TW593520B - Adhesive components and process for manufacture - Google Patents

Abstract

Resins and oligomer materials and/or combinations thereof grafted with an unsaturated acid or anhydride, such as maleic anhydride, are disclosed herein. The grafted materials are useful in adhesive formulations, particularly in hot melt adhesive applications.

Description

593520 A7 _B7 V. Description of the invention (1) Background The present invention relates to grafted hydrocarbon resins and oligomer compositions, including (but not limited to) adhesives and tacky components of the grafted graft composition, And methods of making and using those compositions. Lower molecular weight resins (usually having a Mη molecular weight ranging from 400 to 1500) can be used in many applications, including tackifiers for adhesives, ink additives, polymer additives, road marking resins, sticky paper glues, and tube wrapping. Certain commercial grades of tall pine esters (TOREs) or terpene phenol resins (TPRs) are used to improve the performance of ethylene vinyl acetate (EVA) -based hot melt adhesives (HMAs). However, TOREs are impaired at application temperatures due to color instability and odor-generating properties. Hydrocarbon resins, especially hydrogenated cycloaliphatic resins, have excellent color stability and odor-generating properties, but exhibit highly omnidirectional properties on polar surfaces, such as polyethylene terephthalate (PET) and acrylic Lacquer, where TORES are often used. The glue industry recognizes this problem but still needs to address it. Therefore, there is a need for a tacky component or hydrocarbon resin that has enhanced HMA properties without the instability and odor associated with TORES or TPRS. U.S. Patent No. 47 19260 discloses a hot melt adhesive composition having improved adhesion to a substrate such as polyethylene, which includes an amorphous polymer including polypropylene and a polycyclic saturated aliphatic hydrocarbon resin and cis- Graft copolymer of butylene dianhydride. It does not disclose the use of an at least partially hydrogenated aromatic hydrocarbon resin. Further, it is generally known that aromatic resins are generally less compatible with saturated hydrocarbon polymers such as those described in US 47 1 9260 and do not exhibit the same advantages of sticking to a substrate such as polyethylene. This paper size applies to Chinese National Standard (CNS) Α4 specification (_ 2] 0X297 mm) (Please read the precautions on the back before filling this page) Clothing ·

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T -5-593520 V. Description of the Invention (2) US 3 16 1 620 discloses a method for reacting cis-butene dianhydride with thermally prepared hydrocarbon resin. It does not disclose at least partially hydrogenated resins or oligomers before reaction with maleic anhydride. EP 0 8 8 5 1 0 discloses a polar synthetic petroleum resin. In the specific examples disclosed therein, the cyclopentadiene oligomer mixture is reacted with a carboxylic acid or anhydride such as phthalic acid or maleic acid and then hydrogenated. The reaction proceeds via the acid group of the unsaturated reaction with the resin oligomer and thus forms an ester group at the point of attachment. The resulting resin products can generally be classified as norbornyl esters. The graft materials disclosed herein are produced via different pathways, i.e., via unsaturated bonds of acids or anhydrides, onto resins as defined herein which are preferably at least partially hydrogenated and more preferably substantially hydrogenated. The performance of hydrocarbon resins, especially hydrogenated aromatic cycloaliphatic resins, on polar surfaces can be improved by modifying these resins to include polar functional properties. Functional components are grafted to conventional hydrocarbon resins and / or resin oligomers and optionally combined with graft resins or graft oligomer materials and other tackifying resins or other tacky components to improve performance and provide Outperforms the advantages of TOREs and TPRs when used in hot melt and other adhesive formulations. In particular, the applicant has found that adhesive materials incorporating these graft components have improved compatibility with polar polymers such as EVA copolymers and exhibited on difficult substrates such as coated packaging surfaces. Good performance. It is stated that a specific embodiment of the present invention is a composition including at least two hydrocarbon resins, one of which is a resin selected from the group consisting of acids, anhydrides, and alcohols. The size of the paper is applicable to Chinese National Standard (CMS) A4 specifications ( 210X297 mm) (Please read the notes on the back before filling out this page) " tv "· Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 593520 A7 ___B7___ V. Description of Invention (3), amines and Fluorene imine, a petroleum hydrocarbon resin grafted with a graft monomer of a derivative thereof, wherein the composition is substantially free of graft oligomerization of cyclopentadiene including a norbornyl group and substituted cyclopentadiene And if the grafting monomer is an acid, anhydride, ammonium or amidine, the saponification of at least two hydrocarbon resins is between 1 and 1000 and where if the grafting monomer is an alcohol, according to ASTM E 222 94 measures hydroxyamidine between 1 and 100. The other hydrocarbon resin may be the same resin (except ungrafted) or any other suitable hydrocarbon resin. Any one of the resins may contain a C5 monomer. Oligomer And cyclopentadiene, oligomers of substituted cyclopentadiene and C9 monomers. The resin mixtures disclosed herein have a variety of properties including those used in hot melt adhesives, tapes, labels, binding and woodworking. The end use of the agent component. Illustrated Figures 1-6 illustrate the comparison between hotmelt adhesives containing graft resins on polyethylene and PET substrates and hotmelt adhesives containing other resin materials. Figure 7-12 illustrates the comparison between hot melt adhesives containing a resin material including a graft oligomer on polyethylene and PET substrates and hot melt adhesives containing other resin materials Figures 13-15 illustrate a hot melt adhesive containing a resin material including a graft oligomer and a hot melt adhesive containing other resin materials on an acrylic-oriented oriented polypropylene-coated cardboard substrate Comparative performance between adhesives This paper size applies the Chinese National Standard (CNS) A4 size (210x297 mm) (Please read the precautions on the back before filling out this page) Clothing · Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Cooperatives- 6- 593520 A7 ______B7 4. Description of the invention (4) Detailed description of resin blends The blends of the resins disclosed herein generally include at least two hydrocarbon resins, one of which is a resin selected from the group consisting of acids, anhydrides, alcohols, and imines. Petroleum hydrocarbon resins grafted with graft monomers of amidines and their derivatives, wherein the resin blend is substantially free of grafted oligos including cyclopentadiene and substituted cyclopentadiene based on norbornyl esters. Polymer and if the grafting monomer is an acid, anhydride, amidine or amidine, the saponification of at least two hydrocarbon resins is between 1 and 100 and where if the grafting monomer is an alcohol, according to AsTM E 222 94 measured hydroxyamidine between κ;! 00. As used herein, a resin material refers to a resin described herein, an oligomer, or a combination thereof, as described herein. Suitable examples of other hydrocarbon resins include: aliphatic hydrocarbon resins, at least partially hydrogenated aliphatic hydrocarbon resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least Partially hydrogenated cycloaliphatic resin, cycloaliphatic / aromatic hydrocarbon resin, at least partially hydrogenated cycloaliphatic / aromatic hydrocarbon resin, aromatic hydrocarbon resin, at least partially hydrogenated aromatic hydrocarbon resin, polyterpene Resin, terpene phenol resin, rosin ester, rosin acid, resin grafted with a graft monomer and a mixture of any two or more thereof. Suitable resins also include other resins having polar functional properties, whether or not produced by the methods described herein or other suitable methods. A specific embodiment is a composition including at least two hydrocarbon resins, wherein at least one resin is a graft resin material grafted with a graft monomer and the other resin is an ungrafted petroleum hydrocarbon resin. "At least two kinds of hydrocarbon resins" also includes hydrocarbon paper size applicable to Chinese National Standard (CNS) A4 specification (2 丨 0X 297 mm) (Please read the precautions on the back before filling this page) Intellectual Property Bureau, Ministry of Economics and Clothing Printed by the employee consumer cooperative 593520 A7 B7 5. In the description of the invention (6), the molar ratio of the graft monomer to at least two hydrocarbon resins is between 1: 4 and 1: 20. In another specific embodiment, the grafting monomer is an alcohol, and the molar ratio of the grafting monomer to the at least two hydrocarbon resins in the resin mixture is between 5: 3 and 1:20, and more preferably 1: 1 to 1: 15 and more preferably 2: 3 to 1: 10. The preferred weight range of the graft monomer in the resin mixture is 0.1-10% by weight, more preferably 0.3-10% by weight, more preferably 0.8-6% by weight, and even more preferably 1-5% by weight, more preferably 1-4% by weight. % Based on the total weight of the mixture. In a specific embodiment in which the grafting monomer is an acid or amidine or a derivative thereof, the grafting monomer preferably contains 0.1 and 10% by weight, more preferably 0.3 to 8% by weight, and more preferably 0.5 to 5 % By weight, based on the total weight of the mixture. In a specific embodiment in which one of the grafting monomers is an acid anhydride or amidine or a derivative thereof, the grafting monomer preferably contains 0.5 and 10% by weight, more preferably 0.8 to 6% by weight, and more 1 to 4% by weight, based on the total weight of the mixture. In a specific embodiment in which the grafting monomer is an alcohol or a derivative thereof, the grafting monomer preferably contains 0.1 and 10% by weight, more preferably 0.3 to 8% by weight, and more preferably 0.5 To 5% by weight, based on the total weight of the mixture, the preferred range of the saponified saponin of the resin mixture is 1-100, more preferably 3-100, more preferably 3-80 or 5-100, more preferably 5-50 or 8-60 , More preferably 10-40, more preferably 10.30, more preferably 15-30, and more preferably 20-30. For example, in a specific embodiment where the grafting monomer is an acid anhydride or amidine, the saponification of the resin mixture is 5-100, more preferably 8-60, more preferably 10-40, more preferably 15-30, and Better 20-30. In a specific embodiment in which the grafting monomer is an acid or amidine, the saponified saponification of the resin mixture is preferably 1-100, more preferably 3-80, and more preferably 5- This paper size is applicable to the Chinese National Standard (CN'S) Α4 specifications (2) 0X297 mm (Please read the notes on the back before filling this page). Order. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -9-593520 A7 __—_ B7 ___ V. Description of the invention ( 7) 50, more preferably 5-40, more preferably 5-30, and more preferably 5-20. In the case where the grafting monomer is an alcohol, the preferred range of the hydroxyamidine of the resin mixture is 1-100, more preferably 3_100, more preferably 3_80 or 5-100, more preferably 5.50 or 8-60, more Better 10-40, better 10-30, better 15-30, and better 20-30. For example, in a specific embodiment in which the grafting monomer is a diol or a poly-alcohol (polyol), the hydroxyamidine of the resin mixture is 5-100, more preferably 8-60, more preferably 10-40, more Better 15-30, and better 20-30. In a specific embodiment in which the grafting monomer is a mono-alcohol, the hydroxyamidine of the resin mixture is preferably 1-100, more preferably 3-80, more preferably 5-50, more preferably 5-40, more 5-30, and more preferably 5-20. For example, a specific embodiment is a composition that includes between 0.1-99% by weight of a graft resin material and between 1-99.9% by weight of other resins. Other specific embodiments include a graft resin material between 0.1-50 wt%, a graft resin material between 0.1-30 wt%, a graft resin material between 0.1-20 wt%, and a graft between 1-25 wt% Resin material, grafted resin material between 2: 15% by weight, grafted resin material between 1-10% by weight, grafted resin material between 5-10% by weight, and 10-30% by weight Grafting material based on total weight of resin blend. In a preferred embodiment, the resin material includes a graft resin and a graft oligomer. The graft oligomer is between 0.1 and 50% by weight, and more preferably between n and 30% by weight. More preferably oligomers between 0.1 and 20% by weight, more preferably 0.1 and 10% by weight grafted oligomers, more preferably between 1 and 30% by weight grafted oligomers, more preferably 1 Graft oligomers between 20% and 20% by weight, and more preferably between 1 and 10% by weight, based on the size of the resin. This paper applies Chinese National Standard (CMS) A4 specifications (21 0X 29 * 7 mm). (%) (Please read the notes on the back before filling out this page) Order printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • 10-593520 A7 B7 5. Description of the invention (8) Total weight of the blend. Preferred ranges are also included between any upper and lower limits described in this paragraph. (Please read the notes on the back before filling this page.) If grafted hydrocarbon resin is used in this article, the grafted hydrocarbon resin, oligomer, and / or resin material, or a combination thereof, indicates that it has been combined with the graft monomer. , Contact, and / or react. Grafting is a method of combining, contacting, or reacting a hydrocarbon resin, an oligomer and / or a resin material with a graft monomer material. Grafting hydrocarbon resins, oligomers, and / or resin materials, or combinations thereof, to include at least some polar functionality produces useful components such as adhesive formulations, especially HMA formulations. These formulations are often designed for use with polar polymers such as EVAs, ethylene methyl acrylates (EMAs), polyacrylates (PAs), polymethacrylates (PMAs), and ethylene alkyl acrylates. Performs well on substrates such as PET, recycled paper, cardboard, and acrylic paint and on other substrates such as wood, glass, ceramics, asphalt, concrete, and metal. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Therefore, specific embodiments of the present invention include grafted and ungrafted hydrocarbon resins (classes) and oligomers (classes), and compositions and mixtures thereof. Specific embodiments also include (but are not limited to): adhesives or tacky components including (i) grafted hydrocarbon resins; (Π) grafted oligomers, (iii) grafted oligomers + Ungrafted resin (class), (iv) grafted hydrocarbon resin + ungrafted resin (class), (v) grafted hydrocarbon resin + ungrafted oligomer, (vi) grafted hydrocarbon resin + grafted oligomer Polymer, (Vii) grafted oligomer + ungrafted oligomer or (viii) grafted hydrocarbon resin + grafted oligomer + ungrafted resin (type) and one or more other suitable combinations thereof. The specific embodiments described herein also include methods of making and using the foregoing materials. This paper size applies to Chinese National Standard (CNS) A4 specifications (2) 0X297 gongs -11-593520 A7 ___B7___ 5. Description of the invention (9) Suitable hydrocarbon resins that can be grafted include: aliphatic hydrocarbon resins, at least partly Hydrogenated aliphatic hydrocarbon resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic resins, cycloaliphatic / aromatic hydrocarbons Resins, at least partially hydrogenated cycloaliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, and mixtures of two or more thereof. Turpentine can also be grafted. Preferably, the resin is at least partially hydrogenated, more preferably substantially hydrogenated, and more preferably contains aromatic carbohydrates. In a specific embodiment, the resin includes a hydrocarbon resin produced by thermal polymerization of dicyclopentadiene (DCPD) or substituted DCPD, which may further include an aliphatic or aromatic monomer as described later. body. In a preferred embodiment, the hydrocarbon resin produced by thermal polymerization of DCPD or substituted DCPD and C9 monomers in the final resin product contains less than 10% aromatics. In another embodiment, the resin comprises a C5 / C9 (aliphatic / aromatic) hydrocarbon resin obtained by the polymerization (preferably thermal or catalytic) of a C5 monomer and a C9 monomer. Another specific embodiment of the graft oligomer is a kind of graft oligomer (dimer, trimer, tetramer, pentamer, hexamer, and heptamer and octamer, as required) Material), preferably from petroleum distillates boiling in the range of 30-210 ° C. The oligomers can be obtained by any suitable method and are often obtained as by-products of resin polymerization, whether by thermal or catalytic reactions. Oligomers can be obtained from methods in which oligomerization and then grafting of appropriate DCPD, (: 5 and / or (: 9 monomer feeds, as described below). Suitable oligomer streams have a range of 1 3 0-5 Between 00, it is better to use the paper size of China National Standard (CNS) A4 (2 丨 0X297 mm) (please read the precautions on the back before filling this page).

