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    • 专利摘要:
    The present invention relates to a hot melt adhesive which is excellent in high speed coating and low temperature spiral coating, and is also excellent in adhesion to polyethylene and a non-woven fabric; and disposable products obtainable by the hot melt adhesive. Shown is a hot melt adhesive including: (A) a homopolymer of propylene having a melting point of 100°C or less which is obtainable through polymerization of propylene using a metallocene catalyst; and (B) an ethylene-based copolymer. The hot melt adhesive excels at high speed coating and excels at low temperature spiral coating, and is also excellent at adhesion to a polyethylene film and a non-woven fabric. When the ethylene-based copolymer (B) is an ethylene/alpha olefin copolymer that is obtainable through polymerization using a metallocene catalyst, the hot melt adhesive is more excellent at adhering to a polyethylene film and a non-woven fabric while maintaining high speed coating capability and low temperature spiral coating capability.
    公开号:BR112014006221B1
    申请号:R112014006221-8
    申请日:2012-09-13
    公开日:2021-05-18
    发明作者:Masahiro Moriguchi；Shigekazu Saito
    申请人:Henkel Ag & Co. Kgaa；
    IPC主号:
    专利说明:

    Reference - Crossover to Related Patent Application
    [0001] This patent application claims benefit under the Paris Convention of Japanese Patent Application No. 2011-203063 filed September 16, 2011, incorporated herein by reference in its entirety. Technical Field
    [0002] The present invention relates to a hot melt adhesive, and more particularly to a hot melt adhesive which is used in the field of disposable products typified by a diaper and a napkin. Background of the Technique
    [0003] A synthetic rubber-based hot melt adhesive containing a thermoplastic block copolymer as a major component has been widely used as a hot melt adhesive that is used in disposable products such as a diaper and napkin and is applied to a base material, for example, a non-woven fabric, a fabric, a polyethylene film and the like.
    [0004] In case of production of disposable products, a non-woven film or fabric is coated with the hot melt adhesive, and high speed re-coating is sometimes employed to improve the production efficiency of the disposable products. However, synthetic rubber based hot melt adhesive can sometimes spread when applied at high speed.
    [0005] One of the means for improving the production efficiency of disposable products includes a process in which a hot melt adhesive typified by an ethylene-propylene copolymer is applied at a high speed.
    [0006] Patent Literatures 1 to 3 show a hot melt adhesive containing an olefin polymer as a main component. It is known that an olefin-based hot melt adhesive is commonly more suitable for use in paper processing than for use in disposable products.
    [0007] Patent Literature 1 shows that a propylene polymer is used as a raw material for a hot melt adhesive (see claim 14 of Patent Literature 1). However, the hot melt adhesive from Patent Literature 1 does not have sufficient adhesion to a polyethylene film. A diaper, sanitary napkin, and the like often has a structure in which an absorbent consisting of a pulp, an absorbent polymer, and the like is wrapped in a fabric and its outlet is covered with a non-woven fabric, a polyethylene film, and the like. Therefore, it is required for hot melt adhesive for disposable products to have strong adhesive strength to the polyethylene film.
    [0008] Patent Literature 2 shows a polyolefin-based hot melt adhesive for disposable products (see [0001] and [0041] of Patent Literature 2). In case of spiral coating a polyethylene film with the hot melt adhesive of Patent Literature 2, it is necessary to lower the viscosity by increasing the temperature in order to face a complicated coating pattern. As shown in Table 1 of Patent Literature 2, the coating temperature of the hot melt adhesive is set to a high temperature (350oF to 365oF). However, ethylene is coated with the hot melt adhesive at the above temperature, the film may melt and the coated hot melt adhesive may shrink due to cooling, resulting in the formation of wrinkles in the film.
    [0009] Patent Literature 3 shows a hot melt adhesive based on propylene (see Patent Literature Claims 3). However, it is also difficult for the Patent Literature 3 hot melt adhesive to be applied by low temperature spiral coating, as is the case with the Patent Literature 2 hot melt adhesive, and it is also difficult to say the strength of peeling between non-woven fabrics is sufficient.
    [00010] Patent Literature 1: WO 2003/087172 A1
    [00011] Patent Literature 2: JP 2003-533551 A
    [00012] Patent Literature 3: JP 2003-518171 A Exposition of the Invention Problems to be Solved by the Invention
    [00013] An object of the present invention is to provide a hot melt adhesive, which is excellent in high speed coating and low temperature spiral coating and is also excellent in adhesion to polyethylene and a non-woven fabric; and disposable products obtainable by the hot melt adhesive. Means for Troubleshooting
    [00014] The present inventors have intensively studied and found that it is possible to obtain a hot melt adhesive which is excellent in high speed coating and is excellent in low temperature spiral coating, and is also excellent in adhesion to polyethylene and a non-woven fabric. , when a propylene homopolymer having narrow molecular weight distribution and also having a low melting point is combined with an ethylene-based copolymer, and that such a hot melt adhesive is suitable for disposable products. Thus, the present invention has been completed.
    [00015] Furthermore, the present inventors have found that when an ethylene/octene copolymer is used as the ethylene-based copolymer which is a component to be combined in the hot melt adhesive, a coating pattern of the hot melt adhesive becomes indiscernible, resulting in satisfactory appearance of disposable products.
    [00016] That is, the present invention provides a hot melt adhesive including: (A) a homopolymer of propylene having a melting point of 100°C or less which is obtainable through polymerization of propylene using a metallocene catalyst; and (B) an ethylene-based copolymer.
    [00017] The present invention provides the hot melt adhesive, in one embodiment, where the ethylene-based copolymer (B) is an ethylene/alpha olefin copolymer that is obtainable through polymerization using a metallocene catalyst. The present invention provides, as a preferred embodiment, the hot melt adhesive, wherein the ethylene/alpha olefin copolymer (B) contains at least one selected from an ethylene/propylene copolymer and an ethylene/octene copolymer.
    [00018] The present invention provides, as another embodiment, the hot melt adhesive, further including: (C) a tack forming resin; and (D) an oil.
    [00019] The present invention provides, as yet another embodiment, the hot melt adhesive including: (E) a wax, where the wax (E) includes a wax modified with carboxylic acid and/or carboxylic anhydride.
