A lump and a container to which a label has been attached using the lump.

Abstract

To provide a lump-like material that exhibits superior bag breakability compared to conventional materials, as well as superior solubility (compatibility) with the contents and stringing resistance during coating, even when a low-viscosity hot-melt adhesive is enclosed within the molten bag, and a container to which a label is attached using this material. [Solution] A mass containing a hot melt adhesive composition within a molten bag, wherein the molten bag has a density of 923-930 kg / m³. 3 A mass comprising a mixed resin film containing a low-density polyethylene resin (A) and an ethylene-vinyl acetate copolymer resin (B), wherein the hot-melt adhesive composition contains a plasticizer (C) and has a viscosity of 500 to 2500 mPa·s at 140°C.

Description

[Technical Field]

[0001] The present invention relates to a mass containing a hot-melt adhesive composition in a molten bag, and a container to which a label is attached using the same. [Background technology]

[0002] Hot melt adhesives, which eliminate the need for a curing period after melting and bonding objects, are gaining renewed attention for their advantage of immediate adhesion upon cooling, and are being widely used in packaging and industrial applications. Furthermore, in response to recent societal changes that emphasize reducing environmental impact, the advantage of not requiring solvents or drying processes during use is also being re-evaluated, leading to even greater expansion of their use.

[0003] As the range of applications for hot melt adhesives expands, there is a growing demand for improved workability. For example, in the summer, lumps of hot melt adhesive would stick together (blocking), resulting in huge lumps when removed from cardboard packaging, significantly reducing workability. Therefore, hot melt adhesives that exhibit tackiness at room temperature were packaged, transported, and stored in a release liner or film, and these were removed and discarded when the hot melt adhesive was used. However, the disposal of these release materials has also become a concern as an environmental burden.

[0004] Therefore, as a method that does not use release agents, a specification using a so-called melt bag (block form) has been developed in which the hot melt adhesive is packaged in a hard material and the hot melt adhesive is melted while still in the package when it is ready to use (Patent Document 1). Since the block form melts the hot melt adhesive while it is still in the melt bag, basic performance such as the solubility (mismatch) of the melt bag and the hot melt, and the ability to break the bag when stored at high temperatures are required. The practical application of the block form avoids the environmental burden caused by the disposal of release agents, and also eliminates the burden of peeling off the release agent each time the block of hot melt adhesive is melted, dramatically improving work efficiency. Furthermore, in recent years, measures have been taken to prevent blocking by increasing the strength of the melting bags (Patent Document 2) or by making their shape embossed (Patent Document 3).

[0005] Polyethylene terephthalate bottles (hereinafter referred to as PET bottles), typically used for beverages, have labels attached, and wrap-around labels are commonly used. Hot-melt adhesives are generally used as the adhesive for wrap-around labels. For hot-melt adhesives used for PET bottle labels, a low-viscosity hot-melt adhesive with a viscosity of 2,500 mPa·s or less at 140°C is preferable to prevent the hot-melt adhesive from splattering and contaminating the labeler in a stringy manner (stringiness) when applied to the label (Patent Document 4). With the increasing use of PET bottles for beverages, there is a growing demand for such low-viscosity hot-melt adhesives packaged in molten bags, but there have been challenges in terms of the stringiness of the molten molten material.

[0006] The present inventors have found that in the inventions described in Patent Documents 1 to 3, when low-viscosity hot melt is enclosed in a molten bag, the hot melt can leach out of the molten bag due to cold flow (a phenomenon in which the hot melt gradually deforms and spreads) during storage, and the molten bag can break during packaging, causing the hot melt adhesive to come to the surface and resulting in a problem where the lumps of material block each other. In other words, a mass-like material that satisfies the solubility of the molten bag and hot melt, the ability to break the bag to prevent blocking, and the stringing properties during coating, while containing a low-viscosity hot melt within the molten bag, had not been developed. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2004-002581 [Patent Document 2] International Publication No. 2014 / 194087 [Patent Document 3] Japanese Patent Publication No. 2019-065164 [Patent Document 4] Japanese Patent Publication No. 2010-090185 [Overview of the project] [Problems that the invention aims to solve]