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -12-593520 A7 B7 V. Description of the invention (1〇) is between 130-410, preferably between 1 3 0-3 50, and more preferably 130_27. Molecular weight (Mη) between 200 and 350, and more preferably between 200 and 320. In one embodiment, the oligomer includes cyclopentadiene and substituted cyclopentadiene monomers. And may further include a C9 monomer. In another specific embodiment, the oligomer includes a c5 monomer and may further include a c9 monomer. Other monomers may also be present, including c4-c6 mono- and di-olefins and terpenes. The oligomer may also contain c9 monomer alone. In various embodiments, it is preferred that the oligomer is hydrogenated at least partially before grafting with the grafting monomer, and more preferably substantially hydrogenated. Appropriate individual examples of cyclopentadiene and substituted cyclopentadiene monomers (including DCPD), C9 monomers and C5 monomers are described below. Suitable oligomers may also include a mixture of one or more of the preferred oligomer materials as described herein. In a preferred embodiment, the hydrocarbon resin and / or oligomer has 1-60%, more preferably 1-40%, more preferably 1-20%, more preferably 1-15%, and more preferably 10-20%. , More preferably 15-20%, more preferably 1-10%, and more preferably 5-10% of the aromatic content, wherein the upper limit and any lower limit of any aromatic content can be combined into a better range of aromatic content. In a specific embodiment, the hydrocarbon resin to be grafted has a softening point of 10-200 ° C, more preferably 10-16 (TC, more preferably 60-1 30 ° C, more preferably 90-1 130 ° C , Better 80-1 20 ° C, better 80-15 (TC, and more preferably 90-110 ° c, where the upper limit and any lower limit of any softening point can be combined into a better range of softening point. Softening point fc) It is preferably measured as the ring and ball softening point according to ASTME-28 (Revised 1 996). As used herein, the aromatic content and olefin content are measured by 1H-NMR such as from directly having a frequency greater than 300 MHz (optimally 400 MHz (frequency (Equivalent)) The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 male H ~ -13-(Please read the precautions on the back before filling this page). Clothing, 1T Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Measurement of iH-NMR spectrum obtained by spectrometer with magnetic field strength of the description of the invention (11). The aromatic content is the integral of aromatic protons to the total number of protons. The olefin proton or olefin proton content is the integral of olefin protons to the total number of protons. The resin and / or oligomer is preferably at least partially hydrogenated and more preferably substantially hydrogenated. At least partially hydrogenated in this context means that the material contains less than 90% olefin protons, more preferably less than 75% olefin protons, more preferably less than 50% olefin protons, more preferably less than 40% olefin protons, and more preferably Less than 25% olefin protons, more preferably less than 15% olefin protons, more preferably less than 10% olefin protons, more preferably less than 9% olefin protons, more preferably less than 8% olefin protons, more preferably less than 7 % Olefin protons, and more preferably less than 6% olefin protons. As used herein, substantially hydrogenated means that the material contains less than 5% olefin protons after hydrogenation (and before reaction with the grafting monomer). , Preferably less than 4% olefin proton, more preferably less than 3% olefin proton, more preferably less than 2% olefin proton, more preferably less than 1% olefin proton, more preferably less than 0.5% olefin proton, more preferably less than 0.1% olefin protons, and more preferably less than 0.05% olefin protons. The degree of hydrogenation is typically performed to minimize and preferably avoid the hydrogenation of aromatic bonds. It is preferred that the resins and / or oligomers are substantially hydrogenated. In the specific embodiment, the salt is opposite to the copolymer (resin / oligomer and graft monomer). The grafting monomer is attached to the resin / oligomer backbone because of the lack of terminal olefinic bonds on the substantially hydrogenated resin / oligomer (as shown by the preferred low olefin proton measurement). As stated, resins and oligomers The polymer preferably includes one or more aromatic monomers. The data below show that aromatic materials produce better performance in adhesive compositions that include an aromatic-containing graft material. In addition, certain grafts Monomers, such as cis-butene dianhydride, have good solubility in aromatic-containing materials, and the paper size is applicable to China National Standard (CNS) A4 (210X297 mm) '" ~~~~ -14 -(Please read the notes on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Description of the invention (12) May allow a more uniform reaction phase and may avoid undesired by-products during the grafting reaction. Grafting monomers Preferred grafting monomers include any unsaturated organic compound containing at least one olefinic bond and at least one polar group (e.g., a carbonyl group), including unsaturated acids and anhydrides and derivatives thereof. Preferably, the organic compound contains ethylenic unsaturation conjugated to a curtain base (-C = 0) and preferably contains at least one α, / 3 olefin bond. Preferred grafting monomers include acids, alcohols, anhydrides, amines, amines, and derivatives thereof. Examples include carboxylic acids, fluorenyl halides or anhydrides, alcohols (phenols, monoalcohols, glycols, and polyalcohols), and derivatives thereof. Representative acids and acid derivatives include carboxylic acids, anhydrides, fluorenyl halides, esters, fluorenamines, fluorenimines and their salts, both metal and non-metal. Examples include maleic acid, trans-butylene acid, acrylic acid, methacrylic acid, itaconic acid, aconitic acid, citraconic acid, dicycloheptene dicarboxylic acid, tetrahydrophthalic acid, crotonic acid, α- Methylcrotonic acid, and cinnamic acid. Cis-butene dianhydride is a particularly good grafting monomer. Specific examples include, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, maleic ester of maleic acid, maleic acid Diethyl maleate, Dibutyl maleate, Dimethyl maleate, Dimethyl maleate, Dimethyl maleate, Diethyl maleate , Acrylamide, methacrylamide, maleimide monoamine, maleimide diamine, maleimide-N-monoethylammoniumamine, maleimide Diacid-N, N-diethylamidamine, maleic acid-N-monobutylamidamine, maleic acid-N, N · This paper size applies to Chinese National Standards (CNS) Α4 Specification (2 丨 〇Χ 297mm) (Please read the precautions on the back before filling out this page) Clothing, 1T Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -15- 593520 A7 B7 V. Description of the Invention (13) Dibutylphosphonium amine, trans-butylenedicarboxylic acid monofluorenylamine, transbutylenedicarboxylic acid difluorenylamine, trans-butylenedicarboxylic acid-N-monobutylphosphonium amine, trans.butanedioic acid_n, n _Dibutyl Fermented Amines' Cis Butylene Z: Amines N-butyl-cis-t-amidine, & phenyl-cis-butanimide, diammonium imine, sodium propionate, sodium methyl-sulfate, potassium succinate, and methylpropionamidine. Preferred grafting monomers include acids, anhydrides, alcohols, amidines, and amines. Hydrocarbon resin manufacturing hydrocarbon trees β are known and manufactured, for example, by Furried-Quarfurt with various feeds (which may be pure monomer feeds or refinery streams containing mixtures of various unsaturated materials) Polymerization. Generally speaking, it is easier to polymerize with relatively pure feed polymerization. For example, pure styrene, pure α-methylstyrene, and mixtures thereof are easier to polymerize than the c8 / C9 refinery stream. Similarly, pure or concentrated pentadiene polymerizes more easily than the C4_c6 refinery stream. However, these pure monomers are more expensive to manufacture than refinery streams that are usually by-products of large volume refineries. Aliphatic hydrocarbon resins can be prepared by cationic polymerization of cracked petroleum feeds C4, C5, and (6 chain hydrocarbons, olefins, and conjugated diolefins referred to herein as c5 monomers. As used herein In the C5 monomer, DCPD monomers removed by hot dipping as described below are preferably excluded. These C5 monomer streams include cationic and thermally polymerizable monomers such as butadiene, isobutene, [, 3-pentadiene (Pentadiene) and 1,4-pentadiene, cyclopentene, pentene, pentene, 2-methyl-1-pentene, 2-methyl-2-butene, 2-methyl Iso-2-pentene, isoprene, cyclohexene, I-3-hexadiene, 1-hexadecadiene, cyclopentadiene, and bicyclo This paper is suitable for mid-range furniture standards ( CNS) M specification (21Q > < 297 public envy (please read the notes on the back before filling this page) Order the printed olefins from the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. -16 593520 A7 ______B7 V. Description of the Invention (Μ) In order to obtain these feeds, the refinery stream preferably removes impurities typically by fractional distillation and processing purification. In some embodiments, the C5 feed stream may include at least some (preferably less) 2% by weight) cyclopentadiene (CPD) and substituted cyclopentadiene (eg, methylcyclopentadiene) components. These components are optionally separated from the C5 monomer stream by hot impregnation as needed Where the feed stream is heated to a temperature between 0 ° C and 160 ° C, preferably between 100 ° C and 150 ° C, for 0.5 to 6 hours, followed by separation of the DCPD monomer In order to reduce the content of cyclopentadiene and / or monocyclopentadiene in the C5 monomer stream to preferably less than 2% by weight. Low temperature hot dipping is preferred in order to limit cyclodiene (cyclopentadiene and methyl Copolymerization of cyclopentadiene) with Cs straight-chain conjugated monoene (isoprene and pentadiene, 3 cis- and trans-). The hot impregnation step is preferably dipolymerized cyclopentadiene And substituted cyclopentadiene to make it easier to separate from the C5 monomer stream. After fractionation and, if performed, hot dipping, the feed is preferably distilled to remove cycloconjugated diene (which is a gel Precursor) (Cyclopentadiene and methylcyclopentadiene to be removed, such as dimers, trimers, etc.). Examples of c5 monomer streams are boiling at -10 to 100 ° C. steam Cracked petroleum stream. Examples of commercially available samples of C5 monomer feed include naphtha petroleum 3-pentadienes from Lyondell Petrochemical Company of Houston, Texas, general pentadiene concentrates or advanced pentadiene concentrates. In the case of Hoogvilet, Dutch Chemical B. V. The resin polymerization feed may also contain C8-C1Q aromatic hydrocarbon monomers (referred to herein as C 9 monomers) such as styrene, indene, and derivatives of styrene. , Indene derivatives, and combinations thereof. Particularly preferred aromatic olefins include styrene, α-methylstyrene, / 5-methylstyrene, indene, methylindenes, and butenyltoluene. C9 monomer This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). Printed by the Consumer Cooperative 593520 A7 B7 V. Description of the invention (15) An example of the flow is at -lot to 210 ° c (if C5 monomer and DCPD components are not present, boiling in the range of 135 ° C to 21 (TC) Of steam cracking petroleum stream. Examples of commercial C9 monomer feeds include LRO-90 from Lyondell Petrochemical Company of Houston, Texas, DSM C9 resin feeds from DSM, Geleen, The Netherlands, RO-60 and RO from Mich. Midland Chemical Company -80, and resin resin 60-L from Terneuzen Dow Chemical Company, Netherlands. In addition to the reactive components, the non-polymerizable components in the feed may include saturated hydrocarbons such as pentane, cyclopentane, or 2-methylpentane that can be codistilled with unsaturated components. This monomer feed can be copolymerized with other C4 or C5 olefins or dimers. However, it is preferred to purify the feed to remove unsaturated materials (e.g., isoprene) that adversely affect the polymerization reaction or cause undesirable colors in the final resin. This is usually done by fractionation. In a specific embodiment, the polymerization is performed using a furried-quarfurt polymerization catalyst such as a Lewis acid (for example, boron trifluoride (BF3), boron trifluoride on or not on a carrier). (AlCl3), aluminum trichloride complex or alkylaluminum halides, especially chloride). Suitable reaction conditions for the furried-quarfurt polymerization include a temperature of -20 ° C to 100 ° C, and a pressure of 100-2000 kPa. In a specific embodiment, C5 and C9 monomers are polymerized by this method. Typically, the feed stream includes 20-80% by weight monomer and 20-80% by weight solvent. Preferably, the feed stream comprises 30-70% by weight monomer and 30-70% by weight solvent. More preferably, the feed stream includes 50-70% by weight monomer and 30-50% by weight solvent. The solvent may include an aromatic solvent, which may be toluene, xylene, other aromatic solvents, aliphatic solvents, and / or one or more mixtures thereof. Solvents This paper is sized for Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-18-593520 A7 B7 V. Description of the invention (16) It is better to be recovered. The solvent may include non-polymerizable components of the feed. The solvent usually contains less than 250 p p m of water, preferably less than 100 p p m of water, and most preferably less than 50 p p m of water. In another specific embodiment, the feed stream includes 30-95% by weight of c5 zirconium, as described above, and 5-70% by weight, including at least one member selected from the group consisting of pure monomers, C9 monomers, and terpenes. Co-feeding. Preferably, the feed stream comprises about 50-85% by weight C5 monomer and about 15-50% by weight co-feed, including at least one member selected from the group consisting of pure monomer, C9 monomer, and terpene reservoir. Typically, the obtained hydrocarbon resin has a number-average molecular weight (Mn) of 400-30,000, a weight-average molecular weight (Mw) of 500-6000, a z-average molecular weight (Mz) of 700- 1 5,000, and between 1.5 and 4. Polydispersity (PD), as measured by Mw / Mn. As used herein, molecular weight (number-average molecular weight (Mη), weight-average molecular weight (Mw), and z-average molecular weight (Mz)) are penetrated by using a Water 1 50 gel with a differential refractive index detector installed Chromatograph and gel size measurement using polystyrene standards calibrated. The samples were operated in tetrahydrofuran (THF) (45 ° C). Molecular weight is reported as polystyrene-equivalent molecular weight and is usually measured in grams / mole. The monomer feed can be copolymerized with (4 or C5 olefins or olefin dimers thereof) as chain transfer agents. Chain transfer agents can be added up to 40% by weight (preferably up to 20% by weight) to obtain The bulk feedstock is made of resin with low and narrow molecular weight distribution. In a way, the chain transfer agent stops the growth of the polymer chain by terminating the chain, and the starting position of the regenerated polymer. The component, its As a chain transfer agent in the reaction, it includes, but is not limited to, 2-methyl-1-butane, 2-methyl-2-butene, or dimers or oligomers of these kinds. This paper applies to f National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) ··· 11 Printed by the Intellectual Property Bureau of the Ministry of Economy Staff Consumer Cooperatives-19- 593520 A7 B7 V. Description of the invention (17) «The transfer agent can be added to the reaction in pure form or diluted in a solvent. DCPD resin and / or its oligomer (also known as CDP oligomer) can be added by a It is obtained or derived by thermal polymerization of DCPD unsaturated monomer feed. In a specific In the embodiment, the feed also includes the aromatic monomer as previously described. In this specific embodiment, (a) the DCPD stream, preferably one at 80-20 ° C (more preferably 140 ° C) To 200 ° C) boiling steam cracked petroleum distillates, including dimers and co-dimers of cyclopentadiene and its methyl derivatives, together with (b) C9 monomers, preferably one at 15 〇-2200 ° C boiling steam cracking petroleum distillates, including methylstyrene, vinyltoluene, indene and methylindene with other 09 and C1Q aromatic hydrocarbons, in a weight ratio (a: b ) Between 90:10 and 50:50, heated to 160-3 20 ° C in a batch polymerization reactor at a pressure of 9.8xl 05-20xl05 bar (more preferably 9.8x105-11 · 7x105 bar) After 1.2 to 4 hours (more preferably 1.5 to 4 hours). In cases where oligomer inclusions are not required, the resulting polymerization product can be steamed to remove inert, unreacted and low molecular weight oligomeric components to produce Resin having a softening point in the range of 80-120 ° C. In a specific embodiment, the resin is preferably obtained by feeding from a feed comprising a C5 monomer and a C9 monomer as previously described. It is obtained or derivatized by thermal polymerization. In a specific embodiment, (a) the C5 monomer, preferably a steam cracking petroleum distillate boiling in the range of 80-200 ° C, together with (b) the C9 monomer, It is preferably a steam cracking petroleum distillate boiling in the range of 150-200 ° C, including a mixture of α-methylstyrene, vinyltoluene, indene, and methylindene with other C8-C1G aromatic hydrocarbons. The ratio (a: b) is between 90:10 and 50:50, in a batch polymerization reactor at 9.8x 1 05-20x 1 05 bar (better 9.8xl05- this paper size applies to the Chinese national standard (CNS ) A4 size (210X 297mm) I ------- install-(Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-20T-593520 A7 B7 V. Description of the invention (18) (Please read the precautions on the back before filling this page) 1 1.7xl05 bar) 160_320 ° C, after 1.2 to 4 hours (more preferably 1.5 to 4 hours). Where oligomer content is not required, the resulting polymerization product can be steamed to remove inert, unreacted, and low molecular weight oligomeric components to produce a resin having a softening point in the range of 80-1 20 ° C. The products of the polymerization process include resins and oligomers (dimers, trimers, tetramers, pentamers, hexamers) including the monomers (classes) of the feed, and heptamers and octamers selected as required Polymer) oligomer by-products. If used in the following, the resin material means resin, oligomer, or a mixture of the two. In a specific embodiment in which the oligomer by-product is produced by thermal polymerization of DCPD and substituted DCPD, the oligomer is typically a (preferably hydrogenated as described below) CDP and methyl CDP with a low content of Acyclic C5 diene compounds such as Diels Alder trimers and tetramers of pentadiene-1,3 and isoprene. The resin material is then preferably hydrogenated to reduce staining and improve color stability. Any method known for the catalytic hydrogenation of resin materials can be used. In particular, the methods disclosed in US 5 1 7 1 793, US 4629766, and the Intellectual Property Office Employee Consumer Cooperatives of the Ministry of Economy printed US 5 502 1 04 and US 43 28090 and WO 95/1 2623 are suitable. Excluded hydrotreating conditions include 100-35 (temperature range of TC and hydrogen pressure between about five atmospheres (506 kPa) and 300 atmospheres (and up to 400 atmospheres), for example, 10- Reaction at 275 atmospheres (10 1 3-27579 kPa). In a specific embodiment, the temperature is in the range including 1 80-3 3 0 ° C and the pressure is in the range including 1 5 1 95-20260 kPa hydrogen. Reactor The volume ratio of hydrogen to feed under standard conditions (25 ° C, 1 atmosphere (101 kPa) pressure) typically ranges from 20: 1 -200: 1; for water-white resin, 1 00: 1 -200 : 1 is the Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-593520 A7 B7 which is better than the paper size. 5. Description of the invention (19). The hydrogenation product can be stripped to remove low molecular weight by-products and Any solvent. This oligomerization by-product is a low-viscosity, almost colorless liquid that boils at 250-400 ° C and is preferably substantially hydrogenated. The hydrogenation of the resin material can be done in batches or via a melt or solution-based method It is generally carried out continuously. The catalyst for the hydrogenation of hydrocarbon resins is typically on a support. Mono- and di-metal catalyst systems based on Group 6, 8, 9, 10 or 11 elements. Catalysts such as nickel on a carrier (for example, nickel on alumina, nickel on charcoal, nickel on silica, Nickel on diatomaceous earth), palladium on the carrier (for example, palladium on silica, palladium on charcoal, palladium on magnesium oxide, etc.) and copper and / or zinc (for example on copper and / or Copper chromite on manganese oxide, copper and zinc on alumina, etc.) are good hydrogenation catalysts. The support materials are typically made of such porous inorganic refractory oxides such as silica, magnesia, silica-magnesium Oxygen, oxidation pins, silica-chromium oxide, titanium oxide, silica-titanium oxide, alumina, silica-alumina, alumina-silicate, etc., and a carrier containing r-alumina is excellent. The support is essentially free of crystalline molecular sieve materials. It is also expected that mixtures of the foregoing oxides, especially when prepared as homogeneously as possible. Support materials that may be used include those disclosed in U.S. Patents 4,860,030, 484696 1, 4500424, and 4,849,093. Appropriate Carriers include alumina, silica, carbon, M gO, Ti02, Zr02, Fe203 or mixtures thereof. Another suitable method for hydrogenating resin materials is described in EP 0082726. EP 0082726 describes a method for catalytic or thermal hydrogenation using a nickel-tungsten catalyst on an r · alumina support. , Where the hydrogen pressure is 1.47 × 107—196 × 107 bar and the temperature is in the range of 25 0-3 30 ° C. After hydrogenation, the reactor mixture can be used in accordance with Chinese National Standard (CNS) A4 specifications (210X29? Gongchu) ) (Please read the precautions on the back before filling out this page) C., 11 Intellectual Property Bureau of the Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives-22- 593520 A7 ___B7 V. Invention Description (2〇) (Please read the back Note for refilling this page) is flashed and further separated to recover the hydrogenated resin material. In a specific embodiment, steam distillation can be used to separate oligomers and is preferably performed at a resin temperature not exceeding 3 25 t. In ~ specific embodiments, the catalyst comprises nickel and / or cobalt and one or more molybdenum, tungsten on one or more alumina or silica supports, wherein the amount of nickel oxide and / or cobalt oxide on the support In the range of 2-10% by weight. The amount of tungsten oxide or molybdenum on the support after preparation ranges from 5 to 25% by weight. Preferably, the catalyst comprises 4-7 wt% nickel oxide and 18-22 wt% tungsten oxide. This method and suitable catalysts are disclosed in more detail in U.S. Patent No. 5,820,749. In another embodiment, the hydrogenation can be performed by using the method and catalyst described in U.S. Patent No. 4,029,766. In particular, a nickel-tungsten catalyst on r-alumina is preferred. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In a specific embodiment, the oligomer is stripped from the resin before hydrogenation. In this embodiment, the oligomer is preferably hydrogenated before grafting. In another embodiment, the oligomer is hydrogenated with the resin and then stripped from the resin to produce a hydrogenated resin and a hydrogenated oligomer. In another specific embodiment, at least some of the oligomers are stripped before hydrogenation and at least some of the hydrogenated oligomers are stripped after hydrogenation. In yet another specific embodiment, the hydrogenated resin / oligomer product can be further processed together into a single mixture as described below. However in another specific embodiment, the oligomer may be derived from any suitable source and argonized (if necessary) prior to grafting such that the oligomer is typically at least partially hydrogenated and preferably substantially prior to grafting hydrogenation. Grafted resin material This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm ^ -23-593520 A7 ____ B7 V. Description of invention (21) (Please read the precautions on the back before filling this page) At least A portion of the resulting resin material is preferably derived from a method as described above, and may then be combined and / or contacted with the graft monomer, typically under appropriate reaction conditions and in a suitable mixing device. In the preferred embodiment In the specific reaction according to the foregoing, the resin and the oligomer can be grafted separately or simultaneously, and if separately, the grafted oligomer can then be selectively combined with the graft as needed. Resin, non-grafted resin, or any other suitable resin, tacky component or composition as described above, and then remixed. Graft monomers printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the grafting monomers are preferred in It is selected from the group consisting of an organic peroxide, an organic perester, and an azo compound to occur in the presence of a radical initiator. Examples of such compounds include benzhydryl peroxide, dichloride Formamyl peroxide, dicumyl peroxide, di-tertiary-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne- 3,1,4-bis (tertiary · butylperoxyisopropyl) benzene, lauryl peroxide, tertiary-butyl peracetate, 2,5-dimethyl-2,5-di (Tertiary-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane, tertiary-butyl perbenzoate , Tertiary-butyl perphenyl acetate, tertiary-butyl perisobutyrate, tertiary-butyl per-secondary-octanoate, tertiary-butyl pervalerate, perpentyl Acid cumyl ester, tertiary-butyl hydroperoxide, tert-butyl perethyl acetate, azoisobutyronitrile, and dimethyl isobutyrate. Peroxide It has a half-life of about 6 minutes and volatile non-aromatic decomposition products at 160 ° C and these minimize color formation. Preferred peroxides include di-tertiary-butyl peroxide and 2, 5-Dimethyl-2,3-di (tertiary-butylperoxy) hexane. The amount of conjugated peroxide typically depends on the weight of the graft monomer. In a specific paper I, the Chinese National Standard (CNS) A4 specification (210X297 mm 1 -24-593520 is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by A7 B7. V. Description of the invention (22) In the embodiment, the reaction mixture The weight ratio of medium grafting monomer: peroxide may be between 1 and 20, more preferably between about 1 and 10, more preferably between about 1 and about 5, and even more preferably about 4. The grafting monomer can be combined with the resin material at 50-200 ° C, more preferably between 70-150 ° C, more preferably between 7 0-1 2 5 ° C, and even more preferably Temperature and pressure between 1 4 0 -1 8 0 ° C, more preferably 140-1 80 ° C, more preferably 1 55- 1 65 t or 1 65- 1 75 ° C It is typically one atmosphere but higher pressures can be used if desired. In a specific embodiment, the reaction temperature is 170-1 85 ° C. In another preferred embodiment, the grafting reaction is greater than 90 ° C, more preferably between 90 ° C and any of the above temperature limits, more preferably between 90 ° C and 150 ° C, and more preferably Occurs at temperatures between 90 ° C and 145t. Generally, the lower limit of the reaction temperature is determined by the softening point of the resin, and the grafting reaction is preferably performed at a temperature above the softening point of the material to be grafted. The graft monomer may be combined so that the weight ratio of the graft monomer: resin material in the reaction mixture is less than 1, more preferably less than 0.5, more preferably less than 3 ·· 10, and more preferably less than 3: 2. . In a preferred embodiment, the reaction mixture is maintained in a homogeneous state. The reaction mixture is preferably agitated or vigorously stirred. During the reaction, the free radical initiator is added all at once or preferably in a continuous or semi-continuous mode with the resin material-graft monomer reaction mixture. The residence time in the reaction zone is preferably less than 75 minutes, more preferably less than 60 minutes, and even more preferably between 30 and 60 minutes. In specific embodiments where only the oligomer is grafted, the reaction temperature is preferably between 50-200 ° C, more preferably between 70-15 ° C, and more preferably between 70-1 25t: Preferably between 1 40- 1 80 ° C, more preferably between 1 40- 1 80 ° C, and the paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the back (Please fill in this page again)

