Adhesive composition containing a modified tackifier

Abstract

The present invention relates to an adhesive composition comprising a polymer (A), a tackifying resin (B) containing a modified resin (B1), and the use thereof.

Description

Technical Field

[0001] The present invention relates to an adhesive composition comprising a polymer (A) and a tackifier resin containing modified rosin (B1), and its use.

Background Art

[0002] There are different types of adhesives that can be hot melt adhesives, pressure sensitive adhesives, water-based adhesives, reactive adhesives, and the like.

[0003] These adhesives typically contain a tackifier based on either a rosin resin, a terpene resin, a hydrocarbon resin, or a mixture thereof. Hydrocarbon resins are based on petroleum raw materials, rosin resins are typically based on natural raw materials obtained from pine trees, and terpene resins are produced from natural sources, wood turpentine oil, or from the kraft sulfate pulping process.

[0004] In some applications, rosin ester resins have much better performance than hydrocarbon resins due to their broad compatibility with polymers and better wetting performance with low-energy surfaces, which has several advantages over hydrocarbon resins. However, it is well known that the price of rosin esters fluctuates greatly, and thus the supply is unstable. The high price and price fluctuations, and the unstable supply of rosin resins have an adverse impact on adhesive manufacturers.

[0005] Some attempts have been made to use acid-modified petroleum resins in adhesive compositions. However, changes in the tackifier can potentially affect the light stability, thermal stability, odor, Gardner color, compatibility with the base polymer, adhesion performance,... of the adhesive composition. These are undesirable for users.

Summary of the Invention

[0006] Therefore, there is a need to provide a new adhesive composition that at least partially overcomes the above disadvantages.

[0007] More preferably, there is a need for an adhesive composition that is less expensive than current adhesive compositions containing rosin ester resins and exhibits good adhesive properties, such as a high fiber tear rate and / or good tackiness and release properties over a wide temperature range. [Modes for carrying out the invention]

[0008] The present invention will now be described in more detail without limitation in the following description. Unless otherwise specified, percentages in this application refer to weight percentages. In this text, the quantities given for a given species can be applied to that species according to all of its definitions, including narrower definitions (as stated in this text).

[0009] A. <Adhesive Compositions> The present invention -Polymer (A), - Tackifying resin (B) containing modified resin (B1) This relates to adhesive compositions containing [specific components].

[0010] <Polymer (A)> Polymer (A) may be selected from the group consisting of polyolefin polymers, styrene block copolymers, polyurethanes, polyamides, acrylic copolymers, and mixtures thereof.

[0011] Any polyolefin polymer known in the art can be used in this invention. Polyolefin polymers include both homopolymers and copolymers.

[0012] The polyolefin polymer is preferably selected from the group consisting of ethylene copolymers, amorphous poly-alpha-olefins (APAOs), metallocene-catalyzed polyolefins, and olefin block copolymers.

[0013] The ethylene copolymer is preferably selected from the group consisting of ethylene-vinyl acetate copolymer (EVA) and ethylene-alkyl acrylate copolymer.

[0014] Ethylene-vinyl acetate copolymers (EVA) can be classified by their vinyl acetate (VA) content and melt flow rate (MFR) or melt index (MI). The most commonly used EVAs contain approximately 19% to 30% by weight of VA. MI values ​​can range from approximately 3 to 2500. EVA polymers are marketed under trade names such as Elvax(R) from DOW Chemical (formerly DuPont), Ateva(R) from Celanese Corporation, Nipoflex(R) from Tosoh, Greenflex(R) from Distrupol, or EVATHENE(R) UE653-04 from USI.

[0015] Preferably, the ethylene-vinyl acetate copolymer contains 20% by weight or more of vinyl acetate.

[0016] The vinyl acetate content is typically the weight percentage of vinyl acetate-derived units in the ethylene-vinyl acetate copolymer.

[0017] The ethylene-vinyl acetate copolymer preferably has a melt index of more than about 100 g / 10 min, more preferably more than 150 g / 10 min, and even more preferably more than 300 g / 10 min.

[0018] The melt index of ethylene-vinyl acetate copolymer is determined according to ASTM D1238, using a load of 2.16 kg and a test temperature of 190°C.

[0019] As used herein, the terms "melt index" and "melt flow rate (MFR)" are interchangeable.

[0020] Ethylene-alkyl acrylate copolymers typically include ethylene-methyl acrylate, ethylene-ethyl acrylate, or ethylene-butyl acrylate copolymers.

[0021] Amorphous poly-alpha-olefins (APAOs) are typically produced intentionally using Ziegler-Natta catalysis and can be manufactured using a variety of monomers, including but not limited to propylene, ethylene, butene, hexene, and octene.

[0022] Examples of APAOs include, but are not limited to, amorphous propylene (APP), amorphous propylene / ethylene (APE), amorphous propylene / butene (APB), amorphous propylene / hexene (APH), and amorphous propylene / ethylene / butene. A wide variety of homopolymers, copolymers, and terpolymers are produced by numerous manufacturers. These include Evonik Industries, which produces Vestoplast(R) polymers; REXtac, LLC, which produces materials in the Rextac(R) RT range; and Eastman Chemical, the manufacturer of polymers in the Eastoflex(R) line. All of them are characterized by having a low degree of crystallinity, as measured by DSC.

[0023] Metallocene-catalyzed polyolefins, also known as polyolefin elastomers, are manufactured using metallocene catalyst technology. Examples of these metallocene polymers include Affinity(R) and Engage(R) polymers from Dow Chemical Company, and L-MODU(R) from Idemitsu (Japan). Metallocene polyolefin polymers are also supplied by several other companies such as ExxonMobil Corporation (USA), LyondellBasel Industries Holdings B.V. (Netherlands), Chevron Phillips Chemical Company LLC (USA), Total SA (France), SABIC (Saudi Arabia), Japan Polychem Corporation Ltd, Braskem AG (Brazil), LG Chem Ltd. (South Korea), etc.

[0024] Olefin block copolymers (OBCs) can be manufactured using chain shuttling catalyst technology that produces a linear block structure of monomers, rather than the random polymers produced by Ziegler-Natta or conventional metallocene technologies. OBCs are manufactured by Dow Chemical under the trade name Infuse(R). OBCs can be crystalline ethylene-octene blocks (hard) and amorphous ethylene-octene blocks (soft). The block structure gives the polymer much better high-temperature resistance and elasticity compared to typical metallocene random polymers of similar density. Some grades of Infuse(R) have a low heat of fusion (about 20 joules / gram), but since the polymer structure is completely different (i.e., block vs random) and is specifically produced to have crystalline regions, they are not considered amorphous poly-alpha-olefins. They differ not only structurally, but also greatly from a physical property perspective in that OBCs have better elastic recovery, compression set, and resistance to high temperatures.

[0025] Polyurethane can be prepared according to methods known in the art, for example, in one or two steps. The reaction may be carried out in the presence of a catalyst. Typical catalysts include organotin, tertiary amines or zinc salts. This is typically prepared by reacting a polyisocyanate with a polyol. Polyurethane can be prepared as disclosed in U.S. Patent No. 5,866,656 or U.S. Patent No. 6,465,104.

[0026] There are also some commercially available thermoplastic polyurethanes. For example, the series <<ELASTOLLAN(R)>> commercialized by BASF, the series <<Estane(R)>> commercialized by LUBRIZOL, the series <<DESMOPAN(R)>> commercialized by COVESTRO or the series <<Pellethane(R)>> commercialized by DOW may be mentioned. For example, Pellethane(R) 2103-70A (more than 98% obtained from methylene diphenyl diisocyanate, 1,4-butanediol and polytetramethylene glycol), or Elastollan(R) 1170 A10, 1175 A10W manufactured by BASF, FJ-146P (polyester-based aromatic thermoplastic polyurethane) manufactured by FWU JI RESINS CHEMICALS, Pearlbond(trademark) 5717 NT2 (polyester-based thermoplastic polyurethane) commercialized by LUBRIZOL.