    [00020] The present invention provides, as another preferred embodiment, hot melt adhesive having a melt viscosity at 150oC of 7000 mPa.s or less.
    [00021] The present invention provides, as a second aspect, disposable products obtainable through use of the above hot melt adhesive. Effects of the Invention
    [00022] Since the hot melt adhesive of the present invention includes: (A) a homopolymer of propylene having a melting point of 100°C or less which is obtainable through polymerization of propylene using a metallocene catalyst; and (B) an ethylene-based copolymer, the adhesive is excellent at high speed coating and low temperature spiral coating, and is also excellent at adhesion to a polyethylene film and a non-woven fabric.
    [00023] When the ethylene-based copolymer (B) is a
    [00024] Ethylene/alpha olefin copolymer which is obtainable through polymerization using a metallocene catalyst, the hot melt adhesive is more excellent in adhesion to a polyethylene film and a non-woven fabric while maintaining high speed coating capability and the ability to spiral coating at low temperature.
    [00025] In the hot melt adhesive of the present invention, when the ethylene/alpha olefin copolymer (B) contains at least one selected from an ethylene/propylene copolymer and an ethylene/octene copolymer, the spiral coating capability at low temperature it is more improved. When the ethylene/octene copolymer is contained, a coating pattern of the adhesive becomes indistinguishable in the case of sticky coatings such as polyethylene film and non-woven fabric by means of spiral coating.
    [00026] When the hot melt adhesive of the present invention further includes: (C) a tack-forming resin; and (D) an oil, hot melt adhesive becomes more excellent in adhesion to a polyethylene film and a non-woven fabric while maintaining high speed coating capability and low temperature spiral coating capability.
    [00027] When the hot melt adhesive of the present invention includes: (E) a wax, and the wax (E) is a wax modified with carboxylic acid and/or carboxylic anhydride, the hot melt adhesive becomes even more excellent in adhesion to a polyethylene film and a non-woven fabric while maintaining high speed coating capability and low temperature spiral coating capability.
    [00028] When the hot melt adhesive of the present invention has a melt viscosity at 150oC of 7000 mPa.s or less, it becomes possible to be applied by low temperature spiral coating of about 150oC and a film as an adhesive it is less likely to be cast at high temperature, and also the film is less likely to shrink even though the temperature of the adhesion part of the film decreases.
    [00029] Since the disposable products of the present invention are obtainable using the above hot melt adhesive, it is efficiently produced on a high speed coating line. Due to the low temperature of around 150oC, the coating line obtains high security and peeling of a non-woven fabric and a film does not occur. The coating pattern is less likely to be indiscernible, resulting in excellent appearance. Mode for Carrying Out the Invention
    [00030] The hot melt adhesive according to the present invention contains, as essential components, two components: (A) a homopolymer of propylene having a melting point of 100°C or less which is obtainable through polymerization of propylene using a catalyst metallocene; and (B) an ethylene-based copolymer.
    [00031] In the present invention, the homopolymer of propylene (A) refers to a homopolymer of propylene, which is produced by using a metallocene catalyst as a polymerization catalyst. The melting point of the homopolymer of propylene (A) is 100°C or less, more preferably 60 to 90°C, and most preferably 65 to 85°C.
    [00032] Melting point refers to a value measured using differential scanning calorimetry (DSC). Specifically, after weighing 10mg of a sample in an aluminum container, the measurement is performed at a temperature rise rate of 5oC/minute using DSC6220 (trademark) manufactured by SII NanoTechnology Inc., and the temperature of an upper point of a melting peak refers to the melting point.
    [00033] When propylene is polymerized using a metallocene catalyst, a homopolymer of propylene having (i) crystallinity and (ii) very narrow molecular weight distribution is synthesized, meaning that complete isotacticity and syndiotacticity can be optionally controlled. Therefore, a polymer, in which the arrangement, ratio, and the like of methyl groups is uniform, is obtained without causing crystallinity shift, and a low crystalline site that can cause a decrease in adhesive strength is less likely to be formed.
    [00034] With respect to (ii), when the molecular weight distribution of the homopolymer of propylene (A) is indicated by the polydispersity (Mw/Mn), it is 1.0 to 3.0. Propylene homopolymer having polydispersity of 1.0 to 3.0 is excellent in adhesion. Molecular weight distribution is a concept that indicates the distribution of a molecular weight of a synthetic polymer, and a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) serves as a indicator. In the present invention, molecular weight distribution is measured by gel permeation chromatography (GPC).
    [00035] Examples of the propylene homopolymer (A) include: (A1) a propylene homopolymer having a weight average molecular weight of 60,000 or less; and (A2) a propylene homopolymer having a weight average molecular weight of more than 60,000. The weight average molecular weight of the propylene homopolymer (A1) is preferably from 30,000 to 60,000, and particularly preferably from 30,000 to 55,000.
    [00036] The weight average molecular weight of the propylene homopolymer (A2) is more than 60,000, preferably more than 60,000 and 90,000 or less, and more preferably more than 60,000 and 80,000 or less.
    [00037] Examples of a commercially available product of propylene homopolymer (A1) include L-MODU X400S (trademark) manufactured by Idemitsu Kosan Co., Ltd., and examples of a commercially available product of propylene homopolymer (A2) include L-MODU X600S (trademark) manufactured by Idemitsu Kosan Co., Ltd.
    [00038] In the present invention, the propylene homopolymer (A) preferably contains the propylene homopolymer (A1), and may also contain the (A2).
    [00039] The propylene homopolymer (A) may not contain the propylene homopolymer (A1), and may contain only the propylene homopolymer (A2).
    [00040] In the present invention, the amount of the propylene homopolymer (A) is preferably from 60 to 95 parts by weight, and particularly preferably from 70 to 90 parts by weight, based on 100 parts by weight of the total weight of the propylene homopolymer (A) and the ethylene-based copolymer (B).
    [00041] When the propylene homopolymer (A) contains both the propylene homopolymer (A1) and the propylene homopolymer (A2), a weight ratio of both polymers is preferably from 1:3 to 3:2 ((A1 ) : (A2)).