-25- 593520 A7 B7__ 5. Description of the invention (23) The temperature is preferably between 1 5 5- 1 65 ° C, and more preferably about 160 ° C. In a specific embodiment, the reaction temperature is from 1 70 to 1 85 ° C. In another preferred embodiment, the grafting reaction occurs at a temperature greater than 90 ° C, more preferably between 90 ° C and any of the above temperature systems, more preferably between 90t and 15 ° C, and more preferably Between 9 ° C and 145 ° C. The amount of grafting monomer added typically depends on the amount of oligomer. Better, oligomer: Mole ratio of grafting monomer is between 5 and 0.2, More preferably between 2 and 0.5, more preferably between about 1.5 and 0.67 and more preferably about 1. Thereafter, the ungrafted oligomer is stripped from the product and selectively recycled to the reaction zone. The resulting grafted oligomer is Polymers usually have a softening between 0-120 ° C, more preferably between 25-120 ° C, more preferably between 50-1 120 ° C and even more preferably between 80-1 10 ° C Dot and 4-1 〇 Garden's color. Garden's color, as used herein, is measured using ASTMD-6166. The grafted oligomer product can then be combined with the resin (grafted or ungrafted), from which it can be combined with Other resins, polymers, and / or other materials are derived or combined and formulated into adhesive materials. In specific embodiments where only the resin is grafted, the reaction temperature is preferably between 50-200 ° C, and more preferably At 70- 1 50 ° C, more preferably 70-1 25 ° C, more preferably 140-180 ° C, more preferably 140-1 80 ° C, more preferably 1 65-1 75 ° C, and more preferably about 170 ° C. In another preferred embodiment, the grafting reaction occurs at a temperature greater than 90 ° C, more preferably between 90 ° C and any of the above mentioned upper limits The amount of grafting monomer added typically depends on the amount of resin. The weight of grafting monomer: resin in the reaction mixture is preferably less than 1: 5, more preferably less than 1: 1, more preferably less than 1: 2 0, and even more preferably about 1: 4 0. Generally, the softening point of the resin caused by grafting is less than 10 ° C, preferably less than this paper size. Applicable to China National Standard (CNS) A4 specification () 10X297 mm (Please read the notes on the back before filling this page) £-， 11 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -26- 593520 Α7 Β7 V. Description of the invention (24) 5 C and a kind of _6 Graft resin between colors (Please read the notes on the back before filling this page) In another embodiment, the oligomer is not stripped from the resin product, and the resin and The oligomers are grafted at the same time. The reaction conditions are similar to the aforementioned graft resins, but the weight ratio of the grafting monomers · resin materials is usually kept below 0.5, more preferably below 0.25 and more preferably below 3: 2 When the grafting is completed, the material can be further stripped if necessary to produce the resin at the desired softening point and / or remove unreacted oligomers. If necessary, separation of the grafted oligomers from the graft resin can also be performed, but It can be used without this further processing. In many specific embodiments including a graft resin and a graft oligomer, the weight ratio of the graft oligomer to graft resin in the resin material will be greater than 0.005, more preferably greater than 0.001, It is more preferably greater than 0.02, more preferably greater than 0.05, and more preferably greater than 0.1. Grafting of resin materials printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics can also be performed via a solution path, in which the resin materials are dispersed in a solvent and combined with the graft monomer, contact and / or react. In addition «3 ^ Alternatively, the grafting monomer may be dispersed in a solvent before being added to the resin material. These pathways allow lower reaction temperatures (as low as 10 (TC) and allow the selection of different peroxides at low reactions and temperatures with a half-life of 6 minutes. Appropriately dissolve U @ bracket (but not limited to) aliphatic solvents, Cycloaliphatic solvents, aromatic solvents, and aromatic-aliphatic solvents. Typical examples include benzene, toluene, xylene, chlorobenzene, n-pentane, n-hexane, n-heptane, n-octane, n-decane, Isoheptane, isodecane, isooctane, cyclohexane, alkylcyclohexane, and combinations of two or more thereof. Salty grafting monomers via olefinic bonds of the grafting monomers such as α, Θ The olefin bond is grafted to the resin material. By using this path, the oligomer is grafted, and the formation of norbornyl ester groups in the grafted resin material is minimized and preferably avoided. This paper applies the Chinese national standard (CNS) ) A4 specification (210X297 mm) 593520 A7 B7 5. Invention description (25). Therefore, the obtained graft resin material does not substantially have a norbornyl ester group, that is, it preferably contains less than 0.5% by weight, more preferably less Less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less 001% by weight of norbornyl ester groups. The obtained graft oligomers and / or graft resins are preferably at least one of (i) a monoalkylmaleic acid, an anhydride or a derivative thereof, or ( ii) / 5-alkyl substituted propionic acid or derivative thereof. The reaction product of the resin material and the graft monomer or the product of the combination of the resin material and the graft monomer may also include oligomerization of some graft monomers. It can be removed before or after the final composition is prepared. The obtained graft resin material preferably has a temperature between 15-2 1 0 ° C, more preferably 15-170 ° C, more preferably 65-1 40 ° C. , More preferably 65-130 ° C, more preferably 80-120 ° C, more preferably 90-110 ° C, and more preferably a softening point of about 85-110 ° C. The graft resin material preferably has less than 120 ° C, preferably less than 110 ° C, more preferably between 25-100 ° C, more preferably between 60-100 ° C, more preferably between 60-80 ° C, and more preferably 3 Glass transition temperature (Tg) between 5 and 70 ° C. Differential scanning calorimetry (DSC, ASTMD 3 4 1-8 8) is used to measure Tg. The obtained graft resin material preferably has a temperature greater than 10, more Preferably greater than 12, more preferably greater than 15, more preferably greater than 16, more preferably greater than 17, It is preferably greater than 18, more preferably greater than 19, more preferably greater than 20, and more preferably greater than 25. Saponified saponin (mg KOH / g resin material). The obtained graft material preferably has greater than 10, more preferably greater than 15, and more preferably greater than 20 In a specific embodiment, the graft oligomer material has a value between 50 and 0.5, more preferably between 10 and 2, more preferably between 5 and 2, and even more preferably between 1.5 and 0.67. And the oligomer of about 1: the molar ratio of the grafting monomer. In some specific embodiments, the grafting monomer in the grafted resin product: the paper size of the tree applies the Chinese National Standard (CNS) A4 Specifications (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -28-593520 A7 ___B7 V. Description of the invention (26) The weight ratio of fat is better than 1, and in other specific embodiments is between 0.0 0 1 and 1, In other specific embodiments, between 0.01 and 1, in other specific embodiments, between 0.01 and 0.3, in other specific embodiments, between 0.02 and 1, and in other specific embodiments, between 0.1 and 1 Time, between 0.3 3 and 1 in other specific embodiments, and between 0.1 and 0.2 in other specific embodiments, wherein the preferred range may be included between any upper and lower limits described in this paragraph . Any of the foregoing embodiments mixed with adhesive components and compositions can be combined with other adhesive components and formulated into pressure-sensitive adhesives, HMAs, or adhesives for use in, for example, tapes, labels, and paper impregnation applications. Press the adhesive. HM A applications include woodworking, packaging, bookbinding or diapers. The specific embodiments described herein can also be formulated as a combination of sealant, rubber compound, tube wrap, carpet lining, pressure-sensitive adhesive, road signs and / or tires. When in the case of HMAs, these compositions can be used directly without further dilution or they can be diluted to a suitable solvent to form a solvent-based adhesive (SB As) or dispersed in water to form a water-based adhesive (WBAs) resin emulsion. Any of the foregoing embodiments may be combined or formulated into an adhesive including a polar polymer. As used herein, polar polymers include those containing polar groups such as esters, ethers, ketones, amidines, amines, alcohols, phenols, halides, acids, anhydrides, sulfurized Homopolymers, copolymers, and terpolymers of species, nitriles, isocyanates, aromatic and heteroaromatic groups. These polar substitutions can be found in the polymer main chain. The paper size of the polymer main chain applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) '-29- (Please read the precautions on the back before filling this page )! ·· 11, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _________ B7 _ V. Description of the invention (27) (Please read the precautions on the back before filling this page) Side chain or connect to the combinable An aryl group on the polymer backbone or a side chain of the polymer backbone. Suitable examples include c2 to C20 olefins (such as ethylene and / or propylene and / or butene) and one or more polar monomers such as vinyl esters or alcohols, acids, anhydrides, propylene or methacrylic acid or esters Copolymers. The polar polymer also includes any thermoplastic copolymer containing a functional group capable of interacting with an unsaturated acid or an acid anhydride present in the resin material. Examples include, but are not limited to, polyesters, polyamides, polyureas, polycarbonates, polyacrylonitrile, polyacrylates, polymethacrylates, ethylene vinyl acetate Esters, halogenated polymers, polyvinyl chlorides, polyethylene terephthalate, polybutylene terephthalate (PBT), polyacetals, acrylic or methacrylic acid, alkyl acrylates, or Polymers (or copolymers) of methacrylates and analogs. Therefore, in a specific embodiment, the graft resin material can be formulated with a polar polymer such as EVA. It optionally includes other components such as one or more tinctures or oils. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Any of the foregoing embodiments may be combined with polyolefin (base polymer) to form an adhesive. Typical base polymers include polyethylene, ethylene copolymerized with one or more C3 to C2G linear, branched or cyclic alpha-olefins, polypropylene, and one or more ethylene and / or C4 to C2G linear, Propylene, polybutene copolymerized with branched or cyclic α-olefins, butene copolymerized with one or more C5 to Cw linear, branched or cyclic α-olefins, low density polyethylene (LPDE) ( Density 0.915 to less than 0.93 5 g / cm3), linear low density polyethylene (LLPDE), ultra-low density polyethylene (density 0.86 to 0.908 g / cm3), very low density polyethylene (density 0.9 〇As of 0.915 g / cm 3), medium and low density polyethylene (density 0.993 5 to less than 0.945 g / cm 3) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -30- 593520 A7 B7 5. Description of the invention (28), high and low density polyethylene (HDPE) (density 0.945 to 0.98 g / cm3). Other hydrocarbon polymers (or copolymers) include: polybutene-1, polyisobutylene, polybutene, polyisoprene, polybutadiene, butyl rubber, amorphous polypropylene, ethylene propylene diene Monomer rubber, natural rubber, styrene butadiene rubber, copolymers and halogenated copolymers of isobutylene and p-alkylstyrene, elastomers such as ethylene · propylene rubber (EPR), vulcanized EPR, EPDM, nylon, poly Carbonates, PET resins, polymers of aromatic monomers such as polystyrene, copolymers of isobutylene and p-alkylstyrene, high molecular weight HDPE, low molecular weight HDPE, graft copolymers, usually polyacrylonitrile homopolymers Or copolymers, thermoplastic polyamides, polyacetals, polyvinylidine and other fluorinated elastomers, polyethylene glycols, polyisobutylene, or blends thereof. Preferred alpha-olefins include propylene, butene, pentene, hexene, heptene, octene, nonene, dodecene, cyclopentene, 3,5,5-trimethylhexene-1,3 A terpolymer of methylpentene-1,4-methylpentene-1 and the above monomers. In another specific embodiment, the copolymer includes a terpolymer of ethylene and / or (ii) a C3 to C20 comonomer, and (iii) a diene. Preferred dienes include butadiene, pentadiene, hexadiene, norbornene, ethylidene norbornene, vinylidene norbornene, dicyclopentadiene, and substituted ones. The structure of these polymers may be linear, substantially linear, short-chain branched, long-chain branched, star-branched, or any other combination thereof. The branches or arms may be the same as or different from the main chain such as a branched-block copolymer or a multi-armed star polymer. Suitable polymers also include block copolymers of styrene and one or more conjugated diene such as SI (styrene-isoprene), SBs (styrene-butadiene-styrene), SB (styrene -Butadiene), SIS (styrene-isoprene-benzene paper standard (CNS) A4 specification (210X 297 mm) ~ -31-(Please read the precautions on the back before filling this page) • Installation · 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _B7 V. Description of the Invention (29) Ethylene) Also suitable are styrene block copolymers comprising tetra- or penta-block copolymers selected from SISI, SISB, SBSB, SBSI, ISISI, ISISB, BSISB, ISBSI, BBSSB, and BSBSI. These block copolymers can be completely or partially hydrogenated to produce a resulting SEBS (styrene-ethylene-butene-styrene) polymer. The structure of the block copolymer includes linear, radial or multi-armed star, or multi-branched and may include various styrene, isoprene, or a combination of butadiene, which may be hydrogenated or not hydrogenation. Any of the foregoing specific embodiments may be mixed with graft polymers or blends of graft polymers and / or non-grafted polymers. Examples of polymers and such blends include, but are not limited to, those described in US 5,936,058. Any of the foregoing embodiments may be mixed with the elastomer to form an adhesive sealant. Preferred elastomers include natural rubber, polyisoprene, polybutadiene, copolymers of butadiene and styrene, copolymers of butadiene and acrylonitrile, butyl rubber, polyprene, ethylene / Elastomer copolymers of propylene rubber and ethylene, propylene and non-conjugated diene, styrene block copolymers such as styrene and / or methylstyrene and alkadiene (such as isoprene or butadiene) Linear, radiant, and / or tapered block copolymers. In a specific embodiment, the base polymer may be a polymer produced using a metallocene catalyst system. Typically, these metallocene homopolymers or copolymers are solutions or slurries using a combination of a mono- or bis-cyclopentadienyl transition metal catalyst and an alumoxane and / or non-coordinating anion activator. Material, partial pressure or gas phase. The catalyst system may or may not be supported and the cyclopentadienyl rings may be substituted or unsubstituted. Titanium, zirconium and bell are the preferred transition metals. Several papers prepared using these catalyst / activator compositions are sized to the Chinese National Standard (CMS) A4 (210X 297 mm) " " ~~ " ~ '-32- (Please read the back first (Notes to fill out this page)