[0027] The acrylic copolymer may be derived from monomers including alkyl methacrylate; alkyl acrylate; hydroxyalkyl acrylate or hydroxyalkyl methacrylate; or vinyl ester or acid monomer.

[0028] Alkyl methacrylates can include alkyl methacrylates having 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, tert-butyl methacrylate, and dodecyl methacrylate.

[0029] Alkyl acrylates can include alkyl acrylates having 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, tert-butyl acrylate, 2-ethylhexyl acrylate, isobomyl acrylate, isobomylmethyl acrylate, ethyl acrylate, isooctyl acrylate, decyl acrylate, and hexyl acrylate.

[0030] Hydroxyalkyl acrylates or hydroxyalkyl methacrylates may include, but are not limited to, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

[0031] Vinyl esters may include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl iso-butyrate, vinyl valerate, and general-purpose vinyl.

[0032] Acid monomers may include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, dimethacrylic acid, maleic acid, and fumaric acid.

[0033] Acrylic copolymers are sold in a wide range of products, for example, by Arkema under the trade name Flexcryl(R).

[0034] A styrene block copolymer is a copolymer containing at least one styrene block, including styrene triblock copolymers and styrene diblock copolymers.

[0035] A styrene block copolymer comprises at least one A block containing styrene and at least one B block containing, for example, elastomer-conjugated dienes (e.g., hydrogenated and unhydrogenated conjugated dienes), sesquiterpenes (e.g., hydrogenated and unhydrogenated sesquiterpenes), and combinations thereof. The A and B blocks are bonded to each other in any bonding mode such that the resulting copolymer exhibits a variety of structures, including, for example, random, linear, branched, radial, star-shaped, comb-shaped, tapered, and combinations thereof. The block copolymer can exhibit any form, including, for example, linear AB blocks, linear ABA blocks, linear A-(BA)nB multiblocks and radial (AB)nY blocks (wherein Y is a polyvalent compound and n is at least an integer of 3), tetrablock copolymers, for example, ABAB, and pentablock copolymers having the structure ABABA.

[0036] Suitable styrene A blocks include, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, and combinations thereof.

[0037] Suitable block elastomer 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, including, for example, ethylene, propylene, butylene and combinations thereof.

[0038] A suitable B-block sesquiterpene is, for example, beta-farnesene.

[0039] The styrene block copolymer preferably has an average styrene content of 15% to 45% by weight, and more preferably 15% to 25% by weight.

[0040] The styrene block copolymer preferably contains 10% to 80% by weight, more preferably 30% to 70% by weight, and even more preferably 40% to 60% by weight of diblocks.

[0041] "Diblock content" refers to the weight percentage of diblock copolymer in the styrene block copolymer.

[0042] 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.

[0043] Preferably, the styrene block copolymer is SIS, SI, or a mixture thereof.

[0044] "SBBS" stands for styrene-butadiene-butylene-styrene triblock copolymer. "SBS" stands for styrene-butadiene-styrene triblock copolymer. "SEBS" stands for styrene-ethylene-butylene-styrene triblock copolymer. "SEPS" stands for styrene-ethylene-propylene-styrene triblock copolymer. "SEEPS" stands for styrene-ethylene-ethylene-propylene-styrene triblock copolymer. "SIBS" stands for styrene-isoprene-butadiene-styrene triblock copolymer. "SIS" stands for styrene-isoprene-styrene triblock copolymer. "Random block SBR" stands for random block styrene-butadiene copolymer (where some of the styrene exists as polystyrene blocks). "Random block SIR" stands for random block isoprene-butadiene copolymer (where some of the styrene exists as polystyrene blocks). "SB" stands for styrene-butadiene diblock copolymer. "SI" stands for styrene-isoprene diblock copolymer. "SEB" stands for styrene-ethylene-butylene diblock copolymer. "SEP" stands for styrene-ethylene-propylene diblock copolymer.

[0045] Useful commercially available styrene block copolymers include the KRATON D and G(R) series from Kraton Polymers, the EUROPRENE Sol T(R) series from Versalis (Eni group), the SOLPRENE(R) series from Dynasol Elastomers, the SINOPEC(R) series from SINOPEC, and the Taipol(R) and Vector(R) series from TSRC Corporation. Other useful examples include the following: -Sinopec(R)YH-1126, a linear SIS triblock copolymer with a styrene content of 16% and a diblock content of 50%; -Sinopec(R)YH-1209, a linear SIS triblock copolymer with a styrene content of 30% and a diblock content of less than 1%; - Kraton(R) D1152, a mixture of linear SBS triblock and SB diblock copolymers, with a styrene content of 29.5% by weight relative to the total weight of the mixture, an average molecular weight of approximately 122,000 g / mol, a melt flow index or MFI of 8.5 g / 10 min at 200°C under a 5 kg load (measured according to ISO 1133), and an SB diblock content of approximately 17% by weight relative to the total weight of the mixture. - Kraton(R) D1161, a mixture of linear SIS triblock and SI diblock copolymers, with a styrene content of 15% by weight relative to the total weight of the mixture, MFI of 9 g / 10 min at 200°C under a 5 kg load (measured according to ISO 1133), an average molecular weight of approximately 220,000 g / mol, and an SI diblock content of approximately 19% by weight relative to the total weight of the mixture. - Taipol(R) SBS 4202, manufactured by TSRC Corporation, a linear SBS triblock copolymer with a styrene content of 40% by weight relative to the total weight of the triblock copolymer, measured according to ASTM D1238 at MFI (3-10 g / 10 min) under a 5 kg load at 190°C, with an average molecular weight of approximately 102,400 g / mol. - Vector(R)4411, manufactured by TSRC Corporation, a linear SIS triblock copolymer with a styrene content of 44% by weight relative to the total weight of the triblock copolymer, measured at 40 g / 10 min under a 5 kg load at 200°C (according to ASTM D1238), with an average molecular weight of approximately 106,000 g / mol. - Europrene(R)SOL TE9326 (linear SIS triblock copolymer, approximately 30% styrene block content, approximately 15% diblock content from Versalis).

[0046] Preferably, polymer (A) has a weight-average molecular weight greater than 5,000 g / mol, more preferably 10,000 g / mol or more. More preferably, it has a molecular weight of 15,000 g / mol or more.

[0047] Preferably, polymer (A) has a melt flow index (MI measured in accordance with ISO 1133) higher than 6 g / 10 min, more preferably higher than 25 g / 10 min, and even more preferably higher than 150 g / 10 min.

[0048] Polymer (A) is preferably selected from the group consisting of ethylene-vinyl acetate copolymer (EVA), styrene block copolymer, and mixtures thereof. More preferably, polymer (A) is styrene block copolymer. Even more preferably, it is SIS, SI, or a mixture thereof.

[0049] The adhesive composition may contain 10% to 70% by weight of polymer (A) (or a mixture of polymer (A)), preferably 15% to 50% by weight, and more preferably 20% to 40% by weight of polymer (A) (or a mixture of polymer (A)), based on the total weight of the adhesive composition.

[0050] <Tackifying resin (B)> The adhesive composition contains a tackifying resin (B) which includes a modified resin (B1).

[0051] The terms "tackifier" and "tackifying resin" are used interchangeably.

[0052] <Modified resin (B1)> According to the present invention, the modified resin (B1) is rosin or rosin ester modified with petroleum resin.

[0053] The modified resin (B1) is preferably not hydrogenated.

[0054] The modified resin (B1) preferably has an acid value in the range of 5 to 32 mg KOH / g, more preferably 10 to 30 mg KOH / g, and even more preferably 12 to 20 mg KOH / g. The acid value is measured in accordance with standard GB / T 2895-2008.

[0055] The modified resin (B1) preferably has a softening point in the range of 80°C to 120°C, and more preferably 90°C to 100°C. The softening point is measured in accordance with standard GB / T 15332-1994.

[0056] The modified resin (B1) preferably has a melt viscosity at 150°C of 5000 mPas or less, more preferably 2000 mPas or less, and even more preferably 500 to 1500 mPas. The melt viscosity is measured in accordance with standard GB / T 2794-2013.