[0008] Therefore, the present invention aims to provide a lump that exhibits superior bag breakage performance, solubility (mismatch) with the contents, and stringing resistance during coating, even when a low-viscosity hot-melt adhesive composition with a viscosity of 500 to 2500 mPa·s at 140°C is contained within the molten bag, compared to conventional materials, and also provides a container to which a label is attached using the lump. [Means for solving the problem]

[0009] This disclosure provides the following bulk materials and containers to which labels are attached using these bulk materials. [1] A mass containing a hot melt adhesive composition in a molten bag, The molten bag has a density of 923-930 kg / m³. 3 It consists of a mixed resin film containing low-density polyethylene resin (A) and ethylene-vinyl acetate copolymer resin (B), A hot melt adhesive composition containing a plasticizer (C) and having a viscosity of 500 to 2500 mPa·s at 140°C, in the form of a lump.

[0010] [2] The mass according to [1], characterized in that the plasticizer (C) contains a plasticizer having a melting point of 35 to 120°C.

[0011] [3] The mass according to [1] or [2], wherein the content of ethylene-vinyl acetate copolymer resin (B) in 100% by mass of the mixed resin film is 10 to 50% by mass.

[0012] [4] The aggregate according to any one of [1] to [3], wherein the vinyl acetate content of the ethylene-vinyl acetate copolymer resin (B) is 5 to 30% by mass.

[0013] [5] Low-density polyethylene resin (A) at 190°C, 2.16 kgf / cm² 2 A mass according to any one of [1] to [4], characterized in that the melt mass flow rate in is 1 to 25 g / 10 min.

[0014] [6] The bulk material according to any one of [1] to [5], characterized in that the film thickness of the melting bag is 10 to 500 μm.

[0015] [7] The bulk material according to any one of [1] to [6], characterized in that the plasticizer (C) contains at least one selected from fatty acids and their derivatives.

[0016] [8] The bulk material according to any one of [1] to [7], characterized in that the hot melt adhesive composition is an alkali-dispersed type hot melt adhesive composition.

[0017] [9] A container to which a label is adhered using the bulk material according to any one of [1] to [8].

[0018]

[10] The container according to [9], characterized in that the material of the container is polyethylene terephthalate or glass.

MODE FOR CARRYING OUT THE INVENTION

[0019] Hereinafter, the present disclosure will be described in detail. Needless to say, other embodiments are also included in the scope of the present disclosure as long as the problems of the present disclosure can be solved.

[0020] In this specification, the numerical range specified using "~" shall include the numerical values described before and after "~" as the range of the lower limit value and the upper limit value. In addition, various components appearing in this specification may be used alone or in combination of two or more, respectively, unless otherwise noted. Further, "parts" and "%" represent "parts by mass" and "mass%" respectively, unless otherwise specified.

[0021] In this specification, "viscosity" is measured according to JIS K6862 (Test method for melt viscosity of hot melt adhesives). In this specification, "melt mass flow rate (hereinafter abbreviated as MFR)" is measured at 190 °C, 2.16 kgf / cm according to JIS K7210 (Test method for flow of thermoplastic plastics). 2This is the meltmass flow rate in [location]. In this specification, the "melting point of the plasticizer" is the value measured using a differential scanning calorimetry device (Shimadzu DSC-60A Plus automatic differential calorimetry device). In this specification, "film thickness" was measured using a PEACOCK DIGITAL THICKNESS GAUGE G2-205 manufactured by Ozaki Seisakusho Co., Ltd.

[0022] Furthermore, in this specification, "hot melt" refers to a material that is solid or viscous at room temperature and melts and softens, becomes fluid, or becomes liquid upon heating.