593520 B7 V. The commercial product of invention description (30) is a trademark of EXCEED® and EXACT® from ExxonMobil Chemical Company of Baytown, Texas or a trademark of ENGAGE® and AFFINITY® of Dow Chemical Company Commercial goods. The copolymer prepared by the above metallocene preferably has a polydispersity of less than 4 and a composition distribution width index (€ 0) of 50% or more, preferably 60% or more, and even more preferably 70% or more. In a specific embodiment, € 81 is 80% or more, even more preferably 90%, or even more preferably 95% or more. In a specific embodiment, the polyethylene copolymer has a CDBI between 60-85% and even more preferably between 65-85%. The Composition Distribution Width Index (CDBI) is a measure of the composition distribution of a monomer within a polymer chain and is measured by the procedure described in PCT Publication WO 93/03 093, published February 18, 1993. When CDBI is determined This includes ignoring portions with a weight average molecular weight (Mw) of less than 15,000. Any of the foregoing specific embodiments may be present in a blend of a resin and a base polymer. Suitable ratios of resin: base polymer include 1: 1 to 2: 1, more preferably 1: 2 to 2: 1 and even more preferably between 3: 1 and 1: 3. Any of the foregoing embodiments may be combined with additives known in the art such as processing oils, performance oils, anti-blocking agents, antistatic agents, antioxidants, cross-linking agents, silica, carbon black, talc, pigments, fillers , Processing aids, XJV stabilizers, neutralizers, lubricants, anti-slip agents, slip agents, surfactants and / or nucleating agents. Examples of common additives include, for example, Irganox® 1010, sand oxide, nitric oxide, polymethyl methoxide, talc, dyes, gadolinium, calcium stearate, carbon black, and glass beads. In HMA applications, suitable synthetic materials include stone paper with a melting point in the range of about 55 ° C to about 130 ° C. Applicable Chinese National Standard (CNS) A4 size (2! 0X 297 mm) (Please Please read the notes on the back before filling this page) D-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -33- 593520 Μ ____ Β7_ V. Description of the invention (31) (Please read the notes on the back before filling this page) Wax and Microcrystalline wax and low molecular weight polyethylene and Fisher- 聚乙烯 busch. The wax content is preferably from about 1 to about 35 weight percent of the total blended composition. In PS A applications, suitable oils include FLEXON® 876 or PRIMOL® 3 52 from ExxonMobil Chemical Company at concentrations of less than 50%. Any of the foregoing embodiments can be formulated as a pressure sensitive adhesive that can be applied to any conventional backing layer such as paper, foil, polymeric film, release liner, woven or non-woven backing material to make, for example, packaging tape, masking tape And tags. A specific example of hot melt pressure sensitivity includes 100 parts by weight of a base polymer, preferably a styrene block copolymer, 50 to 150 phr (parts per 100 parts by weight of the base polymer) of the resin described herein, 0-50 p hr, better 10-50 p hr, better 15-50 phr, better 20-50 phr, better 25-50 phr, better 30-50 phr, better 35-50 phr, more 40-50 phr, 45-50 phr extender oil, and 0-5 phr antioxidant. The resin material formulation of this article printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs provides the advantage of hot-melt pressure-sensitive adhesives, which is to increase the amount of oil used in the formulation by more than 10 parts per 100 parts of polymer ( phr), better 10-50 phr, better 15 phi * or more, better 15-50 phr, better 20 phr or more, better 20-50 phr, more than 25 phr, better 25-5 0 phr More than 30 phr, more preferably 30-50 phr, more preferably 3 5-50 0 phi *, more preferably 40-50 phr, and the ability to maintain the cohesive strength of the adhesive formulation (such as in hot shear and As shown in SAFT measurements). The components selected as needed in the specific embodiment of HMA are plasticizers or other additives such as oils, tackifiers, surfactants, extenders, masterbatches, and the like. Preferred plasticizers include mineral oils, polybutenes, terephthalates, and the like. Very good plasticizers include phthalate esters. This paper is restored to the standard applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm)-'34-593520 A7 B7 5. Description of the invention (32) such as phthalic acid Diisodecyl ester (DIop), diisononyl phthalate (DINP), dioctyl phthalate (DOP). Particularly preferred oils include aliphatic naphthenic oils. Another optional component of the HMA composition is a low molecular weight product such as a wax, an oil, or a low Mn polymer. Below 00). Preferred oils include aliphatic naphthenic oils, white oils, or the like. Preferred low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene, and hexene. Particularly preferred polymers include polyisobutylene having an η of less than 1,000. Examples of such polymers are available from ExxonMobil Chemical Company under the trade name PARAPOL ™ 950. PARAPOLtm 950 is a liquid polybutene having a Mn of 950 and a dynamic viscosity of 220 cSt at 100 ° C (as measured by ASTMD 445). polymer. Suitable specific examples of HMAs typically include 20-70% by weight of the resin materials or blends described herein, 30-80% by weight of the base polymer, and 0-35% by weight of rhenium. Specific embodiments of HMAs can be used for disposable diapers and sanitary napkin bottom structures, disposable goods, printing, converting, packaging, marking, binding, woodworking, and other flexible attachments in assembly applications . Specific examples include: baby diaper leg elastics, diaper front tape, diaper fixed leg cuffs, diaper bottom structure, diaper core stabilization, diaper liquid transfer layer, diaper outer cover laminated structure, diaper elastic cuff laminated structure, women Core stabilizing effect of sanitary napkins, adhesive strips for feminine sanitary napkins, industrial filtration combined, laminated structure of industrial filter material, laminated structure of filter cover, laminated structure of surgical gown, laminated structure of surgical curtain, and perishable products Paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page), 1. Printed by the R Industrial Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Invention Instructions (33) Packaging. Suitable specific examples of woodworking applications include 30-50% by weight of the base polymer, preferably EVA, 1S-35% by weight of the resin described herein, and 20-50% by weight of fillers such as calcium carbonate, barium sulfate, Silica or Chin dioxide. Suitable specific examples of binding applications include 3 to 45% by weight of the base polymer, preferably EVA, 3,545% by weight of the resin described herein, and 10 to 25% by weight of wax. The resin material of the present invention can be used to improve the elongation properties of the adhesive forming the part. Compared to some conventional resins, when the adhesive is combined with a resin material or blend as described herein, an improvement in elongation properties is seen. It is believed that the resin material of the present invention can be used to reduce the setting time of the thermosol adhesive forming the part. Conventional HMAs have a setting time of about 2 seconds. The resin material described herein can be reduced to 1.5 seconds or less, 1.4 seconds or less, 1.3 seconds or less, 1.2 seconds or less, 1.1 seconds or less, or Even a setting time of 1 second or less. Polymer Additives Specific embodiments of the present invention have novel utility as polymer additives in many applications. Other materials exist depending on the application. Many kinds of polymers have been previously described herein. They can be used in polymer processing, for example in various molding applications where good spiral flow is required and where physical properties need to be retained. A wide range of polymers, from polypropylene to engineering thermoplastics, is in this category. The resin of the present invention also aids adhesion, stickiness, and tackiness. A wide range of polymers, such as polyolefin films, tire rubber components or rubber overmolded articles, fall into this category. They can also be added to the ink formulation to apply the Chinese National Standard (CNS) a4 specification (210X297 mm) at this paper size (please read the precautions on the back before filling this page). Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. -36- 593520 A7 B7 V. Description of the invention (34) Helps the components and the adhesion to the substrate. Other applications are coating drying and concrete hardening. Road Sign Additives The specific embodiments disclosed herein can be formulated into thermoplastic road sign (TRM) compositions. These gj | formulations include resins, plasticizers or oils, pigments, fillers, glass beads. The graft material of the present invention can be used as a host tree of a road marking composition or as an additive to a road marking composition. The signpost composition containing the graft material of the present invention may additionally include EVA, polyisobutylene, block copolymers including styrene and conjugated diene such as isoprene or butadiene (including but not limited to SI, SIS , SB, and / or SBS), polyethylene wax, turpentine, turpentine derivatives, maleic acid / anhydride modified hydrocarbon resin. The graft materials of the present invention help disperse fillers and pigments to produce improved flow and color properties. A specific example of a TRM application includes a resin material or blend as described herein, 2-20 weight% pigment, such as Ti02, 1-10 weight% oil, 0- 7% by weight of the base polymer, and the balance contains a filler such as glass beads, sand, calcium carbonate, silica or others as described herein. Crosslinking and Reactive Processing Embodiments of the present invention have further advantages as polymer additives in inks and architectural and road marking applications. They are able to generate and participate in cross-linking in the composition medium by cross-linking with another component of the adhesive formulation. The best examples of acid anhydrides or acid groups on the resin can be used with them or with other paper sizes. Chinese National Standard (CNS) A4 specification (210X 297 mm) ---- 燊-(Please read the back Please fill in this page again for attention) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -37- 593520 A 7 _B7___ V. Description of the invention (35) lies in the crosslinking of the polymer in the composition medium. Some polymers containing amine or alcohol functionality will react directly with the graft resin material, for example, these polymers containing some vinyl alcohol groups. When a crosslinker is added, other polymers will crosslink. In these specific examples, the amount of crosslinker added typically depends on the amount of graft monomer present. Typical amounts include between 100: 1 and 1: 1, more preferably 1: 1 in parts of crosslinking agent, each part of the grafting monomer (molar ratio) present in the formulation. These include such polymers containing some acrylic acids such as ethylene alkyl-acrylate acrylic terpolymers or polymers containing cis-butene dianhydride or acid groups such as ethylene-propylene diene grafted with cis-butene dianhydride rubber. Such cross-linking can be achieved in a number of ways, including the addition of a bifunctional agent having a reaction with an acid or anhydride group. Examples of such materials are those containing alcohol and amine functional properties such as glycols, diamines, and especially primary amines. Materials with these functional groups can be mixed or have different substituents, such as diamines, where one group is primary and the other is tertiary. Weaker cross-linking can be achieved via interactions that do not form covalent bonds such as ions and hydrogen bonds. Examples of materials that can be crosslinked in this manner are divalent metal ions such as Ca + + or diamines containing quaternary amines. Films One or more films containing the ingredients disclosed herein can be used as single- or multilayer films or laminates and may be made by any conventional method, including simple blow extrusion, biaxially oriented methods (such as scaffolding, Encapsulation, or double-bubble method), simple cast / board extrusion-lamination, coextrusion, lamination, extrusion lamination, and coextrusion lamination, blow molding and casting, etc. If multi-layer film is required, the paper size can be adapted to Chinese National Standard (CMS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page).

