of claims 1 to 3, wherein the modified resin (B1) is not hydrogenated.

5. The adhesive composition according to any one of claims 1 to 4, wherein the acid value of the modified resin (B1) is in the range of 5 to 32 mg KOH / g, preferably 10 to 30 mg KOH / g, and more preferably 12 to 20 mg KOH / g.

6. The adhesive composition according to any one of claims 1 to 5, wherein the average molecular weight (Mw) of the modified resin (B1) is less than or equal to 10,000 g / mol, preferably less than or equal to 5,000 g / mol, and more preferably less than or equal to 2,000 g / mol.

7. The adhesive composition according to any one of claims 1 to 6, wherein the modified resin (B1) is prepared by reacting as follows: i) Rosin resin, polyols, and petroleum resins; or ii) Rosin ester resins and petroleum resins.

8. The adhesive composition according to claim 7, wherein: - In reaction i), the weight ratio of rosin resin to petroleum resin ranges from 99:1 to 55:45; - In reaction ii), the weight ratio of rosin ester resin to petroleum resin ranges from 99:1 to 55:

45.

9. The adhesive composition according to any one of claims 7 or 8, wherein the petroleum resin is selected from C5 resin, C9 resin and C5 / C9 resin.

10. The adhesive composition according to any one of claims 1 to 9, wherein the modified resin (B1) is prepared by reacting as follows: -i) rosin, a polyol selected from glycerol or pentaerythritol, and a petroleum resin selected from C5 resin, C9 resin, and C5 / C9 resin, wherein the petroleum resin is preferably unhydrogenated; or -ii) Rosin ester resins based on glycerol or pentaerythritol, and petroleum resins selected from C5 resins, C9 resins and C5 / C9 resins, wherein the petroleum resins are preferably unhydrogenated.

11. The adhesive composition according to any one of claims 1 to 10, wherein, based on the total weight of the adhesive composition, the adhesive composition comprises 1% to 70% by weight, more preferably 10% to 60% by weight, and even more preferably 20% to 60% by weight of tackifying resin (B).

12. The adhesive composition according to any one of claims 1 to 11, wherein the adhesive composition further comprises a plasticizer (C1), said plasticizer (C1) preferably selected from the group consisting of free olefin oligomers, low molecular weight polyolefins such as liquid polybutene, low molecular weight non-aromatic polymers, phthalates, mineral oils, waxes, vegetable oils and animal oils and their derivatives.

13. The adhesive composition according to any one of claims 1 to 12, wherein the adhesive composition does not contain polycaprolactone.

14. The adhesive composition according to any one of claims 1 to 13, characterized in that... The adhesive composition is a hot melt adhesive composition, a pressure-sensitive adhesive composition (PSA), or a hot melt pressure-sensitive adhesive composition (HMPSA), preferably a hot melt pressure-sensitive adhesive composition or a hot melt adhesive composition.

15. The adhesive composition as defined in any one of claims 1 to 14 is used for bonding two substrates together or as a coating on a substrate surface.

16. An article comprising an adhesive composition according to any one of claims 1 to 14, preferably the article being selected from the group consisting of tapes, labels, boxes, cartons, bags, and disposable absorbent articles.

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