[0057] The average molecular weight (Mw) of the modified resin (B1) is preferably 10,000 g / mol or less, more preferably 5,000 g / mol or less, and even more preferably 2,000 g / mol or less.

[0058] Mw is measured by GPC using polystyrene as a standard. More specifically, the measurement is performed in a Waters e2695 GPC instrument equipped with IR and UV detectors, using polystyrene of different molecular weights to construct a calibration curve under the following conditions (within the calibration range of 600 to 300,000 g / mol): 0.1 g of sample is dissolved in 10 ml of THF and 0.01 ml of toluene, the solution is filtered through a 0.45 μm filter and injected into a 2 ml vial into the instrument for analysis.

[0059] Preferably, the modified resin (B1) has a Gardner color of less than 6, more preferably in the range of 1 to 5. The Gardner color is measured in accordance with the standard ASTM D1544-04.

[0060] The modified resin (B1) is preferably, i) Rosin resin, polyol, petroleum resin; or ii) Prepared by the reaction of rosin ester resin and petroleum resin (or preferably derived therefrom).

[0061] Reactions i) and ii) can be carried out in the presence of a catalyst.

[0062] Reactions i) and ii) can be carried out at a temperature in the range of 220°C to 270°C, preferably 250°C to 270°C.

[0063] Reactions i) and ii) can be carried out for 1 to 12 hours, preferably 5 to 8 hours.

[0064] In reaction i), the weight ratio of rosin resin to petroleum resin is preferably in the range of 99:1 to 55:45.

[0065] In reaction ii), the weight ratio of rosin ester resin to petroleum resin is preferably in the range of 99:1 to 55:45.

[0066] The rosin resin may be any rosin resin known to those skilled in the art. The rosin may 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, dimerized rosin, polymerized rosin, and mixtures thereof.

[0067] Rosin resins include non-hydrogenated resins, fully hydrogenated resins, and partially hydrogenated resins.

[0068] More preferably, the rosin resin is gum rosin.

[0069] Polyols contain two or more hydroxyl groups.

[0070] The polyol is preferably selected from the group consisting of diols, triols, tetrol, pentol, hexol, and mixtures thereof.

[0071] In the case of a mixture, if a diol is present in the mixture, its weight content, based on the sum of the weight contents of all polyols, is less than 20 wt%, and more preferably less than 10 wt%.

[0072] The diol can be selected from the group consisting of glycols, propylene glycols, butanediols, and mixtures thereof.

[0073] The triol can be selected from the group consisting of glycerol, trimethylolpropane, and mixtures thereof.

[0074] Tetrol can be selected from the group consisting of pentaerythritol, tetragriol, and mixtures thereof.

[0075] Preferably, the polyol is selected from triols such as glycerol and pentaerythritol, tetrol and mixtures thereof, and more preferably, the polyol is tetrol such as pentaerythritol.

[0076] Petroleum resin is preferably, -C5 resin; -C9 resin; -C5 / C9 resin; -DCPD resin; - Selected from the group consisting of these mixtures.

[0077] As used herein, the term “C5 resin” means an aliphatic C5 hydrocarbon resin produced from the polymerization of monomers containing C5 and / or C6 olefin species that boil at a range of about 20°C to about 200°C at atmospheric pressure. These monomers are typically produced from petroleum processing, e.g., cracking. Aliphatic C5 hydrocarbon resins can be produced by any method known in the art. Aliphatic C5 hydrocarbon thermoplastic resins can be prepared from the cationic polymerization of cracked petroleum feedstocks containing C5 and C6 paraffins, olefins, and diolefins, also called “C5 monomers.” These monomer streams consist of cationic polymerizable monomers such as 1,3-pentadiene, which is a major reactive component along with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene, for example. Polymerization is typically catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chlorides). In addition to the reactive components, non-polymerizable components in the feedstock may, in some cases, include saturated hydrocarbons co-distilled with unsaturated components such as pentane, cyclopentane, or 2-methylpentane. Aliphatic C5 hydrocarbon resins can also be produced using solid acid catalysts. Aliphatic C5 hydrocarbon resins include non-hydrogenated resins, partially hydrogenated resins, or fully hydrogenated resins. Aliphatic C5 thermoplastic resins can be obtained as Piccotac(R)C5 and Eastotac(R)C5 H2 thermoplastic resins from Eastman Chemical Company (Kingsport, Tennessee, USA).

[0078] As used herein, the term “C5 / C9 resin” refers to an aliphatic / aromatic hydrocarbon C5 / C9 resin produced from the polymerization of monomers comprising at least one unsaturated aromatic C8, C9, and / or C10 species that boils in the range of about 100°C to about 300°C at atmospheric pressure, and at least one monomer comprising a C5 and / or C6 olefin species that boils in the range of about 20°C to about 200°C at atmospheric pressure. The C5 and / or C6 species typically include paraffins, olefins, and diolefins, also called “C5 monomers.” These monomer streams typically consist of cationic polymerizable monomers such as 1,3-pentadiene, which is a major reactive component along with 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 called “C9 monomers.” These monomer streams consist of cationic polymerizable monomers such as styrene, alpha-methylstyrene, beta-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. Cationic polymerization can be catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chlorides). Alphatic C5 / aromatic C9 hydrocarbon resins can also be produced using solid acid catalysts. In addition to the reactive components, non-polymerizable components may include xylene, ethylbenzene, cumene, ethyltoluene, indan, methylindan, naphthalene, and other similarly designated aromatic hydrocarbons. In some embodiments, the non-polymerizable components of the feed stream are incorporated into thermoplastic resins via alkylation reactions. Alphatic C5 / aromatic C9 hydrocarbon resins include non-hydrogenated resins, partially hydrogenated resins, and hydrogenated resins. Aliphatic C5 / aromatic C9 resins can be obtained from Eastman Chemical Company as Piccotac(R) thermoplastic resins. The ratio of C5 to C9 is not limited.In other words, the amount of C5 monomer in a C5 / C9 thermoplastic resin can be anywhere from 0.1% to 100%, and vice versa, and the amount of C9 monomer in a C5 / C9 thermoplastic resin can be anywhere from 0.1% to 100%.

[0079] As used herein, the term “C9 resin” refers to aromatic C9 hydrocarbon thermoplastic resins, which are resins produced from the polymerization of monomers containing unsaturated aromatic C8, C9, and / or C10 species that boil in the range of about 100°C to about 300°C at atmospheric pressure. These monomers are typically produced from petroleum processing, e.g., 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 distillates resulting from naphtha cracking, and are called “C9 monomers.” These monomer streams typically consist of cationic 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 having 4 to 6 carbon atoms during polymerization are also present. Polymerization can be catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chlorides). In addition to reactive components, non-polymerizable components include, but are not limited to, aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, indan, methylindan, naphthalene, and other similar chemical species. In some embodiments, the non-polymerizable components of the feed stream are incorporated into the thermoplastic resin via alkylation reactions. C9 hydrocarbon resins include non-hydrogenated, partially hydrogenated, or fully hydrogenated resins. Aromatic C9 hydrocarbon resins can be obtained as Picco(R) C9 thermoplastic resins, and aliphatic hydrogenated and aliphatic / aromatic partially hydrogenated C9 H2 hydrocarbon thermoplastic resins can be obtained from Eastman Chemical Company as Regalite(R) thermoplastic resins.

[0080] As used herein, the term “DCPD resin” refers to dicyclopentadiene (DCPD) resin, most commonly formed by ring-opening metathesis polymerization (ROMP) or thermal polymerization of dicyclopentadiene in the presence of a strong acid catalyst, such as an aqueous solution of maleic acid or sulfuric acid. Dicyclopentadiene is also, in some embodiments, formed by a Diels-Alder reaction from two cyclopentadiene molecules and exists in two stereoisomers, namely endo-DCPD and exo-DCPD. Typically, more than 90% of DCPD molecules present in commercially available DCPD are in the endo form. DCPD resins include aromatically modified DCPD resins, as well as hydrogenated, partially hydrogenated, and unhydrogenated resins, but in most cases only H2 DCPD is described herein because it is the most readily available commercially available form of DCPD. Aromatically modified DCPD can also be considered as DCPD thermoplastic resin. Aromatic modification is, for example, by C9 resin oil, styrene, or alpha-methylstyrene (AMS). Hydrogenated and partially hydrogenated DCPD, as well as hydrogenated and partially hydrogenated aromatically modified DCPD resins, are commercially available as Escorez(R) 5000 series resins (ExxonMobil Chemical Company, Texas, USA).