[0023] <Flat bag> The molten bag is used to package hot-melt adhesive compositions. However, this is not limited to packaging other articles if it can contribute technically to them. The molten bag used in this invention has a density of 923-930 kg / m³. 3 The molten bag is made of a mixed resin film containing low-density polyethylene resin (A) and ethylene-vinyl acetate copolymer resin (B). The molten bag can be manufactured by heating and melting the mixed resin film and forming a film using a known method. It is desirable that the film thickness of the molten bag be as uniform as possible.

[0024] From the viewpoint of meltability and bag-breaking properties, it is preferable that the mixed resin film contains 50 to 90% by mass of low-density polyethylene resin (A) in 100% by mass, and more preferably 70 to 90% by mass. Furthermore, from the viewpoint of bag-breaking properties and solubility, it is preferable that the mixed resin film contains 10 to 50% by mass of ethylene-vinyl acetate copolymer resin (B) in 100% by mass, and more preferably 10 to 30% by mass.

[0025] The film thickness of the molten bag is preferably 10 to 500 μm, more preferably 20 to 200 μm, and even more preferably 30 to 100 μm. Having the film thickness within this range makes it easier to achieve both solubility and bag breakability.

[0026] [Low-density polyethylene resin (A)] The density of low-density polyethylene (A) is 923-930 kg / m³. 3 Its density is 923-930 kg / m³. 3 This results in excellent bag-breaking and solubility. The MFR of low-density polyethylene resin (A) is preferably 1 to 25 g / 10 min, and more preferably 7 to 25 g / 10 min, from the viewpoint of melting and bag-breaking properties.

[0027] [Ethylene-vinyl acetate copolymer resin (B)] The ethylene-vinyl acetate copolymer resin (B) is not particularly limited as long as it is a copolymer of ethylene and vinyl acetate. From the viewpoint of bag breakability and solubility, the vinyl acetate content of the ethylene-vinyl acetate copolymer resin (B) is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass. The vinyl acetate content refers to the percentage (by mass) of vinyl acetate contained in the ethylene-vinyl acetate copolymer resin.

[0028] (Method for manufacturing mixed resin film) The method for manufacturing the film used in the melt bag is not particularly limited as long as it can produce a mass of the hot melt adhesive composition targeted by the present invention, but examples include known melt casting methods, T-die methods, inflation methods, and other melt extrusion methods. The thermoplastic film in the embodiment of the present invention may be a single-layer film or a multi-layer film consisting of two or more layers. The surface of the thermoplastic film may be roughened and have irregularities. It is not particularly limited as long as a mass containing the hot-melt adhesive composition targeted by the present invention can be obtained.

[0029] <Hot melt adhesive composition> The hot melt adhesive composition contains a plasticizer (C) from the viewpoint of bag-breaking ability and stringing ability, and has a viscosity of 500 to 2500 mPa·s at 140°C. More preferably, the viscosity of the hot melt adhesive composition is 700 to 1300 mPa·s. The content of plasticizer (C) in 100% by mass of the hot melt adhesive composition is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass. Having the plasticizer (C) content within this range further improves the stringiness of the hot melt adhesive composition and the ability to break the bag when the bulk is stored at high temperatures.

[0030] [Plasticizer (C)] Plasticizers (C) include alcohol-based, fatty acid-based, phthalate-based, adipic acid-based, epoxy-based, polyester-based, phosphoric acid-based, and their derivatives, as well as oils. The purpose of adding plasticizers is to reduce the melt viscosity of hot melt adhesives, impart flexibility, and improve wetting of the adherend.

[0031] Alcohol-based plasticizers are organic compounds with 14 to 50 carbon atoms having at least one hydroxyl group, and their derivatives. Examples of alcohol derivatives include ethers, aldehydes, ketones, fatty acids, esters, amines, and ethoxylated alcohols.