    [00042] The weight average molecular weight (Mw) means a value measured by gel permeation chromatography (GPC). Specifically, the value can be measured by using the following apparatus and measurement process. RI manufactured by Waters Corporation is used as a detector. TSKGEL GMHHR-H(S)HT manufactured by TOSOH CORPORATION is used as a GPC column. A sample is dissolved in 1,2,4-trichloro benzene and allowed to flow at a flow rate of 1.0 mL/minute and a measurement temperature of 145oC, and then the weight average molecular weight is determined by a weight conversion using a derived calibration curve based on polypropylene.
    [00043] Since the number average molecular weight (Mn) is also determined by the same process, the molecular weight distribution is also calculated by GPC.
    [00044] When the hot melt adhesive of the present invention contains the homopolymer of propylene (A1), low temperature spiral coating capability is improved while maintaining adhesion to a polyethylene film and a non-woven fabric.
    [00045] In the present invention, the ethylene-based copolymer (B) refers to a copolymer of ethylene and a copolymerizable monomer that is copolymerizable with ethylene.
    [00046] Examples of the copolymerizable monomer include:
    [00047] alpha olefin such as ethylene, propylene, octene and butene; (esters) of carboxylic acid such as vinyl acetate, (meth)acrylic acid, (meth)aryl acid ester, maleic acid and maleic acid ester;
    [00048] Carboxylic anhydrides such as maleic anhydride, phthalic anhydride, and succinic anhydride; and the like.
    [00049] These copolymerizable monomers can be copolymerized alone with ethylene, or two or more types of copolymerizable monomers can be copolymerized.
    [00050] As used herein, (meth)acrylic acid refers to a concept including both methacrylic acid and acrylic acid. Specific examples of the (meth)acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethyl hexyl acrylate, 2-hydroxy ethyl acrylate, acrylate of isooctyl, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate and the like.
    [00051] Therefore, in the present invention, examples of the ethylene-based copolymer (B) include an ethylene/alpha olefin copolymer, an ethylene/carboxylic acid copolymer, an ethylene/carboxylic acid ester copolymer and a copolymer of ethylene/carboxylic anhydride.
    [00052] The ethylene copolymer (B) of the present invention is preferably the ethylene/alpha olefin copolymer. The ethylene/alpha olefin copolymer is particularly preferably an ethylene/alpha olefin copolymer obtained by polymerization using a metallocene catalyst.
    [00053] When the hot melt adhesive of the present invention contains the ethylene/alpha olefin copolymer obtained by polymerization using a metallocene catalyst, the low temperature spiral coating capability is improved and the adhesion to a polyethylene film and a non-woven fabric fabric is more excellent.
    [00054] Examples of the ethylene/alpha olefin copolymer obtained by polymerization using a metallocene catalyst include an ethylene/propylene copolymer, an ethylene/octene copolymer, an ethylene/butene copolymer and an ethylene/propylene copolymer /butene, and ethylene/propylene copolymer and ethylene/octene copolymer are particularly desirable.
    [00055] When the hot melt adhesive of the present invention contains at least one selected from the ethylene/propylene copolymer and the ethylene/octene copolymer, the spiral coating ability is further improved.
    [00056] A melt index at 230°C of the ethylene/propylene copolymer is preferably 200 g/10 minutes or less, more preferably 10 to 50 g/10 minutes, and most preferably 20 to 30 g/10 minutes. When the melt index is within the above range, the peel strength of the hot melt adhesive is improved.
    [00057] As used herein, melt index means an indicator that indicates fluidity of a resin. A given quantity of a synthetic resin is heated to a prescribed temperature (eg 230o) in a cylindrical vessel heated by a heater, pressurized under a prescribed load (eg 2.16 kg) and then extruded through an opening ( nozzle) provided at the bottom of the vessel, and thus the melt index is represented by the amount of resin extruded for 10 minutes. One unit (g/10 minutes) is used. The melt index is measured using the measurement process defined in ASTM D1238.
    [00058] The hot melt adhesive containing the ethylene/octene copolymer can improve appearance of disposable products since a coating pattern of the adhesive is indistinguishable even if adhesives such as a polyethylene film and a non-woven fabric are coated by spiral coating with the adhesive.
    [00059] As a preferred embodiment of the present invention, when the ethylene-based copolymer (B) is the ethylene/propylene copolymer obtained by polymerization using a metallocene catalyst, the propylene homopolymer (A) preferably contains both, the propylene homopolymer (A1) and propylene homopolymer (A2). When component (A) and component (B) are used in combination as mentioned above, the peel strength of the hot melt adhesive is markedly improved.
    [00060] As another preferred embodiment of the present invention, when the ethylene-based copolymer (B) is the ethylene/octene copolymer obtained by polymerization using a metallocene catalyst, the propylene homopolymer (A) preferably contains only the propylene homopolymer (A1). When component (A) and component ()B) are used in combination as mentioned above, the coating pattern of the hot adhesive becomes barely indistinguishable, and thus the appearance of disposable products is markedly improved .
    [00061] The ethylene/octene copolymer is preferably a block copolymer as compared to a random copolymer. When the ethylene/octene copolymer is a block copolymer, hot melt adhesive excellent in peel strength is obtainable.
    [00062] It is preferred that the hot melt adhesive for disposables of the present invention further includes: (C) a tack forming resin. The tackifying resin (C) is preferably blended in an amount of 20 to 180 parts by weight, more preferably 40 to 150 parts by weight, and particularly preferably 60 to 150 parts by weight, based on 100 parts by weight by weight total of the propylene homopolymer (A) and the wax (B).
    [00063] When the tack-forming resin (C) is combined in the above ratio, the hot melt adhesive can be applied by spiral coating at a low temperature of 150oC or less. Furthermore, the hot melt adhesive can be uniformly applied to a polyethylene film and a non-woven fabric, and thus the obtained adhesive is more suitable for the production of disposable products.