， 1T Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-38- 593520 A7 ____B7_ V. Invention Description (36) (Please read the notes on the back before filling this page) System technology such as adhesive lamination or extrusion lamination Obtained from a single layer blown or cast film that can be combined with another layer. Monolayer and coextruded films can also be produced by biaxial orientation. Extrusion fit is another suitable method. A heat-sealing film comprising a sealing layer as described herein may be extruded and bonded to a substrate in the form of a single layer or a multilayer co-extruded substrate. Multiple extrudates can be prepared via multiple extruders on multiple stations in series. These layers can be coextruded with other layers (etc.) of the multilayer film, or the sealing layer can be laminated on other layers (etc.) or substrates, including paper, boxes, oriented polypropylene storage, polyamide, polyester, Polyethylene, polyethylene terephthalate, metal and metallized substrates and other substrates discussed herein. The film printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be obtained by a flat film or a tubular method, which can then be oriented uniaxially in the film plane or in two mutually perpendicular directions. One or more thin film layers may be oriented to the same or different degrees in the transverse and / or longitudinal direction. This orientation can occur before or after the individual layers. For example, a polyethylene layer can be extruded and laminated or laminated on an oriented polypropylene or oriented polyester layer or polyethylene and polypropylene can be co-extruded into a film and then oriented. Likewise, oriented polypropylene reservoirs can be laminated to oriented polyethylene or oriented polyethylene can be cloth coated onto polypropylene and the composition can be optionally oriented even further, as desired. The film is typically oriented in a machine direction (MD) of up to 15, preferably between 5 and 7, and a transverse (TD) orientation in a ratio of up to 15, preferably 7 to 9. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions. The film layers may comprise any polyolefin, such as the polar polymers described herein, including cationic polymers of polymers or copolymers of paired disubstituted olefins, heteroatomic olefins, and / or styrene monomers. Preferred paired di-substituted olefins include isobutene, isopentene, isoheptene, isohexane, isooctene, and iso-paper. Applicable to China National Standard (CN7S) A4 (210X297 mm) -39- Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Consumption Cooperative 593520 Μ B7 _ 5. Description of the invention (37) decene, and isododecene. Preferred alpha-heteroatom olefins include vinyl ether and vinyl carbazole, and preferred styrene monomers include styrene, alkylstyrene, p-alkylstyrene, alpha-methylstyrene, and chloro-styrene. , And bromo-p-methylstyrene. Examples of preferred cationic polymers include butyl rubber, isobutylene copolymerized with p-styrene, polystyrene, and polystyrene. Other preferred layers may be paper, wood, cardboard, metal , Metal foils (such as aluminum boxes and tin fans), metallized surfaces, glass (including silicon oxide (SiOx) coatings on the film surface with evaporated sand oxide), fabrics, spunbond fibers, and non-wovens ( Especially polypropylene spunbond fibers or non-woven fabrics), and substrates coated with inks, dyes, pigments, PVC and the like. These films can vary in thickness depending on the desired application, however films with a thickness of 1 to 25 microns are usually suitable. Films intended for packaging are typically between 10 and 60 microns thick. In many cases, the sealing layer should have a thickness between 5 and 60 microns, more preferably between 10 and 50 microns, and most preferably between 15 and 30 microns. The sealing layer may be on the inner and outer surfaces of the film or the sealing layer may be present only on the inner or outer surface. Film additives such as adhesives, anti-blocking agents, antioxidants, slip additives, pigments, fillers, processing aids, UV stabilizers, neutralizers, lubricants, surfactants and / or nucleating agents may also be used Exist in one or more films. Preferred additives include silicon dioxide, titanium dioxide, polydimethylmethoxide, talc, dyes, osmium, calcium stearate, carbon black, low molecular weight resins, and glass beads. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-40- 593520 A7 B7 V. Description of the Invention (38) (Please read the notes on the back before filling this page) In a specific embodiment, the layer (etc.) may contain a cross-linking agent. Preferred crosslinking agents include alcohols, polyols, amines, diamines and / or triamines. Examples of the crosslinking agent which can be used in the present invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylaminopropylamine, and / or methanediamine. Preferred antioxidants include actinide-based antioxidants, such as Irganox 1010, Irganox, 1076, both of which are available from Cibaggaki and 3,5 tertiary-butyl 4-hydroxytoluene. Preferred oils include paraffin or naphtha oils. For example, Primol 352, or Primol 876, available from ExxonMobil Chemical France S.A., Paris, France. More preferred oils include aliphatic naphthenic oils, white oils or the like. Preferred plasticizers and / or adjuvants include mineral oils, polybutenes, phthalates and the like. Particularly good plasticizers include phthalates such as diisoundecyl phthalate (DIUP), diisononyl phthalate (DINP), and dioctyl phthalate ( DOP) and polybutenes, such as Parapol 950 and Parapol 1300 available from ExxonMobil Chemical Company of Houston, Texas. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs print better film processing aids, lubricants, waxes, and / or oils including low-molecular-weight products such as rhenium, oil, or low-Mη polymers, (low means less than 5000, better (Mη below 4000, more preferably below 3000, even more preferably below 2500). Preferred waxes include polar or non-polar waxes, functionalized waxes, polypropylene tinctures, polyethylene waxes, and tincture modifiers. Preferred waxes include ESC OMER 101. Preferred low Mn polymers include lower alpha-olefins such as propylene, butene, pentene, hexene, and similar polymers. Particularly preferred polymers include polybutenes having a Mn of less than 1,000. An example of this type of polymer is obtained from Exxon Chemical Paper Standard Applicable Chinese National Standard (CNS) A4 Specification (210X 297 mm) I-41-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _____B7__ V. Description of the Invention (39) Trademark of the company PARAPOL95 0. PARAPOL 95 0 is a liquid polybutene polymer with a dynamic viscosity of ηη of 950 and 220 cSt of 100 C (as measured by ASTM D 44 5). In another embodiment, one or more layers may be modified by corona treatment, electron beam radiation, r radiation, flame treatment or microwave modification. In a preferred embodiment, one or both surface layers are modified by corona treatment. Sex. The film can be used as a stretched and / or adhesive film. Stretch / bond films can be used in a variety of bundling, packaging, and stacking operations. To impart or improve the adhesion properties of special films, many known tackifying additives have been used. Common tackifier additives include polyisobutylene, terpene resins, and hydrogenated turpentine and turpentine. The adhesive properties of the film can also be modified by known physical methods known as corona discharge. Some polymers (such as ethylene methyl acrylate copolymers) do not require a tackifier additive and can be used as a tackifier without a tackifier. The stretch / bond film may include a slip layer that includes any suitable polyolefin or polyolefin (eg, polyethylene, polypropylene, ethylene, and propylene copolymers) and is obtained from small amounts of other olefins (especially C4 to C12 olefins). ) A composition of copolymerized polymers of ethylene and / or propylene. Particularly preferred are polypropylene and linear low density polyethylene (LLDPE). Suitable polypropylenes are normally solid and isotactic, i.e., greater than 90% hot heptane is insoluble and has a wide melt flow rate of about 0.1 to about 300 g / 10 minutes. In addition, the slip layer may include one or more anti-blocking (slip and anti-blocking) additives, which may be added during the manufacture of the hydrocarbons or later to improve the slip properties of this layer. These additives are known in the art and include, for example, silica, silicate, diatomaceous earth, talc and various lubricants. These additives are preferably from about 100 ppm to about 20,000 ppm. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 > (297 mm) " ~ -42- (Please read first (Notes on the back then fill out this page)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 V. Description of the invention (40), more preferably between about 500 ppm and about 10,000 ppm, based on the weight of the slip layer, the quantity is used. If desired, the slip layer may also include one or more other additives as described above. Examples In the following examples, HMAs were prepared as follows. The components of the HMA formulation were introduced into a Z-blade mixer previously heated at 180 ° under a nitrogen blanket. The wax was introduced after 10 minutes and mixing continued for another 60 minutes. Stop the mixer, stop the nitrogen blanket and pour the blend into a plate. The blend was further cooled under a nitrogen blanket and covered with release paper. HMA samples for testing were prepared as follows. The adhesive was introduced into the accumeter's funnel and melted at 150 t under nitrogen. Cutting and coating the desired substrate carrier strip with melt adhesive (200 // thick polyethylene film, 100 // thick PET film, 90 // thick aluminum and / or acrylic coated oriented polypropylene ( OPP) film cardboard). For the T-peel test, HMA samples for testing were prepared by cutting coated and uncoated substrates into pieces of about 25 cm in length and 10 cm in width. The uncoated substrate is placed on top of the coated substrate. The samples were wrapped in release paper, which was heat-pressed at a given temperature depending on the substrate (1 10 ° C for polyethylene acrylic coated OPP cardboard, 1 500 ° C for aluminum hydroxide, Polypropylene and polyethylene terephthalate (PET)) were further laminated for 30 seconds under a pressure of 4,400 pounds (114 psi / 783 kPa). Using a paper cutter, cut a 2 cm wide strip from the laminated sample (etc.) in the coating direction. The T-peel strength was measured with a tensile tester (Zwick). Measure F-average peel force (g / cm) (paper size of each layer applies Chinese National Standard (CNS) A4 specification (210X297 mm) '" -43- (Please read the precautions on the back before filling in this page)