[0081] Preferably, the petroleum resin is not DCPD resin.

[0082] Preferably, the petroleum resin is not hydrogenated.

[0083] Preferably, the petroleum resin is not an acid-modified resin, such as a maleic anhydride-modified resin.

[0084] More preferably, the petroleum resin is selected from C5 resin, C9 resin, and C5 / C9 resin.

[0085] Examples of commercially available petroleum resins include Escorez(R) 5400, a hydrogenated dicyclopentadiene resin available from ExxonMobil Chemical, with a softening temperature of 100°C; Quintone(R) DX390N, a non-hydrogenated aliphatic / aromatic petroleum hydrocarbon resin sold by Zeon Company, with a softening temperature of 90°C; Sukorez(R) SU400, a hydrogenated aliphatic / aromatic petroleum hydrocarbon resin sold by Kolon Company; HH2-1003 (C5 / C9 petroleum hydrocarbon resin) sold by Henghe Materials and Science Technology Co. LTD; M-90Z, a C5 / C9 petroleum hydrocarbon resin sold by Luha; Escorez(R) 2203LC (C5 / C9 resin) sold by ExxonMobil Chemical; and Sukorez(R) SU 120 (fully hydrogenated resin DCPD) sold by ExxonMobil Chemical.

[0086] Rosin ester resins can be natural and modified rosin glycols, glycerols, and / or pentaerythritol esters (typically as described above). This includes hydrogenated versions of these.

[0087] Preferably, the rosin ester is a glycerol ester of pale wood rosin, a glycerol ester of hydrogenated rosin, a glycerol ester of polymerized rosin, a pentaerythritol ester of pale 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 pale wood rosin ester obtained from a mixture of glycerol and pentaerythritol, a hydrogenated rosin ester obtained from a mixture of glycerol and pentaerythritol, an ester of polymerized rosin obtained from a mixture of glycerol and pentaerythritol, or a phenol-modified pentaerythritol ester of rosin.

[0088] More preferably, the rosin ester is a pentaerythritol ester or glycerol ester of gum rosin.

[0089] Examples of commercially available rosin esters include Kraton's Sylvalite(R)RE 100L or RE 100S (pentaerythritol-based tall oil rosin ester), Sylvalite(R)RE 85L (glycerol ester of tall oil rosin); and Kraton's Sylvalite(R) 9,000 (fully hydrogenated tall oil rosin ester).

[0090] Additionally, the modified resin (B1) can be purchased from several suppliers on the market, such as KOMOTAC(R)KE100H provided by KOMO Co.,Ltd in Guangdong Province.

[0091] More preferably, the modified resin (B1) is -i) Polyols selected from gumrosin, glycerol, or pentaerythritol, and petroleum resins selected from C5 resins, C9 resins, and C5 / C9 resins (the petroleum resins are preferably not hydrogenated); or -ii) Prepared by reacting (or deriving from) a rosin ester resin based on glycerol or pentaerythritol with a petroleum resin selected from C5 resin, C9 resin and C5 / C9 resin (the petroleum resin is preferably not hydrogenated).

[0092] Preferably, the modified resin (B1) does not contain maleic anhydride or groups derived from maleic acid.

[0093] Preferably, the modified resin (B1) is not acid-modified, and more preferably, it is not maleic acid-modified or maleic anhydride-modified.

[0094] <Additional tackifiers> The tackifying resin (B) (in addition to the tackifying agent (B1)) - Petroleum resin (B2); or -Rosin resin (B3); or -Rosin ester resin (B4); or -These mixtures may further be included.

[0095] The above descriptions of rosin resins, rosin ester resins, and petroleum resins apply herein to tackifiers (B2), (B3), and (B4).

[0096] The tackifying resin (B) may contain 40% to 100% by weight, preferably 60% to 100% by weight, and more preferably 80% to 100% by weight of modified resin (B1) relative to the total weight of the tackifying resin (B).

[0097] The adhesive composition contains, based on the total weight of the adhesive composition, preferably 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).

[0098] <Plasticizer (C1)> The adhesive composition may further contain a plasticizer (C1). Any plasticizer known to those skilled in the art can be used.

[0099] The plasticizer (C1) may be selected from the group consisting of 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 derivatives thereof.

[0100] The plasticizer (C1) includes polyethylene, polypropylene, polybutene, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, etc., with an average molecular weight of approximately 350 g / mol to approximately 10,000 g / mol.

[0101] The mineral oil is preferably selected from the group consisting of naphthenic oil, paraffinic oil, or any mixture thereof.

[0102] Naphthenic oils and paraffinic oils are petroleum-based oils that are mixtures of naphthenic hydrocarbons (aliphatic saturated or unsaturated C4-C7 membered hydrocarbon rings, preferably aliphatic saturated or unsaturated C4-C6 membered rings; examples include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane), paraffinic hydrocarbons (saturated, straight-chain or branched-chain alkanes), and aromatic hydrocarbons (aromatic hydrocarbon rings that may be monocyclic or polycyclic, preferably aromatic C6 membered hydrocarbon rings).

[0103] The classification of naphthenic oils and paraffinic oils is based on the amount 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 30% to 40% by weight relative to the total weight of the mineral oil.

[0104] Examples of commercially available mineral oils include naphthenic oil from NYNAS sold under the trade names NYFLEX(R)223 and NYFLEX(R)222B, or naphthenic oil from Karamay sold under the trade name KN4010.

[0105] Suitable vegetable and animal oils include glycerol esters of common fatty acids and their derivative products.

[0106] The wax may 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.

[0107] "Paraffin wax" refers to wax derived from crude oil. It generally consists of a complex mixture of hydrocarbons having the following general properties: non-reactive; non-toxic; good water barrier; clean combustion fuel; and colorless. Paraffin wax is characterized by a clearly defined crystalline structure. The melting point of paraffin wax is generally between approximately 43 and 71°C. Paraffin wax often contains large amounts of straight-chain hydrocarbons, and may also contain branched hydrocarbons such as isoparaffins and other branched materials, as well as cycloalkanes such as cycloparaffins and other ring-containing materials.

[0108] "Fischer-Tropsch wax" refers to the wax obtained by the so-called Fischer-Tropsch process. The Fischer-Tropsch process involves converting synthesis gas, mainly hydrogen and carbon monoxide, into hydrocarbons. The conversion is carried out by contacting the synthesis gas with a Fischer-Tropsch catalyst, usually an iron or cobalt-based catalyst, in a fixed-bed or slurry-bed reactor under low or high Fischer-Tropsch operating conditions. In this way, a mixture of hydrocarbons with different boiling point ranges is obtained. Fischer-Tropsch wax is then recovered from this hydrocarbon mixture, for example, by distillation. Fischer-Tropsch wax typically has a composition in which about 80% by volume has a boiling point at atmospheric pressure equivalent temperature ("AET") above 550°C.

[0109] "EVA wax" refers to an oligomeric polymer compound prepared by a method involving copolymerization of ethylene monomer and vinyl acetate monomer, having the following properties: (a) solid at room temperature; (b) low melting point; and (c) insoluble in water. EVA copolymers of EVA wax can be functionalized or modified in any possible way.

[0110] As used herein, the term “polyolefin wax” refers to a polymer or long-chain entity composed of olefinic monomer units. This type of material is commercially available from Westlake Chemical Corporation in Houston, Texas, under the trade name “Epolene,” and from Honeywell Corporation in Morristown, New Jersey, under the trade names “A-C.”