    [00064] Examples of the tack-forming resin (C) include a natural rosin, a modified rosin, a hydrogenated rosin, a glycerol ester of a natural rosin, a glycerol ester of a modified rosin, a penta erythritol ester of a natural rosin, a penta erythritol ester of a modified rosin, a penta erythritol ester of a hydrogenated rosin, a copolymer of a natural terpene, a terpolymer of a natural terpene, hydrogenated derivatives of a copolymer of a hydrogenated terpene, a polyterpene resin, hydrogenated derivatives of a phenol-based modified terpene resin, an aliphatic petroleum hydrocarbon resin, hydrogenated derivatives of an aliphatic petroleum hydrocarbon resin, an aromatic petroleum hydrocarbon resin, hydrogenated derivatives of an aliphatic hydrocarbon resin aromatic petroleum, a cyclic aliphatic petroleum hydrocarbon resin, and hydrogenated derivatives of a resin of cyclic aliphatic petroleum hydrocarbon. These tack-forming resins can be used alone or in combination. It is also possible to use, as the tack-forming resin, a liquid-type tack-forming resin as long as it has a colorless light yellow color tone and has substantially no odor, and also has satisfactory thermal stability. Taking these characteristics comprehensively into account, the tack-forming resin is preferably hydrogenated derivative of resins, and particularly preferably a resin based on hydrogenated di-cyclopentadiene.
    [00065] It is possible to use, as the tack-forming resin (C), commercially available products. Examples of these commercially available products include Alcon P100 (trademark) and Alcon M100 (trademark) manufactured by Arakawa Chemical Industries Ltd.; Clearon M105 (trademark) manufactured by Yasuhara Chemical Co., LTD.; ECR5400 (trademark) and ECR179EX (trademark) manufactured by Exxon Corporation; and Quinton DX390 (trademark) manufactured by Zeon Corporation. These commercially available tack-forming resins can be used alone, or in combination.
    [00066] The hot melt adhesive of the present invention may further include: an oil (D). Oil (D) is combined as a plasticizer for the purpose of decreasing the melt viscosity of the hot melt adhesive, providing flexibility to the hot melt adhesive, and improving the wetting ability of the hot melt adhesive for a stick. Oil combination (D) allows low temperature spiral coating.
    [00067] Examples of oil (D) include paraffin based oils, naphthene based oils, and aromatics based oils.
    [00068] It is possible to use, like oil (D), commercially available products. Examples include Diana Fresia S32 (trademark), Diana Process Oil PW-90 (trademark) and Process Oil NS-100 (trademark) manufactured by Idemitsu Kosan Co., Ltd.; PHAZOL35 (trademark) manufactured by SK Lubricants; KN4010 (trademark) manufactured by PetroChina Company; White Oil Broom 350 (trademark) and DN oil KP-68 (trademark) manufactured by Kukdong Oil & Chemical Co., Ltd; Enerper M1930 (trademark) manufactured by BP Chemicals Ltd.; Kaydol (trademark) manufactured by Esso Corp. These oils (D) can be used alone, or in combination.
    [00069] The hot melt adhesive of the present invention preferably contains: (E) a wax. As used herein, "wax" refers to an organic substance having a weight average molecular weight of less than 10,000, which is solid at normal temperature and becomes liquid when heated, and is commonly regarded as a "wax". There is no particular limitation on the wax as far as the hot melt adhesive according to the invention can be obtained, if it has wax-like properties.
    [00070] The wax (E) preferably contains: (E1) an olefin wax modified with carboxylic acid or carboxylic anhydride.
    [00071] In the present invention the "olefin wax (E1) modified with carboxylic acid or carboxylic anhydride" refers to an olefin wax that is chemically or physically processed with carboxylic acid or carboxylic anhydride, and there is no particular limitation as far as the purpose of the hot melt adhesive of the present invention is obtainable. Examples of physical or chemical processing include oxidation, polymerization, combination, synthesis and the like.
    [00072] Examples of the wax (E1) include a wax that is obtainable through graft polymerization of carboxylic acid or carboxylic anhydride with an olefin wax; and a wax that is obtainable through copolymerization of carboxylic acid or carboxylic anhydride in the synthesis of an olefin wax through polymerization.
    [00073] Hence, the wax can be an olefin wax that is modified as a result of introducing carboxylic acid or carboxylic anhydride into the "olefin wax" using various reactions.
    [00074] There is no particular limitation on the "carboxylic acid" and/or "carboxylic anhydride" to be used to modify the olefin wax as far as the hot melt adhesive objective of the present invention is achievable.
    [00075] Specific examples of the carboxylic acid or carboxylic anhydride include maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, itaconic acid, acrylic acid, methacrylic acid and the like. These carboxylic acids and/or carboxylic anhydrides can be used alone, or in combination. Maleic acid and maleic anhydride are particularly preferable.
    [00076] The "carboxylic acid" and/or "carboxylic anhydride" to be used to modify the olefin wax refers to a wax that is obtainable by copolymerizing two or more types of olefins, and there is no particular limitation as to object wax (E1) according to the present invention is obtainable. Therefore, a wax obtained by homopolymerizing an olefin type is not included in the olefin wax.
    [00077] Specific examples of the olefin wax include a polyethylene wax, a polypropylene wax, a polyethylene/polypropylene wax, a polyethylene/polybutylene wax, a polyethylene/polybutene wax and the like.
    [00078] Therefore, the wax (E1) in the present invention is particularly preferably a polyolefin wax modified with maleic anhydride.
    [00079] The "wax (E)" may include, in addition to the wax (E1), a base wax, and specific examples thereof include: synthetic waxes such as a Fischer - Tropsch wax, a polyolefin wax (eg. polyethylene, polypropylene wax, and a polyethylene/polypropylene wax); petroleum waxes such as a paraffin wax and a microcrystalline wax; and natural waxes like a castor wax.
    [00080] The above base wax can be modified. A substance to modify the base wax can be various carboxylic acid derivatives as much as a polar group can be introduced. Examples of the "carboxylic acid derivative" include: carboxylic acid esters such as ethyl acetate and vinyl acetate; acid halides such as benzoyl bromide; amides such as benzamide, N-methyl acetamide and N,N-dimethyl formamide; imides such as succinimide; acyl azide such as acetyl azide; hydrazides such as propanoyl hydrazide; hydroxamic acids such as chloroacetyl hydroxamic acid; lactones such as Y-butyrolactone; and lactams such as δ-caprolactam.
    [00081] Modified base wax does not contain: olefin wax (E1) modified with carboxylic acid or carboxylic anhydride.