593520 A7 B7 V. Description of the invention (41) (Please read the notes on the back before filling this page) The average pressure plate is at least 3 test samples). When a sharp jump is indicated, 2/3 of the maximum peak is recorded. The types of failure are also recorded in Tables 1-5: Adhesive Failure (AF), Cohesive Failure (CF), Jump or not jump, and Tear. The shear adhesive failure temperature (SAFT) and thermal shear test samples were prepared the same as the T-peel samples, except that a 25x70 mm strip was used and placed on a pre-treated stainless steel plate. SAFT consists of attaching a coated substrate of a selected substrate to stainless steel with a contact area of 12.5x25 mm, suspending the sample in an oven fixed at 25 ° C and hanging a weight of 500 grams from the bottom of the strip. The temperature was increased at 0.41 / min and the combined destruction temperature was measured. Shear adhesive failure temperature is the average of three experiments. The Ministry of Economic Affairs, Intellectual Property Bureau, Employee Consumer Cooperative printed thermal shearing by 25 mm wide strips of a selected substrate coated with an adhesive formulation (which adheres to a stainless steel plate with a contact area of 12.5x25 mm (Top) Hanging weight of 1,000 grams to measure. The samples were placed in a ventilated oven at 40 ° C for 30 minutes. The temperature increased by 10 ° C during 30 minutes until stress failure occurred, up to 110 ° C. These tests are typically performed individually and recorded to determine the confidence of the adhesion. The result is expressed as the equivalent of a minute measured at 60 ° C, that is, when damage occurs, each 10 ° C increases by more than 60 ° C, and 30 minutes is added to the time. Saponified samarium, as used herein, is measured according to the following steps. 1N of KOH alcohol solution was dissolved in 25 ml of toluene / isopropanol (1: 1 weight ratio) in a powder resin material to be evaluated. After refluxing for 30 minutes and cooling to room temperature, a phenolphthaleine: ^ · * agent titration solution was used to 0.1 NHC1. Blank experiments were performed with no resin material. This paper size applies Chinese National Standard (CNS) A4 specifications (210X297) Centrifuge) -44-593520 A7 B7 V. Description of the invention (42) Then calculate saponified tritium (mg 1 <: 011 /) by dividing 56.1 (approximate molecular weight of ΟΟΗ) x volume of standard HC1 x equivalent concentration of HCl by the weight of the resin material Grams of resin). Acid osmium, as used herein, is measured according to the following steps. 2 grams of powdered resin material to be evaluated are dissolved in 30 ml of toluene / isopropanol (2: 1 weight ratio). After the sample is completely dissolved, It was titrated at a potential of 0.1N tetrabutylammonium hydroxide (TBA〇 烈) under vigorous stirring, using a Pt titrode and an Ag / AgCl electrode with saturated LiCl electrolyte in saturated ethanol. A blank experiment was performed with no resin material. 56.1 (approximate molecular weight of KOH) multiplied by the volume of TBAOH used to titrate the sample minus the volume of TBAOH of the titration blank multiplied by the equivalent concentration of TBAOH divided by the weight of the material値. Acid 値 is expressed in milligrams of potassium hydroxide per gram of resin, (mg KOH per gram of resin). In the following examples, all parts, ratios, and percentages are by weight unless otherwise indicated. Use the following materials : (Please read the precautions on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper is suitable for commercial use (iicNS—) Α4 ^ Τ7Γ〇χ 297 mm) -45-593520 A7 B7 5 Description of the invention (43) i fi? ≪ 4 ^^ lo—! I? «[S > 10— fi? ≪ 4s > Ιο— (%) Feeding S 栽 ho 氍 κ]

OOCN 61 6rn (Please read the notes on the back before filling out this page) Binding · Ordering (1) i inch ε6.0 S6.0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (Lai φοι / position) s 00 inch οείη 09 8S0 inch τη 6Ι0εςτη _3MS8S3 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -46- 593520

7 7 A B V. Description of the invention (44) i

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0.9 inch §10011 | 《pcn6ds) s5Mi: iu / u ε§% 28S3 ExxonMobil Chemical Company Ciba-Geigy Extender Oil Phenolic Antioxidant Flexon⑧ 876 Irganox⑧ 1010,1076 SEOSISH -00¾ P009 _μ? SQHN oss-umulunqos i ^ i.smHNmvwd 1ΪΡΗ --------- install-(Please read the precautions on the back before filling out this page) Order the standard of the standard for a country in China with a suitable I ruler paper I s