[0111] The wax may be a commercially available wax. Examples of commercially available waxes suitable for the present invention include Shell's Fischer-Tropsch wax, sold under the trade names 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), as well as Sasol's Fischer-Tropsch wax, sold under the trade name C-80M (freezing point 80-85°C). Other examples include Sinopec's 64# paraffin wax, which has a melting point of 64-66°C, and Honeywell's EVA wax, sold under the trade name AC-400A, which has a vinyl acetate content of 13% by weight, a dropping point of 92°C, and a viscosity of 595 mPa.s at 140°C.

[0112] Preferably, the plasticizer (C1) in the adhesive composition is selected from mineral oil or wax.

[0113] The adhesive composition may contain 0% to 50% by weight, preferably 1% to 40% by weight, and more preferably 5% to 20% by weight of a plasticizer (C1), based on the total weight of the adhesive composition.

[0114] <Antioxidant (C2)> The adhesive composition may also contain an antioxidant (C2).

[0115] The adhesive composition contains an antioxidant in an amount of about 0 to about 5% by weight, preferably 0 to about 3% by weight, more preferably about 0.1 to about 3% by weight, and more preferably about 0.1 to 2% by weight, based on the total weight of the adhesive composition.

[0116] Appropriate antioxidants are incorporated to help protect the polymers, and consequently the entire adhesive system, from the effects of thermal and oxidative degradation that normally occur during the manufacture and application of the adhesive composition, as well as during the normal exposure of the final product to the surrounding environment. Such degradation typically manifests as deterioration of the appearance, physical properties, and performance characteristics of the hot-melt adhesive composition.

[0117] Among the applicable antioxidants, high molecular weight hindered phenols and polyfunctional phenols, such as sulfur and phosphorus-containing phenols, can be mentioned. Hindered phenols are well known to those skilled in the art and can be characterized as phenol compounds that also contain sterically bulky radicals adjacent to their phenolic hydroxyl group. In particular, tertiary butyl groups are generally substituted on the benzene ring at least one ortho position relative to the phenolic hydroxyl group. The presence of these sterically bulky substituents near the hydroxyl group helps to reduce its stretching frequency and, consequently, its reactivity. This steric hindrance gives phenol compounds their stabilizing properties. Representative hindered phenols include 1,3,5-trimethyl-2,4,6-tris(3-5-di-tert-butyl-4-hydroxybenzyl)benzene; pentaerythritol tetrakis-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-H Examples include droxyphenoxy)-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-octylthio)ethyl-3,5-di-tert-butyl-4-hydroxybenzoate and sorbitol hexa-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0118] The performance of these antioxidants can be further enhanced by using (1) synergists, such as thiodipropionates and phosphates; an example of which is diarylthiodipropionate (DLTDP); and (2) chelating agents and metal deactivators, such as ethylenediaminetetraacetic acid, its salts, and disalithyralpropylenediimine.

[0119] Suitable antioxidants include those commercially available from BASF under the trade names Irganox(R)1010 (tetrakis(methylene(3,5-di-ter-butyl-4-hydroxyhydrocinnamate))methane), Irgafos(R)168 (tris(2,4-di-tert-butylphenyl)phosphate), and Irganox(R)PS800 (propanoic acid, 3,3'-thiobis-1,1'-didodecyl ester), from Shuangjian under the trade name Chinox(R)1010 (pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)), from Everspring Chemical under the trade names Evernox(R)1010 and Everfos(R)168, from Songwon under the trade names Songnox(R)10 and 1680, and from BASF under the trade name l'Irganox PS800.

[0120] <Other additives (C3)> The adhesive composition may further contain at least one other additive in an amount preferably 0 to 10% by weight, for example, 0.1 to 10% by weight, relative to the total weight of the adhesive composition.

[0121] Additives may be selected from the group consisting of inert colorants (e.g., titanium dioxide), fillers (e.g., talc, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass microspheres, ceramic microspheres, thermoplastic microspheres, and mixtures thereof), surfactants, crosslinking agents, nucleating agents, reactive compounds, flame retardant minerals or organic agents, ultraviolet (UV) and / or infrared (IR) light absorbers (e.g., HALS hindered amine light stabilizers), UV and / or IR fluorescent agents, and mixtures thereof. Any other additives of these are well known in the art.

[0122] The type of additive typically depends on the end-use of the adhesive composition.

[0123] Preferably, the adhesive composition does not contain polycaprolactone.

[0124] <Adhesive composition> The adhesive composition may be a hot melt adhesive composition, a pressure-sensitive adhesive composition (PSA), or a hot melt pressure-sensitive adhesive composition (HMPSA).

[0125] Pressure-sensitive adhesives (PSAs) are substances that impart immediate tackiness to a support layer coated with them at ambient temperature (23°C). This immediate tackiness allows for instantaneous adhesion of the self-adhesive support to all types of substrates under the influence of gentle, short-duration pressure. PSAs are widely used in the manufacture of self-adhesive labels attached to articles (e.g., packaging) for the purpose of presenting information (barcodes, names, prices, etc.) and / or for decorative purposes. PSAs are also used in the manufacture of self-adhesive tapes for a variety of applications. Examples include, in addition to the transparent adhesive tapes widely used in everyday life, molding and assembly of corrugated packaging; surface protection for painting work in the construction industry; maintenance of electrical cables in the transportation industry; and adhesive bonding of carpets attached with double-sided adhesive tape.

[0126] Hot melt adhesives, or hot melts (HMs), are substances that are solid at ambient temperature (23°C) and contain neither water nor solvents. They are applied in a molten state and solidify upon cooling, thus forming joints that attach the substrates to be assembled due to their adhesive strength. Certain hot melts are formulated to give the support coated with them relatively hard and tack-free properties. Other hot melts result in supports with relatively soft characteristics and high tackiness. These are PSAs widely used in the manufacture of self-adhesive articles (e.g., self-adhesive labels). Corresponding adhesives are indicated by the name "hot melt pressure-sensitive adhesive" (or HMPSA). Thus, HMPSAs are a different category from hot melts, HMs. Therefore, due to their adhesive strength, they also allow labels or tapes to be firmly attached to the desired substrate, whether it is packaging to be labeled or boards to be assembled, for example.

[0127] Preferably, the adhesive composition is a hot-melt pressure-sensitive adhesive composition or a hot-melt adhesive composition.

[0128] In one embodiment, if the adhesive composition is a hot-melt pressure-sensitive adhesive composition, it is preferably, -10% to 70% by weight of polymer (A) selected from styrene block copolymers; - A tackifying resin (B) in an amount of 1% to 70% by weight, comprising a modified resin (B1) and any petroleum resin (B2); -0% to 50% by weight of plasticizer (C1); and Contains -0% to 5% by weight of antioxidant (C2).

[0129] In another embodiment, if the adhesive composition is a hot melt adhesive composition, it is preferably, A polymer (A) selected from ethylene copolymers in an amount of -10% to 70% by weight; - A tackifying resin (B) in an amount of 1% to 70% by weight, comprising a modified resin (B1) and any petroleum resin (B2); -0% to 50% by weight of plasticizer (C1); and Contains -0% to 5% by weight of antioxidant (C2).

[0130] In another embodiment, the adhesive composition is -10% to 70% by weight of a polymer selected from amorphous poly-alpha-olefins (A); - A tackifying resin (B) in an amount of 1% to 70% by weight, comprising a modified resin (B1) and any petroleum resin (B2); -0% to 50% by weight of plasticizer (C1); and Contains -0% to 5% by weight of antioxidant (C2).

[0131] In another embodiment, if the adhesive composition is a hot melt adhesive composition, the adhesive is -10% to 70% by weight of a polymer selected from polyurethane (A); - A tackifying resin (B) in an amount of 1% to 70% by weight, comprising a modified resin (B1) and any petroleum resin (B2); -0% to 50% by weight of plasticizer (C1); and Contains -0% to 5% by weight of antioxidant (C2).

[0132] The adhesive composition preferably has a viscosity in the range of 500 to 10,000 mPas at 170°C, more preferably in the range of 600 to 8,000 mPas. The viscosity is measured in accordance with standard GB / T 2794-2013.