[0032] Fatty acids are aliphatic carboxylic acids that have at least one carboxyl group, and may also have a hydroxyl group. Fatty acids are broadly classified into saturated fatty acids and unsaturated fatty acids. Saturated fatty acids are acids that do not have double or triple bonds in their carbon chain. Unsaturated fatty acids are acids that have double or triple bonds in their carbon chain.

[0033] Examples of saturated fatty acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, tricosylic acid, 12-hydroxystearic acid, and synthetic saturated fatty acids (e.g., Unisid 350, 425, 550, 700: manufactured by NuCera a).

[0034] Examples of unsaturated fatty acids include monounsaturated fatty acids (unsaturated fatty acids containing one double bond) such as myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, and vaccenic acid; diunsaturated fatty acids (unsaturated fatty acids containing two double bonds) such as linoleic acid; triunsaturated fatty acids (unsaturated fatty acids containing three double bonds) such as alpha-linolenic acid, gamma-linolenic acid, pinolenic acid (18 carbon atoms); eleostearic acid and beta-eleostearic acid; tetraunsaturated fatty acids (unsaturated fatty acids containing four double bonds) such as stearidonic acid; and pentaunsaturated fatty acids (unsaturated fatty acids containing five double bonds) such as boseopentaenoic acid.

[0035] Examples of fatty acid derivatives include oils and fats, hydrogenated oils, fatty acid amides, fatty acid alkyl esters, monoglycerides, diglycerides, sorbitan fatty acid esters, diglycerin fatty acid esters, etc. Oils and fats and hydrogenated oils are preferred, and hydrogenated oils are more preferred. Hydrogenated oils are particularly preferred, and examples include hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated castor oil, hydrogenated soybean oil, hydrogenated beef tallow oil, hydrogenated rapeseed rice wax, and slightly hydrogenated horse oil.

[0036] Phthalate plasticizers are plasticizers that have a phthalate skeleton and are generally compounds obtained by the esterification reaction of phthalic acid. They possess a phthalate structure and are usually produced by the reaction of a divalent acid with an alcohol. Representative phthalate plasticizers include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, and diisodecyl phthalate.

[0037] Adipic acid-based plasticizers are plasticizers that have an adipic acid skeleton and are generally compounds obtained by the esterification reaction of adipic acid with an alcohol, such as diethyl adipate, dibutyl adipate, and octyl adipate.

[0038] Epoxy plasticizers are plasticizers having an epoxy skeleton, and are generally compounds obtained by epoxidation reactions, such as glycidyl ethers, bisphenol A diglycidyl ethers, and alkyl epoxy compounds.

[0039] Polyester-based plasticizers are plasticizers having a polyester backbone, and are usually compounds obtained by the esterification reaction of a divalent or polyvalent carboxylic acid with an alcohol. Examples include adipic acid diesters, sebacate acid diesters, trimethyl esters, polybutylene succinates, and polyethylene glycols.

[0040] Phosphate-based plasticizers are plasticizers obtained by the esterification reaction of phosphoric acid, and are usually compounds obtained by the esterification reaction of a divalent or polyvalent carboxylic acid with an alcohol, such as triferric acid, tributyl phosphate, dibutyl phosphate ester, and triisobutyl phosphate.

[0041] Oils are broadly classified into paraffinic process oils, naphthenic process oils, and aromatic process oils.

[0042] Process oils are mixtures of aromatic rings, naphthenic rings, and paraffinic chains. In this application, naphthenic process oils refer to those in which naphthenic ring carbons account for 35 to 46% by mass of the total carbon of the process oil. Furthermore, process oils in which aromatic carbons account for 30% by mass or more of the total carbon are classified as aromatic process oils, and process oils in which paraffinic chain carbons account for 50% by mass or more of the total carbon are classified as paraffinic process oils.

[0043] The plasticizer (C) is preferably composed of at least one selected from fatty acids and their derivatives, in terms of compatibility. Fatty acids and their derivatives may be used in combination with other plasticizers.