    [00082] In the present invention, the wax (E) preferably contains, in addition to (E1), a Fischer - Tropsch wax (E2) mentioned as the base wax. "Fischer-Tropsch wax (E2)" refers to a wax that is synthesized through the Fischer-Tropsch process and is commonly thought of as a Fischer-Tropsch wax. Fischer-Tropsch wax is fractionated from a wax whose component molecules have a comparatively wide carbon number distribution so that component molecules have a narrow carbon number distribution. Examples of typical Fischer-Tropsch waxes include Sasol H1 (trademark) and Sasol C80 (trademark), both of which are commercially available from Sasol Wax.
    [00083] In the present invention, the melting point of the wax (E1) is preferably from 100 to 130oC, and the melting point of the base wax, preferably the wax (E2) is preferably from 60 to 90oC. The process for measuring the melting point is the same as that for measuring the melting point of component (A).
    [00084] An acid value of the wax (E) is preferably from 5 to 200 mg KOH/g, and more preferably from 20 to 160 mg KOH/g. The acid value can be measured in accordance with ASTM D1308 or BWM 3.01A.
    [00085] If necessary, the hot melt adhesive according to the present invention can still contain various additives. Examples of the various additives include a stabilizing agent and a fine particle filler material.
    [00086] The "stabilizing agent" is combined in order to prevent decrease in molecular weight, occurrence of gelling, coloration, odor and the like of the hot melt adhesive due to heat, thereby improving stability of the hot melt adhesive, and there is no particular limitation as far as the hot melt adhesive object of the present invention is obtainable. Examples of the "stabilizing agent" include an antioxidant and an ultraviolet absorber.
    [00087] The "ultraviolet absorber" is used in order to improve light fastness of the hot melt adhesive. The "antioxidant" is used in order to prevent oxidative degradation of the hot melt adhesive. There is no particular limitation on the antioxidant and ultraviolet absorber as far as they are commonly used in disposable products and the object disposable products mentioned below are obtainable.
    [00088] Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Examples of the ultraviolet absorber include a benzotriazole based ultraviolet absorber and a benzophenone based ultraviolet absorber. These additives can be used alone, or in combination.
    [00089] It is possible to use, as the stabilizer, commercially available products. Examples include SUMILIZER GM (trademark), SUMILIZER TPD (trademark), and SUMILIZER TPS (trademark) manufactured by Sumitomo Chemical Co. Ltd.; Irganox 1010 (trademark), IRGANOXI HP2225FF (trademark), IRGAFOS 168 (trademark) and IRGANOX 1520 (trademark) manufactured by Ciba Specialty Chemicals Inc.; and JF77 (trademark) manufactured by Johoku Chemical Co., Ltd. These stabilizers can be used alone, or in combination.
    [00090] The hot melt adhesive for disposable products of the present invention may further include a fine particle filler material. The fine particle filler material can be commonly used fine particle filler material, and there is no particular limitation as far as the hot melt adhesive object of the present invention can be obtained. Examples of the "fine particle filler material" include mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea-based resin, styrene beads, calcined clay, starch and the like. These particles preferably have a spherical shape, and there is no particular limitation on size (diameter in case of a spherical shape).
    [00091] The hot melt adhesive for disposable products of the present invention can be produced by combining components (A) and (B), optionally combining components (C)-(E), if necessary combining various additives, and melting of mixing with heating, followed by mixing. Specifically, the hot melt adhesive can be produced by charging the above components into a melt mixing vessel equipped with an agitator, followed by heating and mixing.
    [00092] With respect to the hot melt adhesive for disposable products according to the present invention, a melt viscosity at 150oC is preferably 7000 mPa.s or less, more preferably 1000 to 6000 mPa.s, and particularly preferably 2000 mPa.s at 6000 mPa.s. The "melt viscosity" is a viscosity of a hot melt adhesive melt and is measured on a Brookfield-type RVT viscometer (stem no. 27).
    [00093] By controlling melt viscosity within the above range, hot melt adhesive is more suitable for low temperature coating. Furthermore, the hot melt adhesive is uniformly applied to a non-woven fabric and is likely to penetrate, and thus the adhesive is more suitable for use in disposable products.
    [00094] As mentioned above, the hot melt adhesive according to the present invention can also be employed in paper processing, book gluing, disposable products and the like, and it is suitable for use in disposable products as it is excellent in adhesion to a non-woven fabric and a polyethylene film.
    [00095] Disposable products can consist of a coating of at least one type of a member selected from the group consisting of a woven fabric, a non-woven fabric, a rubber, a resin, papers, a polyolefin film with the adhesive hot melt according to the present invention. The polyolefin film is preferably a polyethylene film for reasons of durability, cost and the like.
    [00096] There is no particular limitation on disposable products as far as they are so called sanitary materials. Specific examples include a paper diaper, a sanitary napkin, a pet sheet, a hospital gown, a white surgical garment, and the like.
    [00097] In the production line of the disposable products, various members (eg fabric, cotton, non-woven fabric, polyolefin film, etc.) of the disposable products are commonly coated with the hot melt adhesive. In the case of coating, hot melt adhesive can be discharged (or ejected) from several weirs (or ejectors).
    [00098] There is no particular limitation on the coating process with the hot melt adhesive as far as object disposable products can be obtained. Such a coating process is roughly classified into a contact coating process and a non-contact coating process. The "contact coating" process refers to a coating process in which a discharger is brought into contact with a member or a film in the case of coating with the hot melt adhesive, while the "non-contact coating" process refers to a coating process in which a discharger is not brought into contact with a member or a film in the case of coating with the hot melt adhesive. Examples of the contact coating process include a slit coater coating process, a roll coater coating process, and the like, and examples of the non-contact coating process include a spiral coating capable of coating in a spiral shape, a coating omega or control seam coating process capable of coating in a wavy shape, a slit spread coating or curtain spread coating process capable of coating in a flat shape, and spot coating capable of coating in a dot shape .
    [00099] The hot melt adhesive of the present invention is suitable for spiral coating. The spiral coating process is a process in which an adhesive is applied through intermittent or continuous application, where air is supplied to form a spiral adhesive and the adhesive is applied to a member (or a base material) without contact.