[0133] The adhesive composition preferably has a softening point in the range of 80°C to 120°C. The softening point is measured in accordance with GB / T 15332-1994.

[0134] The adhesive composition of the present invention advantageously exhibits good adhesive properties (e.g., a good compromise between 180° peel and loop tack, or high fiber peel strength over a wide temperature range).

[0135] The adhesive composition of the present invention exhibits advantages such as low odor, low cost, and low color, in addition to good adhesive performance (adhesion, fiber release, etc.).

[0136] B. <Method for preparing adhesive compositions> The present invention also relates to a method for preparing the above-mentioned adhesive composition.

[0137] The adhesive composition of the present invention can be manufactured using any of the techniques known in the art.

[0138] For example, an adhesive composition may be prepared by mixing a polymer (A) and a tackifying resin (B) in a molten state. Any other components or additives of the above composition, in particular at least one antioxidant, may be mixed with the above components. Another method for preparing an adhesive composition is to add the tackifying resin (B) to the polymer (A) in the presence of a plasticizer or other additive, which is optional.

[0139] Preferably, the mixing step is carried out at a temperature of 140-180°C. The components are preferably mixed for at least 1 hour.

[0140] The adhesive composition according to the present invention can be prepared in the presence of two oxygen atoms (such as in an air atmosphere), or preferably in an inert atmosphere, such as carbon dioxide or nitrogen, in order to limit potential decomposition by oxidation reactions.

[0141] C.〈Use〉 The present invention relates to the use of adhesive compositions as defined herein for bonding two substrates together or as a coating on the surface of a substrate.

[0142] The adhesive composition can be used in a wide range of applications, including but not limited to disposable articles, packaging (e.g., cases, cartons, trays, etc.), processing, lamination, pressure-sensitive adhesives, tapes, labels, assembly, bookbinding, wood bonding (e.g., edge banding, profile wrapping, etc.), transportation, reflective coatings, road markings, and more.

[0143] The adhesive compositions defined above may be applied to any substrate. Preferred substrates include wood, paper, cardboard, plastic, thermoplastic resin, rubber, metal, metal foil (e.g., aluminum foil and tin foil), metallized surfaces, cloth, nonwoven fabric (especially polypropylene spunbond fibers or nonwoven fabrics), spunbond fibers, cardboard, stone, gypsum, glass (including silicon dioxide (SiOx) coatings applied by evaporating silicon dioxide onto the film surface), foam, rock, ceramic, film, polymer foam (e.g., polyurethane foam), substrates coated with inks, dyes, pigments, PVDC, etc., or combinations thereof.

[0144] In certain embodiments, the adhesive compositions of the present invention can be used in packaging. The packaging may be useful as, for example, cartons, containers, crates, cases, corrugated cases, or trays. More specifically, the packaging may be useful as, to name just a few exemplary uses, cereal products, cracker products, beer packaging, frozen foods, paper bags, drinking cups, milk cartons, juice cartons, drinking cups, or containers for transporting fresh produce.

[0145] The packaging is formed by applying an adhesive composition to at least a portion of one or more packaging elements. The packaging elements may be formed from paper, cardboard, container cardboard, tag board, corrugated cardboard, chipboard, kraft, thick cardboard, fiberboard, plastic resin, metal, metal alloy, foil, film, plastic film, laminate, sheet, or any combination thereof. In one embodiment, the adhesive composition may be used to bond or bond two or more packaging elements together, and the packaging elements may be formed from the same or different types of materials. Thus, the packaging elements may be formed individually from paper, cardboard, container cardboard, tag board, corrugated cardboard, chipboard, kraft, thick cardboard, fiberboard, plastic resin, metal, metal alloy, foil, film, plastic film, laminate, sheet, or any combination thereof. One or more packaging elements may also be individually coated using paper, foil, metal, metal alloy, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamide, homopolymers thereof, and combinations and copolymers thereof.

[0146] The adhesive composition of the present invention can be used to make adhesive tapes or to adhere labels to various articles (e.g., containers, magazines, etc.). The labels / tapes can be selected from a variety of materials, including paper and non-paper films (e.g., polypropylene (e.g., polypropylene (PP), oriented polypropylene (OP), and biaxially oriented polypropylene (BOPP)), polyethylene, etc.). The container may be made of metal (e.g., aluminum or steel) or plastic (polyethylene terephthalate (PET), high-density polyethylene (HDPE), and polypropylene). The label may be a spot label, i.e., a label that does not extend completely around the container. Alternatively, the label may be a wrap-around label, i.e., a label that completely wraps around the entire container. If the label is a wrap-around label, it may be supplied in a roll into the applicator. Alternatively, the labels may be pre-cut and fed from a stack. In the wrap-around label application method, the label stock is supplied to the label station. Pickup adhesive and wrap adhesive are then applied to the label, often from the same adhesive pot. The pickup adhesive adheres the leading edge of the label to the container. The wrap adhesive then adheres the overlap, where the wrap around the label overlaps itself.

[0147] The adhesive composition is also useful in a variety of applications and structures including, for example, disposable absorbent articles such as disposable diapers, adult incontinence products, sanitary napkins, medical dressings (e.g., wound care products), bandages, surgical pads, pet training pads (e.g., puppy pads), and meat packaging products, as well as components of absorbent articles such as absorbent elements, absorbent cores, impermeable layers (e.g., backsheets), tissue (e.g., packaging tissue), absorbent layers, and woven and nonwoven web layers (e.g., outer fabric, absorbent tissue), and elastic materials. The adhesive compositions are useful on substrates made from various fibers, including, for example, natural cellulose fibers (e.g., wood pulp, cotton, viscose, starch, etc.), silk, PLA (polylactic acid), PHA (polyhydroxyl alkanoate), PBS (polybutylene succinate), PBAT (polybutylene adipate terephthalate), and wool; synthetic fibers such as nylon, rayon, polyester, acrylic, polypropylene, polyethylene, polyvinyl chloride, polyurethane, and glass; regenerated fibers, and various combinations thereof. The hot-melt adhesive compositions are useful on various films, including polyethylene, polypropylene, ethylene vinyl acetate, ethylene copolymer, and bio-based films (e.g., PLA, PHA, starch, etc.). Various application techniques can be used to apply the compositions to the substrates, including, for example, slot coating, spraying including spiral spraying and random spraying, screen printing, foaming, engraving rollers, extrusion, and melt-blown application techniques.

[0148] In disposable articles, the adhesive composition can be used as an elastic mounting adhesive, a positioning adhesive, and / or a core stabilizing adhesive.

[0149] The adhesive composition can be used in woodworking methods. The woodworking method involves forming a woodworking product by applying the adhesive composition to at least a portion of a structural element. The structural element may include, but is not limited to, various materials such as wood, plywood, plastic, or veneer. For example, the structural element may also include wood, wood fiberboard, gypsum board, gypsum, wall panels, plywood, PVC, melamine, polyester, impregnated paper, and sheet lock. The woodworking method can be used, for example, to form indoor furniture, outdoor furniture, trim, molding, doors, sashes, windows, woodworking products, and cabinets.

[0150] The present invention also relates to an article comprising an adhesive composition as defined herein.

[0151] The articles may be selected from the group consisting of tapes, labels, cases, cartons, bags, and disposable absorbent articles.

[0152] <Pattern> Embodiment 1: An adhesive composition, -Polymer (A); - An adhesive composition comprising a modified resin (B1) and a tackifying resin (B).

[0153] Embodiment 2: The adhesive composition according to Embodiment 1, wherein polymer (A) is selected from the group consisting of polyolefin polymers, styrene block copolymers, polyurethanes, polyamides, acrylic copolymers, and mixtures thereof.

[0154] Embodiment 3: The adhesive composition according to Embodiment 2, wherein the polyolefin polymer is selected from the group consisting of ethylene copolymers, amorphous poly-alpha-olefins (APAOs), metallocene-catalyzed polyolefins, and olefin block copolymers.

[0155] Embodiment 4: The adhesive composition according to Embodiment 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.