[0044] The plasticizer (C) may be liquid at room temperature, but it is preferable to include a plasticizer with a melting point of 35 to 120°C in order to improve the bag-breaking and string-like properties of the lump. It is more preferable to include a plasticizer with a melting point of 40 to 100°C, and even more preferable to include a plasticizer with a melting point of 50 to 95°C. Two or more types of plasticizer (C) may be included. It is preferable to include at least one selected from fatty acids and their derivatives as the plasticizer (C) in order to improve the bag-breaking properties of the lump.

[0045] The hot melt adhesive composition may contain, in addition to the plasticizer (C), thermoplastic elastomers, tackifiers, colorants, antiblocking agents, waxes, inorganic fillers, antioxidants, fillers, flame retardants, antistatic agents, light stabilizers, UV absorbers, heavy metal deactivators, fluorescent whitening agents, and other components.

[0046] (Thermoplastic elastomer) Thermoplastic elastomers are polymer materials that, at room temperature, have properties similar to vulcanized rubber and are elastic, while at high temperatures, they function like ordinary thermoplastic resins, allowing existing molding machines to be used as is. Because thermoplastic elastomers contain both elastic rubber components (soft segments) and molecularly restricting components (hard segments) that prevent plastic deformation, they possess properties intermediate between rubber and plastic. Thermoplastic elastomers generally consist of a polystyrene block and a rubber intermediate block. The polystyrene portion forms physical crosslinks (domains) that act as crosslinking points, while the intermediate rubber block provides the product with rubber elasticity. The intermediate soft segment can be polybutadiene (B), polyisoprene (I), or polyolefin elastomers (ethylene-propylene (EP), ethylene-butylene (EB), or butylene-butadiene (BB)). Depending on the arrangement of these segments with the hard polystyrene (S) segment, they are classified into linear and radial types.

[0047] (Adhesion agent) Examples of tackifiers include phenol resins, modified phenol resins, terpene phenol resins, xylene phenol resins, cyclopentadiene-phenol resins, xylene resins, aliphatic, alicyclic, aromatic petroleum resins, polymerized rosin, hydrogenated aliphatic, alicyclic, aromatic petroleum resins, phenol-modified petroleum resins, rosin ester resins, hydrogenated rosin, acid-modified rosin, hydrogenated rosin ester resins, low molecular weight polystyrene resins, terpene resins, and hydrogenated terpene resins. In particular, tackifiers with an acid value of 100 to 300 mg KOH / g are suitable for alkali-dispersible hot-melt adhesive compositions. Examples include hydrogenated rosin, acid-modified rosin, and polymerized rosin.

[0048] (Coloring agent) The coloring agent can be any conventionally known coloring agent such as red, blue, green, or yellow. The coloring agent can be a pigment, dye, or pigment, and examples include monoazo, disazo, azo lake, benzimidazolon, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and phthalocyanine. Pigment types include pigments, perylene, monoazo, condensed azo, isoindolinone, titanium dioxide, and carbon.

[0049] (Blocking prevention agent) Examples of antiblocking agents include unsaturated fatty acid amides such as silicones, stearate amide, oleate amide, erucate amide, oleamide, and behenate amide.

[0050] (wax) Waxes include natural waxes (animal-based waxes such as beeswax, plant-based waxes such as wood wax and rice bran wax, mineral-based waxes such as ozokerite, and petroleum-based waxes such as paraffin wax and microcrystalline wax) and synthetic waxes (Fischer-Tropsch wax, polyethylene wax, polypropylene, and modified waxes such as acids).

[0051] (Inorganic filler) Inorganic fillers include metals, metal oxides, and metal hydroxides in particulate and fibrous forms. Specifically, these include glass fibers, carbon fibers, calcium silicate, calcium titanate, aluminum borate fibers, flake glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, monocalcium phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium dioxide, silicon dioxide, magnesium oxide, calcium silicate, sodium alumina silicate, magnesium silicate, carbon nanotubes, graphite, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, and apatite.