    [000100] It is extremely useful for the production of the disposable products that the hot melt adhesive can be applied in a wide width through spray coating. The hot melt adhesive capable of being applied over a wide width is capable of decreasing the coating width by adjusting the hot air pressure.
    [000101] When it is difficult to apply the hot melt adhesive over a wide width, a lot of spreader nozzles to obtain sufficient bonding area are required, and thus it is unsuitable for the production of comparatively small disposable products such as a plastic liner. urine collection, and disposable products having a complicated shape.
    [000102] Therefore, the hot melt adhesive of the present invention is suitable for disposable products since the spiral coating can be carried out in a wide width.
    [000103] The hot melt adhesive of the present invention is useful for the production of disposable products due to satisfactory coating ability at 150oC or less. In case of coating with the hot melt adhesive at a high temperature, since a polyethylene film as a base material of the disposable products can be melted and thermally contracted, the appearance of the disposable products is drastically impaired. In case of application of hot melt adhesive at 150oC or less, the appearance of a non-woven fabric and the polyethylene film as a base material of the disposable products barely changes and thus the appearance of the products is not impaired.
    [000104] The hot melt adhesive of the present invention is suitable for producing the disposable products within a short time as it is excellent in high speed coating capability. When the base material to be transported at high speed is coated with the hot melt adhesive, breakage of the base material due to friction sometimes arises in the contact type coating process. The hot melt adhesive of the present invention is suitable for spiral coating as a type of non-contact coating and is therefore suitable for high speed coating, and thus it is possible to improve the production efficiency of the disposable products. Furthermore, the hot melt adhesive of the present invention suitable for high speed coating minimizes coating pattern disturbance.
    [000105] The hot melt adhesive of the present invention has satisfactory thermal stability and is uniformly melted in a high temperature tank at 100 to 200oC and does not cause phase separation. A hot melt adhesive having poor thermal stability easily causes phase separation of components in the high temperature tank. Phase separation can cause clogging of a tank filter and transfer piping.
    [000106] Main embodiments of the present invention are shown below.
    [000107] A hot melt adhesive including: (A) a homopolymer of propylene having a melting point of 100°C or less which is obtainable through polymerization of propylene using a metallocene catalyst; and (B) an ethylene-based copolymer.
    [000108] The hot melt adhesive according to 1 above, wherein the ethylene-based copolymer (B) is an ethylene/alpha olefin copolymer which is obtainable through polymerization using a metallocene catalyst.
    [000109] The hot melt adhesive according to 2 above, wherein the ethylene/alpha olefin copolymer (B) contains at least one selected from an ethylene/propylene copolymer and an ethylene/octene copolymer.
    [000110] The hot melt adhesive according to any one of 1 to 3 above, further including: (C) a tack forming resin; and (D) an oil.
    [000111] The hot melt adhesive according to any one of 1 to 4 above, further including: (E) a wax, where the wax (E) includes a wax modified with carboxylic acid and/or carboxylic anhydride.
    [000112] Hot melt adhesive according to any one of 1 to 5 above, wherein the adhesive has a melt viscosity at 150oC of 7000 mPa.s or less.
    [000113] Disposable products obtainable through use of hot melt adhesive in accordance with any one to 6 above. Examples
    [000114] The present invention will be described for the purpose of describing the present invention in a more detailed and specific manner by way of examples. These are exemplars of the present invention and are not to be considered limiting.
    [000115] Components for combining (or formulating) a hot melt adhesive are shown below.
    [000116] Propylene homopolymer having a melting point of 100oC or less which is obtained by polymerization using a metallocene catalyst (A1) Propylene homopolymer having a melting point of 75oC and a weight average molecular weight of 45000, manufactured by Idemitsu Kosan Co., Ltd. under the trademark of "L-MODU X400S". (A2) Propylene homopolymer having a melting point of 80°C and a weight average molecular weight of 70,000, manufactured by Idemitsu Kosan Co., Ltd. under the trademark "L-MODU X600S". (A’3) Propylene homopolymer having a melting point of 145oC obtained by polymerization using a metallocene catalyst, manufactured by Clariant K.K. under the trademark "Pliocene PP6102". (A’4) Propylene homopolymer having a melting point of 145oC obtained by polymerization using a Ziegler - Natta catalyst, manufactured by Eastman Chemical Company under the trademark "Eastoflex P1010". (A’5) Polyethylene homopolymer having a melting point of 128°C obtained by polymerization using a metallocene catalyst, manufactured by Clariant K.K. under the trademark "Licocene PE4201GR". (8) Ethylene-based copolymer (81) propylene/ethylene copolymer having a melt index of 200 (g/10 minutes: 230oC) obtained by polymerization using a metallocene catalyst, manufactured by Exxon Móbil Corporation under the trademark of "Vistamaxx 2330". (82) Propylene/ethylene copolymer having a melt index of 20 (g/10 minutes: 230°C) obtained by polymerization using a metallocene catalyst, manufactured by Exxon Mobil Corporation under the trademark "Vistamaxx 6202". (83) Propylene/ethylene copolymer (having a random propylene/ethylene copolymerization structure) having a melt index of 25 (g/10 minutes: 230oC) obtained by polymerization using a metallocene catalyst, manufactured by Dow Chemical Company under Trademark of "VERSIFY 4301". (84) Ethylene/octene copolymer (having an ethylene/octene block structure) having a melt index of 15 (g/10 minutes: 190°C) which is obtained through polymerization using a metallocene catalyst, manufactured by Dow Chemical Company under the registered trademark of "INFUSE 9807". (85) Ethylene/octene copolymer (having a random ethylene/octene copolymerization structure) having a melt index of 13 (g/10 minutes: 190oC) obtained by polymerization using a metallocene catalyst, manufactured by Dow Chemical under Trademark of "ENGAGE 8137". (86) Ethylene/octene copolymer (having a random ethylene/octene copolymerization