[0156] Embodiment 5: The adhesive composition according to Embodiment 4, wherein the styrene block copolymer is SIS, SI, or a mixture thereof.

[0157] Embodiment 6: The adhesive composition according to any one of Embodiments 1 to 5, wherein polymer (A) has a weight-average molecular weight of 15,000 g / mol or more.

[0158] Embodiment 7: The adhesive composition according to any one of Embodiments 1 to 6, wherein polymer (A) is selected from the group consisting of ethylene-vinyl acetate copolymer (EVA), styrene block copolymer, and mixtures thereof.

[0159] Embodiment 8: The adhesive composition according to any one of Embodiments 1 to 7, wherein the adhesive composition comprises 10% to 70% by weight of polymer (A) (or a mixture of polymer (A)), preferably 15% to 50% by weight, and more preferably 20% to 40% by weight of polymer (A) (or a mixture of polymer (A)), based on the total weight of the adhesive composition.

[0160] Embodiment 9: The adhesive composition according to any one of Embodiments 1 to 8, wherein the modified resin (B1) is not hydrogenated.

[0161] Embodiment 10: The adhesive composition according to any one of Embodiments 1 to 9, wherein the modified resin (B1) has an acid value 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.

[0162] Embodiment 11: The adhesive composition according to any one of Embodiments 1 to 10, wherein the modified resin (B1) has a melt viscosity at 150°C of 5,000 mPas or less, preferably 2,000 mPas or less, and more preferably 500 to 1,500 mPas.

[0163] Embodiment 12: The adhesive composition according to any one of Embodiments 1 to 11, wherein the modified resin (B1) has an average molecular weight (Mw) of 10,000 g / mol or less, preferably 5,000 g / mol or less, and more preferably 2,000 g / mol or less.

[0164] Embodiment 13: The adhesive composition according to any one of Embodiments 1 to 12, wherein the modified resin (B1) has a Gardner color of less than 6, preferably in the range of 1 to 5.

[0165] Embodiment 14: Modified resin (B1) iii) Rosin resins, polyols, and petroleum resins; or iv) An adhesive composition according to any one of embodiments 1 to 13, prepared by reacting a rosin ester resin and a petroleum resin.

[0166] Appearance 15: In reaction i), the weight ratio of rosin resin to petroleum resin is in the range of 99:1 to 55:45; -In reaction ii), the weight ratio of rosin ester resin to petroleum resin is in the range of 99:1 to 55:45, the adhesive composition according to embodiment 14.

[0167] Embodiment 16: The adhesive composition according to any one of Embodiments 14 or 15, wherein the rosin resin is selected from the group consisting of gum rosin, wood rosin, tall oil rosin, distilled rosin, dimerized rosin, polymerized rosin, and mixtures thereof, and the rosin resin is preferably gum rosin.

[0168] Embodiment 17: The adhesive composition according to any one of Embodiments 14 to 16, wherein the polyol is selected from, for example, glycerol, triols such as pentaerythritol, tetrol, and mixtures thereof, and more preferably the polyol is tetrol such as pentaerythritol.

[0169] Embodiment 18: Petroleum resin, -C5 resin; -C9 resin; -C5 / C9 resin; -DCPD resin; -An adhesive composition according to any one of embodiments 14 to 17, selected from the group consisting of these mixtures.

[0170] Embodiment 19: The adhesive composition according to any one of Embodiments 14 to 18, wherein the petroleum resin is not a DCPD resin.

[0171] Embodiment 20: The adhesive composition according to any one of Embodiments 14 to 19, wherein the petroleum resin is not hydrogenated.

[0172] Embodiment 21: The adhesive composition according to any one of Embodiments 14 to 20, wherein the petroleum resin is selected from C5 resin, C9 resin, and C5 / C9 resin.

[0173] Embodiment 22: The adhesive composition according to any one of Embodiments 14 to 21, wherein the rosin ester is a glycerol ester of pale wood rosin, a glycerol ester of hydrogenated rosin, a glycerol ester of polymerized rosin, a pentaerythritol ester of pale 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 pale wood rosin ester obtained from a mixture of glycerol and pentaerythritol, a hydrogenated rosin ester obtained from a mixture of glycerol and pentaerythritol, an ester of polymerized rosin obtained from a mixture of glycerol and pentaerythritol, or a phenol-modified pentaerythritol ester of rosin.

[0174] Embodiment 23: The adhesive composition according to any one of Embodiments 14 to 22, wherein the rosin ester is pentaerythritol or glycerol ester of gum rosin.

[0175] Embodiment 24: Modified resin (B1) -i) Polyols selected from gumrosin, glycerol, or pentaerythritol, and petroleum resins selected from C5 resins, C9 resins, and C5 / C9 resins (preferably not hydrogenated); or -ii) An adhesive composition according to any one of embodiments 1 to 23, prepared by reacting (or deriving from) a rosin ester resin based on glycerol or pentaerythritol with a petroleum resin selected from C5 resin, C9 resin and C5 / C9 resin (the petroleum resin is preferably not hydrogenated).

[0176] Embodiment 25: The adhesive composition according to any one of Embodiments 1 to 24, wherein the tackifying resin (B) comprises 40% to 100% by weight, preferably 60% to 100% by weight, and more preferably 80% to 100% by weight of a modified resin (B1) based on the total weight of the tackifying resin (B).

[0177] Embodiment 26: The adhesive composition according to any one of Embodiments 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 a tackifying resin (B) based on the total weight of the adhesive composition.

[0178] Embodiment 27: The adhesive composition according to any one of Embodiments 1 to 26, further comprising a plasticizer (C1).

[0179] Embodiment 28: The adhesive composition according to Embodiment 27, wherein the plasticizer (C1) is selected from the group consisting of 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 derivatives thereof.

[0180] Embodiment 29: The adhesive composition according to Embodiment 27 or 28, wherein the plasticizer (C1) in the adhesive composition is selected from mineral oil or wax.

[0181] Embodiment 30: The adhesive composition according to any one of Embodiments 1 to 29, wherein the adhesive composition contains 0% to 50% by weight, preferably 1% to 40% by weight, and more preferably 5% to 20% by weight of a plasticizer (C1) based on the total weight of the adhesive composition.

[0182] Embodiment 31: An adhesive composition according to any one of Embodiments 1 to 30, which does not contain polycaprolactone.

[0183] Embodiment 32: An adhesive composition according to any one of Embodiments 1 to 31, which 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.

[0184] Embodiment 33: The adhesive composition is a hot melt pressure-sensitive adhesive composition, -10% to 70% by weight of polymer (A) selected from styrene block copolymers; - A tackifying resin (B) in an amount of 1% to 70% by weight, comprising a modified resin (B1) and any petroleum resin (B2); -0% to 50% by weight of plasticizer (C1); and - An adhesive composition according to any one of embodiments 1 to 32, comprising -0% to 5% by weight of an antioxidant (C2).

[0185] Embodiment 34: The adhesive composition is A polymer (A) in an amount of -10% to 70% by weight, selected from ethylene copolymers; - A tackifying resin (B) in an amount of 1% to 70% by weight, comprising a modified resin (B1) and any petroleum resin (B2); -0% to 50% by weight of plasticizer (C1); and The adhesive composition according to any one of embodiments 1 to 32, which is a hot melt adhesive composition containing an antioxidant (C2) in an amount of -0% to 5% by weight.

[0186] Embodiment 35: The adhesive composition according to any one of Embodiments 1 to 34, wherein the adhesive composition has a viscosity in the range of 500 to 10,000 mPas, more preferably in the range of 600 to 8,000 mPas, at 170°C.

[0187] Embodiment 36: Use of the adhesive composition according to any one of Embodiments 1 to 34 for bonding two substrates together or as a coating on the surface of a substrate.

[0188] Embodiment 37: Uses of the embodiment 36 in a variety of applications including, but not limited to, disposable articles, packaging (e.g., cases, cartons, trays, ...), processing, lamination, pressure-sensitive adhesives, tapes, labels, assembly, bookbinding, wood bonding (e.g., edge banding, profile wrapping, ...), transport, reflective coatings, road markings, etc.