[0052] (Antioxidant) Examples of antioxidants include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl]propionate, tris(2,4-di-t-butylphenyl)phosphite, and bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite. These antioxidants may be used alone or in combination of two or more.

[0053] (Filler) Examples of fillers include wet silica, aluminum hydroxide, aluminum oxide, magnesium oxide, montmorillonite, mica, smectite, organic montmorillonite, organic mica, and organic smectite.

[0054] (Flame retardant) Examples of flame retardants include phosphorus-containing compound flame retardants, halogen-containing compound flame retardants, sulfonic acid metal salt flame retardants, and silicon-containing compound flame retardants.

[0055] (Antistatic agent) Examples of antistatic agents include fatty acid esters of alkylamine ethylene oxide adducts, anionic surfactants (e.g., alkylbenzene sulfonates, higher alcohol sulfate salts, etc.), cationic surfactants (e.g., aliphatic amine salts, quaternary ammonium salts, etc.), and amphoteric surfactants (e.g., imidazoline type, betaine type, etc.).

[0056] (Light stabilizer) Examples of light stabilizers include hindered amine compounds and benzoate compounds.

[0057] (UV absorber) Examples of the aforementioned ultraviolet absorbers include benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers.

[0058] (Heavy metal deactivator) Examples of heavy metal deactivators include salicylic acid derivatives, hydrazide derivatives, and oxalamide derivatives.

[0059] (Fluorescent whitening agent) Examples of fluorescent whitening agents include stilbene-based, coumarin-based, oxazole-based, and naphthalimide-based agents.

[0060] <Method for producing hot melt adhesive composition> The method of manufacturing a hot melt adhesive composition is not particularly limited, as long as a hot melt adhesive composition can be obtained. An example of a manufacturing method is given below. A melting vessel equipped with a stirrer is heated to about 150°C, a plasticizer (C) is heated and melted, a thermoplastic elastomer is mixed and dispersed in the melted plasticizer, a tackifier is added, and the mixture is further mixed to produce the composition.

[0061] <Bulky form> The present invention provides a mass containing the hot-melt adhesive composition within a molten bag. The mass of the mass is preferably between 10g and 5000g. A mass within this range is preferable because it is easy to handle and offers excellent workability in terms of the number of filling cycles. The film thickness of the molten bag can be appropriately adjusted according to the mass.

[0062] The hot-melt adhesive composition enclosed in the melt bag may be an alkali-dispersed hot-melt adhesive composition. PET bottles filled with soft drinks, seasonings, etc., and bottles filled with beer, sake, etc., are recycled or reused. Typically, during the recycling or reuse process, there is a step to remove labels attached to PET bottles and bottles, which is generally done with a 1.5-4% by mass sodium hydroxide aqueous solution at about 85-95°C. Therefore, alkali-dispersed hot-melt adhesive compositions are used for label applications. The present invention is suitable as a bulk body in which such an alkali-dispersed hot-melt adhesive composition is packaged. As a tackifier used in an alkali-dispersible hot-melt adhesive composition, it is preferable to include a tackifier with an acid value of 100 to 300 mg KOH / g from the viewpoint of alkali dispersibility of the hot-melt adhesive composition. Rosin-based tackifiers are one example. The acid value is the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 g of the sample, and is a value measured in accordance with JIS K5601-2-1 Acid Value (Titration Method).

[0063] (Method for manufacturing a mass) In the present invention, the method for producing a mass containing the hot melt adhesive composition is not particularly limited as long as a mass containing the hot melt adhesive composition for which the present invention is aimed can be obtained. For example, the following methods can be cited. A hot-melt adhesive composition is left at room temperature to solidify in a molten state to produce a block of the hot-melt adhesive composition. The block of the hot-melt adhesive composition is then packaged in a mixed resin film (molten bag) to produce a mass. Alternatively, a block of the hot-melt adhesive composition may be manufactured by pouring a heat-melted hot-melt adhesive composition onto a mixed resin film and allowing it to solidify, while simultaneously packaging the block of the hot-melt adhesive composition in the mixed resin film (molten bag).