Centimeter 7 9 2 X -47- 593520 kl _B7_ V. Description of the Invention (45) Example 1 (Comparison) (Please read the precautions on the back before filling out this page) Thermal polymerization of hydrogenated aromatic hydrocarbons containing DCPD resin (available Escorez (R) 5600 from ExxonMobil Chemical Company, with a softening point of 103 ° C, Mn 270, and Tg 5 5 ° C) was mixed in the HMA formulation according to Table 1 Example 2 (Comparative) Sylvalite® from Arizona Chemical Company RE100 (softening point 96 ° C, Mn 95 0, Mw 1110, saponified hydrazone 26, and acid hydrazone 5.5) were mixed with the homopine esters in the HMA formulation according to Table 1. Example 3 (comparative) Sylvalite® RE100 (softening point 10CTC, Mn 810, Mw 1060, saponified rhenium 28, and acid hydration 13, 7) from Arizona Chemical Company was blended in a HMA formulation according to Table 1 In. Example 4 (comparative) Terpene phenolic resin printed by Dertophene T (softening point 95 ° C, Mn 4 90, Mw 700, and initial color 4.5 Garden) from Resiniques Terpeniques' Consumer Consumption Cooperative printed on the basis of In the HMA formulation of Table 1. Examples 1-4 were then examined using polyethylene-to-polyethylene and PET-to-PET T-peel, and thermal shear and SAFT on polyethylene to stainless steel and PET to stainless steel. The results obtained from Examples 1-4 are shown in the table and used as a reference for comparison of later examples. This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) -48- 593520 A7 __B7 V. Description of the invention (46) Example 5 100 grams of thermally polymerized hydrogenated aromatic hydrocarbons containing DCPD resin, and tested in Example 1 The Es corez® 5 6000 resin is the same, but without antioxidants. It contains 7.5% aromatic protons and 0.01% olefin protons, has a softening point of 103, and is equipped with a perturbator 2 5 under nitrogen. The 0 ml flask was heated to and maintained at 170 ° C. 5.5 grams of dibutyl maleate are added. At 15 minute intervals, aliquots of 0.75 ml of 2,5-dimethyl-2,5-bis (tertiary-butylperoxy) hexane (Luperox® 101) were added. After the peroxide addition was complete, the mixture was further stirred under a nitrogen stream for 75 minutes to remove volatile materials. The resulting reaction product was decanted from the reactor, cooled and analyzed. The graft resin product had a Gardner color of 3.5 (50% by weight in toluene), a softening point of 84 ° C, and a saponified samarium of 17. Example 6 100 grams of a thermally polymerized partially hydrogenated aromatic hydrocarbon containing DCPD resin, the same as the Escorez® 5600 resin tested in Example 1, but without antioxidants, with a softening point of 103 ° C, 7.5% aromatic protons And 0.01% olefin protons (indicated by 1H-NMR spectrum), heated to and maintained at 1 70 ° C in a 500 ml flask equipped with a stirrer under nitrogen. When liquid, 1.23 grams of cis-butene dianhydride powder was added and mixed. Five 0.1 ml aliquots of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane (Luperox 101) were added to the stirred liquid at 15 minute intervals and reacted under nitrogen. Flowing is continued for another 60 minutes to remove volatile peroxide decomposition products and any residual unreacted maleic anhydride. The melt was poured from the reaction flask and allowed to cool and solidify. The paper size of the obtained grafted tree is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back before filling this page). 49-593520 A7 ____ B7 V. Description of the invention (47) The fat product has a softening point of 105 ° C, a Gardner color of 3.5, and a saponification of 1.0. Example 7 250 grams of thermally polymerized DCPD resin partially hydrogenated Aromatic hydrocarbons, the same as the Escorez® 5600 resin tested in Example 1, but without antioxidants, with a softening point of 103 ° C, 7.5% aromatic protons and 0.01% olefin protons (indicated by 1H-NMR spectrum), under nitrogen Next, a 500 ml flask equipped with a stirrer was heated to and maintained at 170 ° C. When liquid, add 6.1 g of cis-butene dianhydride powder and mix. Five 0.25 ml aliquots of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane were added at 10 minute intervals and the reaction was continued under nitrogen flow for another 20 minutes to The volatile peroxide decomposition products and any residual unreacted maleic anhydride were removed. The melt was poured from the reaction flask and allowed to cool and solidify. The obtained graft resin product had a softening point of 105 ° C, a Gardner color of 3.6, and a saponified hydrazone of 20. Example 8 100 grams of a thermally polymerized partially hydrogenated aromatic hydrocarbon containing a DCPD resin, the same as the Escorez® 5600 resin tested in Example 1, but without antioxidants, with a softening point of 103 ° C, 7.5% aromatic protons, and 0.01 % Olefin protons (indicated by 1H-NMR spectrum), heated to and maintained at 170 ° C in a 500 ml flask equipped with a stirrer under nitrogen. When liquid, add 4.9 grams of cis-butene dianhydride powder and mix. Add four 0.5 ml aliquots of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane at a 15-minute interval, and the Chinese paper standard (CNS) A4 applies Specifications (210/297 mm) (Please read the precautions on the back before filling out this page) • Binding and printing printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs -50- 593520 A7 ___B7 V. Description of the invention (48) (Please Read the notes on the back before filling this page) The reaction is continued under nitrogen flow for another 7 5 minutes to remove the volatile peroxide decomposition products and any remaining unreacted cis-butadiene dianhydride. The melt was poured from the reaction flask and allowed to cool and solidify. The obtained graft resin product had a softening point of 112 ° C, a Gardner color of 8 and a saponified tincture of 40. Examples 9-12 The graft resins obtained from Examples 5-8 were mixed in the HMA formulation according to Table 1. Then use T-peel for polyethylene-to-polyethylene and PET-to-PET, and heat shear and SAFT inspection for polyethylene-to-stainless steel and PET-to-stainless steel. Example 9-12. Results from Example 9-1 2 are shown in Table 1 and Figures 1-6. Note the T-peel: only the peel force (F-average) is shown. When the sample has only a sharp jump, it is equivalent to zero adhesive force. Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs. These results show that most of the resins used on the polyethylene substrate are similar to those in Reference Examples 1-4. On the other hand, the thermal shear and SAFT of the graft resin were superior to those of Reference Examples 1-4, especially Examples 6/10, 7/11, and 8/12 in which the graft monomer was cis-butene dianhydride. These results also show that compared to the unstretched graft resins of Example 1 and the tall oleoresin of Examples 2 and 3 on polar substrates, these graft resins have better adhesion, which shows only a sharp jump. As shown in Figure 1-6, the results of hot shear and SAFT show that the graft resins of Examples 6/10, 7/1 1 and 8/1 2 are equal to or better than Reference Examples 1-4. Example 13 Commercial manufacturer of thermally polymerized aromatic hydrocarbons containing DCPD hydrocarbon resins from ExxonMobil manufacturing plant in Notre Dame de Gravenchon, France _______ This paper size applies to China National Standard (CNS) A4 (210X 297 mm) -51-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 B7 ______ V. Product Stripper in the Method of Invention (49) Over 700 grams of cyclopentadiene, methylcyclopentadiene, and oligomers of C9-C1 () aromatic olefins were hydrogenated trimer and tetramer mixtures from the overhead distillate stream. The resulting oligomers contained no antioxidants and contained 7.4% aromatic protons and 0% olefin protons. The oligomers were stirred in a 2 liter flask under nitrogen at 160 ° C with 70 g of cis-butene dianhydride powder. Six 0 ml portions of 2,5-dimethyl-2,5-di (tertiary-butylperoxy) hexane were added at 0, 10, 20, 30, 45 and 75 minutes. The reaction was continued for another 45 minutes under nitrogen flow through the flask to remove any volatile components. The reactor was cooled to 140 ° C and the product was poured into a cold paraffin solvent (exxsol D available from ExxonMobil Chemical Company) having a boiling point in the range of 160-192 ° C as determined by ASTM D-1078. The insoluble product was filtered and washed with heptane to remove residual traces of unreacted oligomers and any peroxide decomposition products. The yield was 120 g of a grafted oligomer with a softening point of 107 ° C, Garden Color 12 (acetone: toluene 1: 1 by weight), and 3,36 saponified samarium. Examples 14-17 The graft oligomers obtained from Example 13 were mixed with a thermally polymerized hydrogenated aromatic hydrocarbon containing a DCPD resin (Escorez® 5 60 0) in various oligomer to resin ratios to form a resin material. The amount of grafted oligomer in the resin material varies between 5 and 30% by weight. The resin material was then mixed in the HMA formulation according to Table 1. T-peeling of polyethylene to polyethylene and PET to PET, and thermal shear and SAFT of polyethylene to stainless steel and PET to stainless steel have been measured. The results obtained from Examples 14-1 7 are shown in Tables 2 and 4 and Figures 7-12. Example 1 The T_Peel test of 5 and 17 is also acrylic coated 0PP thick paperboard (applicable to China (CNS) A4 size (210 × 297 mm) with AC paper size) ~ " -52-(Please read the back first Please note this page and fill in this page) £ ·-, 1T 593520 A7 _ _B7 ____ V. Description of the invention (5) and comparison with the similar results produced by the HMA formulation prepared in Example 2. These results are shown in Table 2 and Figs. Table 2 and Figures 7-1 2 illustrate all comparable behaviors of a resin material containing a graft oligomer on a polyethylene substrate when compared with Reference Examples 1-4. These results also indicate that on polar substrates such as PET, resin materials containing grafted oligomers achieve significant advantages, especially adhesion. These results also indicate that when compared with Reference Examples 1-4, the shear and SAFT of the resin material containing the grafted oligomer were significantly higher. The results from Table 5 and Figures 13-15 also show that the resin material containing the grafted oligomers has a performance that exceeds that of the high turpentyl esters tested on the acrylic-coated OPP cardboard in Example 2, especially the adhesion (please first (Please read the notes on the back and fill in this page again) • Binding and ordering Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 18-23 Packaging tape formulations with the composition shown in Table 3 in the WinkwcKth AZ mixer on 1 4 5 ° C was mixed at a leaf speed of 5 9 RPM. Ten minutes after the set temperature of 145 t was reached, nitrogen gas charging was started and block copolymers were added and mixed, 1/5 of the total resin, and Irganox antioxidant. The time when the block copolymer is added is considered the start time. After 10 minutes of mixing, add an additional 2/5 of the total resin. When shear was observed, the remaining 1/5 of the resin was added. 30 minutes after the start time, add all the oil and mix the ingredients until 70 minutes from the start time. The mixture is then poured into a plate and covered with release paper. Samples were prepared by coating a Mylar substrate at 175 ° C with a accumeter coater to a total coating weight of about 19 g / m2. Prior to testing, all samples were conditioned for at least 16 hours at 23 ° C and 50% relative humidity. Samples The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm). -53- 593520 A7 __B7_ V. Description of the invention (51) The requirements of the test for rear view are cut into strips. The following test procedure was used in Example 18-23 °. Ball adhesion was tested by the procedure of Test Method 6 according to the PSTC test method. Cut the sample 2.5 cm wide and 25 cm long and remove the release liner. The sample was fixed on the experimental table with the adhesive side. The ball adhesion tester is placed on the sample with its longitudinal axis. Remove the steel ball (5.6 g, 7/16 inch (1.11 cm) diameter) from the solvent with tweezers and wipe dry with paper. The tweezers were used to place the dried ball in the wooden bowl of the ball adhesion tester in the release position, released and rolled on the adhesive layer. Measure the distance (cm) from the center of the ball to the inclined end of the ball adhesion tester. Repeat the measurement on two additional samples taken from the same pressure-sensitive material and record the average measurement in the table. The force required to separate the adhesive ring from the standard test strip at the defined rate was evaluated for ring adhesion. Stainless steel sheets were stored in Nappar 6 solvent. Prior to the test they were blotted dry with absorbent paper and cleaned with acetone. The test was carried out in the sample application direction. The adhesive covered and cut the test samples (2.5 cm wide and 22 cm long) with release paper. The release liner was then removed from the test sample. A ring is formed on the outside with an adhesive layer. The adhesive was paper protected at both ends of the ring so that there was no direct contact between the adhesive and the air clip of the peel tester. The two protected ring ends are clamped at a distance of 15 mm from the vertically hanging ring. The clean test piece is placed on the ring adhesive fixture with the length direction of the piece placed vertically on the ring plane. The tensile tester started contacting the ring of the adhesive film with the test piece at a set speed of 300 mm / min. The sample is applied to the test piece without any force other than the weight of the sample itself. Once the ring has made full contact with the test stop the machine and start recording. At the speed of 300 mm / min, the test paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) — -54-(Please read the precautions on the back before filling this page) • Loading.- Order printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 593520 A7 _B7 _ ^ _ V. Description of Invention (52) (Please read the precautions on the back before filling this page) Samples are separated from samples. Measure at least 3 test specimens of the same formulation and record the maximum force required to completely separate the rings. The tritium given in the table is the average tritium for the three trials. Intellectual Property Bureau of the Ministry of Economic Affairs (industrial and consumer cooperative printing 1 80 ° peel adhesion evaluation sample peel adhesion. Peel adhesion evaluation peels pressure-sensitive adhesive from a standard test piece at a defined angle (in this case, lSCT) and speed Required strength. Stainless steel sheets are stored in a solvent (Nappar 6). Prior to testing, the test pieces are dried with absorbent paper and cleaned with acetone. The test is performed in the direction of sample application. Adhesion of the sample to be tested The surface is covered with release paper and cut into 25 mm wide and 22 cm long samples. Remove the part of the release liner from the strip, the end is loose. The part of the sample without the release paper sticks clean and adjusted in the length direction. There is no force on the test piece. The sample is placed in an automatic unwinder and set at a speed of 60 cm / min. The sample (etc.) is rolled up and down twice. The sample is tested within one minute of preparation. Peel off three centimeters at the loose end The release paper on the sample. The metal piece of the test sample is clamped vertically in the lower clip. The loose end of the sample is folded back (180 °) and fixed on the upper clip. Record the need to peel the sample from the metal piece. Strength. Measure three samples per glue sample and obtain the average of each curve, ignoring the extreme peaks and the start / end portions of the plot. In the case of a sharp jump, record the average of 2/3 of the highest peak. Thick cardboard Shear was measured by hanging a 25-mm wide strip of a sample coated with an adhesive formulation that adhered to a cardboard with a contact area of 12.5 x 25 mm to a weight of 1,000 grams. The sample was placed at 40 ° C. Ventilate the oven. Record the time until stress failure occurs. Typically, these tests are individually performed and recorded to determine the credibility of the adhesion. S AFT (shear adhesive failure temperature) method is used to measure when the temperature is 0.4t This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0 > < 297 male f) -55-593520 A7 ___________B7_ V. Description of the invention (53) / minute when it is subjected to a defined stress The SAFT test was performed as follows. The stainless steel sheet stored in the solvent (Nappar 6) was dried with absorbent paper and cleaned with acetone. The test was performed in the coating direction of the sample. A 2.5 cm wide and a minimum 6 cm long Release paper Cover the sample and remove the release liner. Strengthen one end of the sample by obtaining a 2.5 cm wide and 3 cm long piece of release liner and adhering a 1.5 cm release liner to one end of the sample. 1 · 5 cm is folded back to cover the adhesive end of the release liner and stapled horizontally twice with a staple. The sample is then placed on a stainless steel test piece without pressure. The contact area between the sample and the cardboard is 25 Mm width x 25 mm height. For SAFT, the contact product between the sample and the stainless steel dish is 25 mm width x l2.5 mm height. The contact area uses a 0.9 kg (2 lb) rubber roller at a moderate speed without other stress on the weight of the roller itself Scroll twice in each width direction. One arm of the shear triangle is then placed in the crease of the release liner so that the portion of the shear triangle that is not in contact with the adhesive. The prepared sample was then mounted on the sample support, a weight of 0.5 kg was fixed on the shear triangle and placed in the oven. The experiment started at 24 ° C. The temperature rises at 0.4 ° C per minute. SAFT records the temperature of adhesion failure. Five tests were performed for each adhesive formulation and the average of the five tests is listed in the table. The data in Table 3 show that shearing on cardboard at 40 ° C significantly increased pressure-sensitive adhesive formulations containing both conventional hydrocarbon resins and the grafted hydrocarbon resins described herein, while producing 3.9 cm balls Adhesiveness, which is far less than 3.0 cm industrially preferred. In Examples 22 and 23, the ball adhesion dropped to 3.0 or below, but most surprisingly, the thermal shear on thick paperboards, 値 even rose to higher levels. Therefore, when the adhesive formulation contains the conventional hydrocarbon resin and the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 feet) (please read the precautions on the back before filling this page). ιτ Printed by S Industrial Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs -56- 593520 A7 ----- B7__ V. Description of the Invention (54) '' 一 ^ -— The graft resin has unexpected thermal shear Enhanced performance. It is apparent from the foregoing description that the materials prepared and the methods according to them are particularly preferred embodiments of a wide range of inventions. It is obvious from the foregoing general description and specific specific embodiments that, while the form of the present invention has been illustrated and described, various modifications may be made without departing from the spirit and scope of the present invention. Therefore, it is not intended that the present invention be limited thereby. In the scope of the following applications representing specific embodiments of the present invention, each subsidiary embodiment of each of the following independent specific embodiments may be implemented with one or more other subsidiary embodiment restrictions so that Other operable embodiments within the scope. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -57- 593520