[0189] Embodiment 38: An article comprising the adhesive composition described in any one of Embodiments 1 to 36.

[0190] Embodiment 39: The article according to Embodiment 38, wherein the article is selected from the group consisting of tapes, labels, cases, cartons, bags, and disposable absorbent articles.

[0191] The scope disclosed herein includes both its lower and upper limits. For example, the expression “range of x to y” or “x to y” includes the limits x and y.

[0192] The following examples will be described without limiting the present invention.

[0193] <Experiment Section> The raw materials shown in the table were used.

[0194] [Table 1]

[0195] <Test Method>: Gardner color is measured in accordance with standard ASTM D1544-04. The acid value is measured in accordance with standard GB / T 2895-2008. The softening point is measured according to standard GB / T 15332-1994. Viscosity is measured in accordance with the GB / T 2794-2013 standard. The viscoelastic properties of the material were analyzed using rheology.

[0196] Temperature scanning was used for the adhesive composition: Temperature scanning was performed using the TA DHR-2 apparatus at 140°C to -10°C on a 25mm parallel plate at 10 rad / s. The cooling rate was set to 5°C / min from 140°C to 40°C and to 2°C / min from 40°C to -10°C.

[0197] <Adhesive Strength>: 180° peel test The adhesive strength of adhesive compositions is given in FINAT Technical Handbook, 6. th As described in FINAT Test Method No. 1 (FTM 1) published in edition 2001, the evaluation is performed by a 180° peel test on a substrate plate. FINAT is the International Federation of Self-Adhesive Label Manufacturers and Converters.

[0198] The principle of this test is as follows: A support layer made of PET film with a thickness of 50 μm is filled with 18 g / m². 2 Apply the specified amount of adhesive composition as a precoat.

[0199] From the self-adhesive support obtained in this way, a test specimen in the form of a rectangular strip (25.4 mm × 175 mm) is cut. This test specimen is fixed to a plate made of a certain substrate. The resulting assembly is left at ambient temperature for 20 minutes. It is then introduced into a tensile testing apparatus capable of peeling or removing the strip at an angle of 180° and a separation speed of 300 mm / min. The apparatus measures the force required to remove the strip under these conditions.

[0200] The results are expressed as N / 2.54cm and shown along with the properties of the plate substrate.

[0201] <Immediate Adhesion>: Loop Adhesion Test The immediate tackiness of the composition is evaluated by the loop tackiness test described in FINAT Test Method No. 9 (FTM9).

[0202] A support layer made of 50 μm thick PET film contains 18 g / m² of HMPSA. 2 A rectangular strip measuring 25.4 mm × 175 mm is obtained by pre-coating with a certain amount of adhesive. The two ends of this strip are joined together to form a loop, with the adhesive layer facing outwards. The two joined ends are placed in the movable jaws of a tensile testing apparatus that can be subjected to a displacement rate of 300 mm / min along the vertical axis with the possibility of reciprocating motion. The lower part of the loop, placed in a vertical position, first contacts a horizontal plate of a certain substrate measuring 25 mm × 30 mm over a square area with sides of approximately 25 mm. Once this contact is established, the direction of displacement of the jaws is reversed. Immediate adhesion is the maximum force required for the loop to completely detach from the substrate.

[0203] The results are expressed as N / 2.54cm and shown along with the properties of the substrate for the horizontal plate.

[0204] Experiments were conducted on each HMPSA composition using 180° peel strength tests and loop tackiness tests. The coating conditions used in each of these experiments are as follows:

[0205] [Table 2] "Temperature" refers to the temperature of the tank containing the adhesive composition to be applied. "Width" refers to the width of the HMPSA coating on the primary substrate. "Add-on" refers to the amount of HMPSA coated onto the primary substrate. "OT" stands for Open Time, which is the time it takes for the HMPSA coated on the primary substrate to move from the nozzle to the compression zone where the secondary substrate is applied to the HMPSA.

[0206] <Fiber tear strength test>: The carton substrate was cut to a standard size of 45 mm x 75 mm. The adhesive was melted and then applied as beads (1 mm to 1.5 mm, melted for 30 minutes) to the standard test specimen from the outside of the carton through the nozzle of an adhesive gun. The beads were approximately 3 grams / linear meter and approximately 40 mm in length. The second substrate was applied to the opposite side and pressed with a 1 kg weight for approximately 3 seconds. The test specimen was left at 23°C for 2 hours, then placed at 5°C, 20°C, and 50°C (refrigerator or oven) for 24 hours. After 24 hours, the substrates of the structure were then separated from each other at the test temperature (e.g., immediately after removing the sample from the pretreatment chamber) by manually pulling the two substrates apart. The surface of the adhesive composition was observed, and the percentage of the surface area of ​​the adhesive composition covered with fibers was determined and recorded. At least three samples were prepared and tested for each adhesive composition. The results were reported in units of fiber tear percentage.

[0207] [Example 1] Preparation of SBC-based HMPSA E1 and E2 (the present invention) and comparative compositions CE1 and CE2

[0208] The adhesive compositions shown in Table 1 below were prepared as follows: Polymer A1 was added to a mixture of plasticizer and antioxidant that had already been heated to 165°C. After obtaining a homogeneous mixture (90 minutes), the resin was added two or three times, and the mixture was stirred for 1 hour.

[0209] The percentages in the table represent weight percentages relative to the total weight of the hot melt adhesive composition.

[0210] [Table 3] CP*: Transparent panel - No visible blemishes on the panel. *CF: Adhesive failure - The adhesive film tears during the test, leaving adhesive residue on both the panel and the front material. **PS: Panel staining - discoloration of the test area, but no sticky residue.**

[0211] [Example 2] Preparation of EVA-based HMA for rigid package application E3 Adhesive composition E3 was prepared by blending the raw materials at 165°C for 2 hours.

[0212] [Table 4]

[0213] Adhesive composition E3 containing modified rosin (B1) advantageously exhibits a high fiber tear rate in the temperature range of 20°C to 50°C.

Claims

1. An adhesive composition, - Polymer (A); - An adhesive composition comprising a tackifying resin (B) containing a modified resin (B1).

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

3. The adhesive composition according to any one of claims 1 to 2, wherein polymer (A) has a weight-average molecular weight of 15,000 g / mol or more.

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 modified resin (B1) has an acid value 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 modified resin (B1) has an average molecular weight (Mw) of 10,000 g / mol or less, preferably 5,000 g / mol or less, and more preferably 2,000 g / mol or less.

7. Modified resin (B1) i) Rosin resins, polyols, and petroleum resins; or ii) Rosin ester resins and petroleum resins An adhesive composition according to any one of claims 1 to 6, prepared by reacting the following:

8. - In reaction i), the weight ratio of rosin resin to petroleum resin is in the range of 99:1 to 55:45; - In reaction ii), the weight ratio of rosin ester resin to petroleum resin is in the range of 99:1 to 55:45, according to claim 7.

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. Modified resin (B1) -i) Polyols selected from gumrosin, glycerol, or pentaerythritol, and petroleum resins selected from C5 resins, C9 resins, and C5 / C9 resins (the petroleum resins are preferably not hydrogenated); or -ii) Rosin ester resins based on glycerol or pentaerythritol, and petroleum resins selected from C5 resins, C9 resins, and C5 / C9 resins (the petroleum resins are preferably not hydrogenated), An adhesive composition according to any one of claims 1 to 9, which is prepared by reacting the following:

11. The adhesive composition according to any one of claims 1 to 10, 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 a tackifying resin (B), based on the total weight of the adhesive composition.

12. The adhesive composition according to any one of claims 1 to 11, further comprising a plasticizer (C1), wherein the plasticizer (C1) is preferably selected from the group consisting of 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 derivatives thereof.

13. An adhesive composition according to any one of claims 1 to 12, which does not contain polycaprolactone.

14. The adhesive composition according to any one of claims 1 to 13, characterized in that it 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. Use of the adhesive composition according to any one of claims 1 to 14 for bonding two substrates together or as a coating on the surface of a substrate.

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

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