[0064] ≪Container≫ In this invention, the term "container" refers to a container made of a solid material to which a label is attached. The material of the container may be glass, plastic, paper, etc., but is not particularly limited. Furthermore, its shape may be round or non-round, such as square. The material of the container is preferably PET or glass, and more preferably PET.

[0065] In the case of PET bottles, labels are used not only by attaching them to a portion of the bottle's body, but also as roll labels that wrap around the entire circumference of the bottle. OPP film is frequently used for such roll labels. The labels of the present invention, whether printed on the back or not, can be adhered equally well. In the present invention, the lump is coated onto a portion of the back of the label. Coating methods include the open-wheel method, the closed-gun method, and the direct-coat method. The open-wheel method and the direct-coat method are preferred as they do not leave any adhesive residue on the PET bottle when peeled off.

[0066] The aggregate of the present invention can be used in the manufacture of sanitary materials, disposable medical drapes, paper, tapes and labels, furniture, textiles, footwear, woodworking, or construction, for example, in roofing membranes or other building laminates. [Examples]

[0067] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention This is not limited to the following embodiments. In the examples, unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "percentage by mass".

[0068] [Method for measuring the acid value of tackifiers] The acid value was measured in accordance with JIS K5601-2-1 Acid Value (Titration Method). Specifically, 1 g of the sample was accurately weighed and placed in a 250 ml flask. 50 ml of ethanol or an equal volume mixture of ethanol and ether was added, and the sample was dissolved by heating. The sample was then titrated with 0.1 N potassium hydroxide solution while occasionally shaking (indicator: phenolphthalein). The titration endpoint was defined as the point at which the pale pink color of the solution persisted for 30 seconds. A blank test was then performed using the same method to correct for the result, and the acid value was determined from the following formula. Acid value = [Amount of 0.1N potassium hydroxide solution consumed (ml) × 5.611] / [Amount of sample (g)]

[0069] [Method for measuring the melting point of plasticizer (C)] The melting point of the plasticizer (C) was measured using a differential scanning calorimetry system (Shimadzu Automatic Differential Calorimeter DSC-60A Plus). Approximately 5 mg of sample was taken, cooled to 0°C, then heated to 170°C at a heating rate of 10°C / min, and then cooled to 0°C at a cooling rate of -20°C / min. After holding at 0°C for 1 minute, heating was repeated at a heating rate of 10°C / min, and the amount of heat exothermic and endothermic heat when heated to 170°C was measured. The melting peak at which the plasticizer dissolved was defined as the melting point.

[0070] [Method for measuring the viscosity of hot melt adhesive] The viscosity of the hot melt adhesive was determined in accordance with JIS K6862 (Method A). 300 g of the hot melt adhesive composition, pre-melted to approximately 150°C, was placed in a test container and stirred thoroughly with a rod thermometer in air. When the temperature reached 140°C, the viscosity was measured using a Type B thermometer (TOKIMEC VISCOMETER MODEL: BM, manufactured by Toki Sangyo Co., Ltd.). A suitable rotor was used as needed.

[0071] The materials listed in Table 1 are explained below.

[0072] [Low-density polyethylene resin (A)] Petrocene 205: Manufactured by Tosoh Corporation, Density: 924 kg / m³ 3 , MFR:3g / 10min Petrosen 230: manufactured by Tosoh Corporation, density: 925 kg / m 3 , MFR: 8 g / 10 min Petrosen 208: manufactured by Tosoh Corporation, density: 924 kg / m 3 , MFR: 23 g / 10 min Petrosen 1384R: manufactured by Tosoh Corporation, density: 928 kg / m 3 , MFR: 7.6 g / 10 min Petrosen 173: manufactured by Tosoh Corporation, density: 924 kg / m 3 , MFR: 0.3 g / lo min Petrosen 209: manufactured by Tosoh Corporation, density: 924 kg / m 3 , MFR: 45 g / 10 min