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X centimeter-58- 593520 A7 B7 V. Description of the invention (56) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs vr > 〇ro O T " H o 1-1 〇 > 200 103 1018 AF + CF PE Tear No Jerking m (N 00 v〇494 pen o No Jerking o Ο 507 pH C No Jerking 152 > 113 〇 < Ν ΓΟ 〇o tH d > 200 102 885 AF + CF PE Tear No Jerking | 00 VO 495 AF + CF Tendency to Jerk 1081 m to 〇o 〇〇 > 200 102 966 CF PE Tear No Jerking | r- v〇o CF Tendency to Jerk 219 174 1093 294 < No Jerking I 126 107 inch 〇 \ ro oo 〇 > 200 102 733 AF PE Tear No Jerking | < N o Jerking inch inch rs inch moo r-1 in d 00 103 1306 1¾ u No Jerking | rH VO VO __293___I u 509 ττ-Η r ^ v〇 ^ T) moo rH 〇145 104 720 < 1 No Jerking | rH o Jerking + AF 228 r- v〇yn to oo rH 1 _ ^ _ 1 00 00 105 1098 PL | o I No Jerking | v〇v〇v〇o Jerking 287 00 KD o Jerking __2JA__ 102 j 100 mo fH o rH o 00 101 874 AF + CF No Jerking jm CN VO o Jerking m < N Example (etc.) 1 Ingredient (parts by weight) | Resin Resin component Graft oligomer (Wt%) Hydrocarbon resin (wt%) 00 (N 〇o Inch 2 ® (D < 〇 〇o C / D ω | Np wax | | FT wax 丨 O 〇Γ X o rt 03 bl) HH Resin cloud point (° c) Resin softening point (° c) T-peel PE / PE (g / cm) Failure Type | T-Peel PE / PE (g / cm) | [Heat Shear PE / ss (Min at 60 ° C) 1 | SAFT PE / ss (° C) 1 | T-Peel PET / PET (g / cm) | Failure Type T-Peel PET / PET (g / cm) Hot Shear PET / ss (min at 60 ° C) SAFT PET / ss (° C) T-Peel AC / AC (g / cm) Failure Type | T-Peel AC / AC (g / cm) | Hot Shear AC / ss (min at 60 ° C) | SAFT PET / ss (° C) | QII — sr1Ql < NI < -9floII-69, 窆 1— 9 £ 一 -JJglBalll-N 昤 Kiiiljrla-lfelsefrl & _Hi ^ (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -59- 593520 A7 B7 V. Description of Invention (57) eCN-oosfcs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, CN 110 o Γ-Η in > 9819 ON (N | 19.2 94.9 (N (N in 110 o TH m > 9819 en 18.5 92.5 IT) 110 o in 4417 ON en 15.8 87.8 110 110 o TH Ό 804 vd 17.5 78.7 o rH rH 110 o rH inch m 252 > 20 (N inch 79.2 00 ο rH rH oor * H 〇503 00 93.5 Example composition (parts by weight) Escorz® 2203 EMFR-100 Escore® 5600 Vector® 4511 Flexon® 876 Irganox® 1076 180 ° peel (N / cm) on SS at 40 ° C on cardboard Shear (min) Ball Adhesiveness (cm) Ring Adhesiveness on SS (N / 25cm) SAFT (° C) Approval for SS ^ Order. (Please read the precautions on the back before filling this page )

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Claims (1)

593520% A8 B8 C8 D8 6. Scope of patent application i Annex 4: Chinese application for patent application without amendment underlined after the amendment of Patent Application No. 91121888 Replaces the amendment of the Republic of China on September 19, 1992 L A composition that includes at least two Hydrocarbon resin, wherein one of the resins is present in an amount of 0.1 to 99% by weight based on the weight of the composition and is a petroleum hydrocarbon resin grafted via a graft monomer of 0.1 to 10% by weight based on the total weight of the composition Wherein the grafted monosystem is selected from the group consisting of: acids, anhydrides, amidines, amidines, alcohols, and derivatives thereof, wherein the composition does not substantially include cyclopentadiene and Grafted oligomers of substituted cyclopentadiene, wherein: if the grafting monomer is an acid, anhydride, amidine, amidine or a derivative thereof, the saponification ratio of at least two hydrocarbon resins is 1 -1 〇〇, or if the grafting monomer is an alcohol or a derivative thereof, the hydroxyamidine measured according to ASTM E 222 94 is 1-100. 2. As for the composition in the scope of the patent application, the other hydrocarbon resin is present in an amount of 1-99.9% by weight based on the weight of the composition and is selected from the group consisting of: aliphatic hydrocarbon resin, at least part of which Parts of hydrogenated aliphatic hydrocarbons. Resins, aliphatic / aromatic hydrocarbon resins, at least partially hydrogenated aliphatic / aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic resins, cycloaliphatic / Aromatic hydrocarbon resins, at least partially hydrogenated cycloaliphatic / aromatic hydrocarbon resins, aromatic hydrocarbon resins, at least partially hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, turpentine esters, turpentine resins Acids and mixtures of any two or more thereof. 3. The composition according to item 1 or 2 of the patent application scope, wherein the grafted petroleum oil resin contains 0-5% olefin protons before grafting. This paper size applies to the Chinese National Standard (CNS) 6 4 grid (210X297 mm) ~ ~ (Please read · «Notes on the back before filling out this page) Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives 593520 Ministry of Economic Affairs Printed by A8, B8, C8, D8, Consumer Cooperative of Intellectual Property Bureau 々, patent application scope 2 4. For the composition of patent application scope item 1 or 2, the graft resin contains 20% aromatic. 5. If the composition of claim 1 or 2, the grafted hydrocarbon resin is selected from the group consisting of C5 monomer oligomer, C9 monomer oligomer, and cyclopentadiene, substituted cyclopentadiene Olefin and C9 monomer oligomers. 6. The composition according to item 1 or 2 of the patent application, wherein the grafted petroleum hydrocarbon resin is an at least partially hydrogenated thermally polymerized aromatic cycloaliphatic hydrocarbon resin. 7. The composition according to item 1 or 2 of the patent application scope The grafted petroleum hydrocarbon resin is obtained by the polymerization of C5 monomer and C9 monomer. 8. The composition according to item 1 or 2 of the patent application, wherein the grafted hydrocarbon resin is selected from the group consisting of cyclopentadiene and substituted oligomers of cyclopentadiene, of which the oligomers Substantially no norbornyl groups and oligomers therein include at least one monoalkylmaleic acid, anhydride or derivative thereof, or / 3-alkyl substituted propionic acid or derivative thereof. 9. The composition according to item 1 or 2 of the patent application scope, including 1 to 75% by weight of a grafted petroleum hydrocarbon resin. 10. If the composition of the scope of claims 1 or 2 of the patent application, 尙 includes at least one polyolefin. 1 1. The composition according to item 10 of the scope of patent application, wherein the polyolefin is selected from the group consisting of polyethylene, ethylene α-olefin (C3-C2 ()) copolymer, polypropylene, propylene α-olefin ( C4-C2G) copolymers, polybutenes, butene olefins (C5-C20) copolymers, polyisobutylene polymers, α-olefin diene copolymers, including block copolymers of styrene and conjugated diene, And its two or this paper size is applicable to the Chinese National Standard (CNS) grid (2Ι0 × 297 mm) (please read the precautions on the back of the order before filling out this page) -2 593520 A8 B8 C8 D8 6. Mixtures with a patent scope of 3 or more. (Please read the notes on the back of the section before filling out this page.) 12. If the composition in the scope of patent application 1 or 2 includes at least one polar polymer. 13. The composition of claim 12 in which the polar polymer is selected from the group consisting of polyesters, polyamides, polyureas, polycarbonates, polyacrylonitrile, and poly Acrylates, polymethacrylates, ethylene vinyl acetate copolymers, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyacetals, ethylene methyl acrylate, Ethylene butyl acrylate and mixtures of two or more thereof. 14. As for the composition in the scope of claims 1 or 2, the polymer includes a polymer including ethylene or propylene, having a CDBI of 50 to 100% and a polydispersity of less than 4. 1 5. If the composition of the scope of claims 1 or 2 of the patent application, rhenium includes at least one rhenium or oil. 16. If the composition of the scope of claims 1 or 2 of the patent application, 尙 includes at least one crosslinking agent. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 17. — A kind of adhesive composition, which contains the resin composition as described in the first or second scope of the patent application. 18. A hot-melt pressure-sensitive agent, including: (a) 100 parts by weight of a styrene block copolymer; (b) 50 to 150 phr of a resin as described in claims 1 or 2 Composition; and (c) 0-5 0 phr extender oil selected from naphthenic oil, aliphatic oil and white oil. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -3-