structure) having a melt index of 500 (g/10 minutes: 190oC) obtained by polymerization using a metallocene catalyst, manufactured by Dow Chemical Company under the registered trademark of "AFFINITY GA1950". (87) Propylene/ethylene copolymer "REXtac 2780a" (trademark), manufactured by Huntsman Corp., which is obtained through polymerization using a Ziegler - Natta catalyst. (88) Propylene/ethylene/butene copolymer obtained by polymerization using a Ziegler - Natta catalyst, manufactured by Evonik under the trademark "VESTOPLAST 703". (89) Ethylene/vinyl acetate copolymer obtained by polymerization using a Ziegler - Natta catalyst, manufactured by TOSOH CORPORATION under the trademark "Ultracene 722" (B'10) Propylene/butene copolymer obtained by polymerization using a Ziegler - Natta catalyst, manufactured by Huntsman Corp. under the trademark of "REXtac 2780A" (B’11) Acrylic copolymer, manufactured by Mitsubischi Rayon Co., Ltd. under the trademark of "BR-106". (C) Tack-forming resin (C1) hydrogenated dicyclopentadiene based resin, manufactured by Exxon Mobil Corporation under the trademark "ECR179EX". (C2) hydrogenated dicyclopentadiene based resin, manufactured by Exxon Mobile Corporation under the trademark "ECR5400". (C3) Hydrogenated cyclic aliphatic petroleum hydrocarbon resin manufactured by Arakawa Chemical Industries, Ltd. under the trademark of "Alcon M100". (C4) Hydrogenated cyclic aliphatic petroleum hydrocarbon resin manufactured by Arakawa Chemical Industries, Ltd. under the trademark of "Alcon P100". (C5) Non-hydrogenated aliphatic aromatic copolymer based resin manufactured by Zeon Corporation under the trademark "Quintone DX390N". (C6) Hydrogenated terpene-based resin manufactured by YASUHARA CHEMICAL CO., LTD. under the trademark of "Clearon M105" (D) Oil (D1) Paraffin oil, manufactured by Idemitsu Kosan Co., Ltd. under the trademark of "DN Oil KP-68" (D2) Paraffin oil, manufactured by SK LUBRICANTS under the trademark of "PHAZOL35" (D3) Paraffin oil, manufactured by Idemitsu Kosan Co., Ltd. under the trademark of "Diana Process Oil PW-90" (D4) Paraffin oil, manufactured by Idemitsu Kosan Co., Ltd. "Diana Fresia S32" (D5) Naphthene oil, manufactured by Idemitsu Kosan Co., Ltd. adds the trademark of "Process Oil NS100" (D6) Naphthene oil, manufactured by PetroChina Company under the trademark " KN4010" (E) Wax modified with carboxylic acid or carboxylic anhydride (E1) Wax modified with maleic acid, manufactured by Clariant KK under the trademark of "Licocene MA6252TP" (E2) Fischer Wax - Tropsch, manufactured by Sasol under the trademark of "Sasol Wax H-1". (F) Antioxidant (F1) hindered phenol-based antioxidant, manufactured by ADEKA Corporation under the trademark "Adekastab AO-60"
    [000117] These components (A) to (F) were combined according to the formulations shown in Tables 1 to 3, and then melt blended at about 150oC over 2 hours using a universal stirrer to prepare hot melt adhesives of Examples 1 to 19 and Comparative Examples 1 to 9. All numerical values with respect to the composition (combination) of the hot melt adhesives shown in Tables 1 to 3 are parts by weight.
    [000118] With respect to the respective hot melt adhesives (Examples and Comparative Examples), thermal stability, coating ability, high speed coating ability and peel strength were evaluated. Summary of the respective assessments is described below. < Thermal Stability>
    [000119] Thermal stability was evaluated based on the presence or absence of phase separation of the hot melt adhesive.
    [000120] Each hot melt adhesive was loaded into a glass bottle and allowed to stand at a temperature of 150oC for 6 hours, and then it was visually observed whether or not phase separation occurred. The weight of each hot melt adhesive was 350 to 400 g and a 450 ml volume glass bottle was used. The glass bottle loaded with the hot melt adhesive was allowed to rest in a dryer after covering with a lid made of aluminum.
    [000121] After a predetermined time, the hot melt adhesive was removed, and the presence or absence of phase separation was quickly visually confirmed.
    [000122] B: phase separation not recognized
    [000123] C: phase separation recognized < Fusion Viscosity Measurement (150oC) >
    [000124] The viscosity at 150oC of each hot melt adhesive was measured according to process B defined in JAI7-1991. The measurement was performed by a No. 27 rotor using a Brookfield viscometer. < Coating Capacity >
    [000125] Using a spiral spreader manufactured by Nordson Corporation, a base coat material was coated with a hot melt adhesive to produce a laminate of the base coat material and a base material fastener (or lamination), and the coating capability was evaluated, and also samples for the evaluation of the peel strength mentioned below were produced. Both the base coat material and the base fastener material are polyethylene terephthalate (PET) films.
    [000126] More specifically, the base coating material was coated with the hot melt adhesive under the conditions of a temperature of each of a hot melt tank and a spiral sparge nozzle of 150oC, a hot air temperature of 180oC , a hot air pressure of 0.32 kgf/cm2, a hot melt adhesive discharge amount of 15 g/minute (corresponding to a coating weight of 5 g/m2), the distance between the nozzle and the material 35 mm coating base, a base material transport speed of 200 m/minute, an opening time of 0.21 second, and a pressure with pressing after coating of 2.0 kgf/cm to produce a laminate (film PET/PET film), and then the coating ability was evaluated. Coating ability was evaluated by confirming a coating width of the hot melt adhesive applied via spiral coating. Evaluation criteria are shown below.
    [000127] A: coating width of 15 mm or more
    [000128] B: cladding width was 12 mm or more and less than 15 mm
    [000129] C: coating width was less than 12 mm < High speed coating capacity >
    [000130] Under the above-mentioned coating capability test conditions, high-speed coating capability was evaluated.
    [000131] In the same manner as in the coating capacity evaluation, except that the hot air pressure was changed to 0.45 kgf/cm2, a test was performed. High speed coating capability was assessed visually. The evaluation criteria are as follows.
    [000132] A: Hot melt adhesive dispersion was not recognized.
    [000133] B: dispersion of hot melt adhesive was slightly recognized.
    [000134] C: pattern was not obtained due to dispersion of hot melt adhesive, or coating width of hot melt adhesive was less than 15mm. < Peeling resistance >
    [000135] Using the same test conditions as in the high speed coating capability, samples of the peel strength were produced.
    [000136] A conventional non-woven fabric (15 g/m2 SMS, no surface treatment) was used as the base lining material, and two types of (1) a conventional non-woven fabric (15 g/m2 SMS without surface treatment) and (2) a conventional polyethylene film (no etching, 30 g/m2, no corona treatment) were used as an anchoring base material.
    [000137] After aging samples in the atmosphere at 23o under 65% U.R. for 24 hours or more, a peeling test was carried out under the same atmosphere. Peeling test was performed by Autograph AGS-J manufactured by Shimadzu Corporation under the following conditions.
    [000138] Stripping direction: direction which is the same as the moving direction of the base material direction (MD), distance between mandrels: 20 mm, stripping speed: 300 mm/minute, stripping length: 50 mm, process analysis: test force mean.
    [000139] With each hot melt adhesive (Examples and Comparative Examples), at least three samples were produced and then measured. Peel strength was determined by the average obtained. Peel strength was evaluated using the following criteria.
    [000140] Base material to be affixed (or laminated) was a non-woven fabric (non-woven fabric/non-woven fabric)
    [000141] A: Peel strength was 2.0 N or more.
    [000142] B: Peel strength was 0.5 N or more and less than 2.0 N.
    [000143] C: Peel strength was less than 0.5 N. (2) Base material to be fixed was a polyethylene film (polyethylene film/non-woven fabric)
    [000144] A: peel strength was 0.20 N or more
    [000145] B: Peel strength was 0.10 N or more and less than 0.20 N.
    [000146] C: Peel strength was less than 0.10 N. < Appearance >
    [000147] When an air permeable polyethylene film is coated with a hot melt adhesive, a coating pattern of the hot melt adhesive applied inside can sometimes be seen through from the outer surface of the film. Hot melt adhesive whose coating pattern is indiscernible is not preferable in view of design properties of disposable products using an air permeable film, and a hot melt adhesive whose coating pattern is indiscernible is desired.
    [000148] In order to assess whether or not a coating pattern is indiscernible, the assessment was carried out through the following procedure.
    [000149] A 50 micron thick PET film was coated with each hot melt adhesive to form a 50 micron thick adhesive layer, and then formed into a 25x10 mm shape to obtain a test piece. The test piece was attached (or placed on the back) to a commercially available air-permeable napkin (ELIS SHIN-SUHADAKAN, No Wing 20.5 cm, manufactured by ELLEAIR PAPER TECH CO., LTD.) and a weight of 1 kg was placed on the fixed part, followed by resting on a tray at 50oC for 3 days. After a predetermined time, the weight was removed and the change in appearance was confirmed. The evaluation criteria are as follows.
    [000150] A: applied hot melt adhesive was indiscernible.
    [000151] B: Applied hot melt adhesive was lightly seen through.
    [000152] C: Applied hot melt adhesive was seen through.



    [000153] As shown in Table 1, the hot melt adhesives of Examples 1 to 11 are excellent in thermal stability, coatability and high speed coatability, and are also excellent in peel strength for a non-woven fabric, and are therefore suitable for use in disposable products using a non-woven fabric, such as a diaper and napkin.
    [000154] In contrast, the hot melt adhesives of Comparative Examples 1 to 9 are inferior in any of the above performances as shown in Table 2. 5


    [000155] As shown in Table 3, the hot melt adhesives of Examples 12 to 19 not only have the satisfactory performances shown above, but also a pattern after coating is indiscernible.
    [000156] Taking design properties of disposable products using an air permeable film into consideration, the hot melt adhesives of Examples 12 to 19 are extremely excellent for disposable products. Industrial Applicability
    [000157] The present invention provides a hot melt adhesive. The hot melt adhesive according to the present invention is suitable for disposable products.
    权利要求:
    Claims (3)
    [0001]
    1. Hot melt adhesive, characterized in that it comprises: (A) a homopolymer of propylene having a melting point of 100oC or less, which is crystalline and has a polydispersity (Mw/Mn) of 1.0 at 3.0, measured by gel permeation chromatography, which is obtained by polymerizing propylene using a metallocene catalyst; and (B) an ethylene/alpha olefin copolymer which is obtained by polymerization using a metallocene catalyst, which is selected from an ethylene/propylene copolymer, an ethylene/octene copolymer, an ethylene/butene copolymer and a copolymer of ethylene/propylene/butene.
    [0002]
    2. Hot melt adhesive according to claim 1, characterized in that the ethylene/alpha olefin copolymer (B) contains at least one selected from an ethylene/propylene copolymer and an ethylene/octene copolymer .
    [0003]
    3. Disposable products, characterized in that they can be obtained using the hot melt adhesive as defined in claim 1 or 2.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014006221B1|2021-05-18|hot melt adhesive and disposable products obtained therefrom
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    同族专利:
    公开号 | 公开日
    CN103797081A|2014-05-14|
    CN103797081B|2017-05-03|
    US20140199545A1|2014-07-17|
    US10370567B2|2019-08-06|
    EP2756049B1|2018-12-19|
    WO2013039261A1|2013-03-21|
    TR201903788T4|2019-04-22|
    US9695340B2|2017-07-04|
    US20170260430A1|2017-09-14|
    MX351783B|2017-10-30|
    RU2607586C2|2017-01-10|
    BR112014006221A2|2017-04-11|
    RU2014115211A|2015-10-27|
    EP2756049A1|2014-07-23|
    CA2848565A1|2013-03-21|
    JP2013064055A|2013-04-11|
    CA2848565C|2018-08-07|
    KR20140070549A|2014-06-10|
    KR20180023007A|2018-03-06|
    KR101831485B1|2018-02-22|
    PT2756049T|2019-02-01|
    JP5850682B2|2016-02-03|
    MX2014003116A|2014-04-25|
    KR101921035B1|2018-11-21|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-22| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-04-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011-203063|2011-09-16|
    JP2011203063A|JP5850682B2|2011-09-16|2011-09-16|Hot melt adhesive|
    PCT/JP2012/074134|WO2013039261A1|2011-09-16|2012-09-13|Hot melt adhesive|
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