[0073] [Other low-density polyethylene resins] Novatec LD LC720: manufactured by Japan Polyethylene Corporation, density: 922 kg / m 3 , MFR: 9.4 g / 10 min

[0074] [Ethylene-vinyl acetate copolymer resin (B)] Ultra-Sen 526: manufactured by Tosoh Corporation, vinyl acetate content: 7% by mass Ultra-Sen 633: manufactured by Tosoh Corporation, vinyl acetate content: 20% by mass Ultra-Sen 710: manufactured by Tosoh Corporation, vinyl acetate content: 28% by mass Ultra-Sen 750: manufactured by Tosoh Corporation, vinyl acetate content: 32% by mass Ultra-Sen 625: manufactured by Tosoh Corporation, vinyl acetate content: 15% by mass

[0075] [Manufacture of mixed resin for melting bag]<OO00320>(Production Example F-1) Low-density polyethylene: 80 parts of Petrosen 205 and ethylene-vinyl acetate copolymer resin: 20 parts of Ultra-Sen 710 were pre-blended, put into the hopper of an extruder, and supplied to the extruder using a screw feeder to obtain a mixed resin of low-density polyethylene resin and ethylene-vinyl acetate copolymer resin.

[0076] (Production Examples F-2 to F-12 and F'-1) Mixed resins for molten bags for production examples F-2 to F-12 and F'-1 were produced in the same manner as production example F-1, using the mixing ratios shown in Table 1.

[0077] (Manufacturing example F'-2) Low-density polyethylene: Petrocene 208 was placed in the hopper of an extruder, and supplied to the extruder using a screw feeder to obtain low-density polyethylene resin.

[0078] [Table 1]

[0079] The materials listed in Tables 2 and 3 are explained below.

[0080] [Thermoplastic elastomer] G1650: Kraton G1650, manufactured by Kraton Polymers, SEBS G1643: Kraton G1643, manufactured by Kraton Polymers, SEBS G1652: Kraton G1652, manufactured by Kraton Polymers, SEBS G1726: Kraton G1726, manufactured by Kraton Polymers, SEBS D1118: Kraton D1118, manufactured by Kraton Polymers, SBS

[0081] [Tackifier] RHR-301 (manufactured by China Wuzhou Sun Shine Forestry & Chemicals Co., LTD of Guangxi) Hydrogenated rosin, acid value: 170mgKOH / g KE-604B: Pine Crystal KE-604B (manufactured by Arakawa Chemical Co., Ltd.) Acrylic-modified rosin, Acid value: 230 mg KOH / g Alcon M-90 (manufactured by Arakawa Chemical Co., Ltd.) Hydrogenated petroleum resin, Acid value: None

[0082] [Plasticizer (C)] Stearic acid (powder): Manufactured by Junsei Chemical Co., Ltd., Melting point: 70℃ Lauric acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Melting point: 44℃ Slightly Hydrogenated Horse Oil (Horse Oil): Manufactured by Yamakei Sangyo Co., Ltd., Melting point: 32-36℃ Beef tallow hardened oil: Manufactured by Yamakei Sangyo Co., Ltd. (Product name: Beef tallow hardened oil), Melting point: 61℃ Hydrogenated rapeseed oil: Manufactured by Yokozeki Oil & Fat Industry Co., Ltd. (Product name: Highly Hydrogenated Rapeseed Oil), Melting point: 68℃ Hydrogenated castor oil: Manufactured by Yamakei Sangyo Co., Ltd., Melting point: 86℃ N90: N-90 (manufactured by Idemitsu Kosan Co., Ltd.), naphthenic process oil, liquid at room temperature, therefore no melting point. PW-90: Diana Process Oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.), paraffin-based process oil, liquid at room temperature, therefore no melting point. PW-380: Diana Process Oil PW-380 (manufactured by Idemitsu Kosan Co., Ltd.), paraffin-based process oil, liquid at room temperature, therefore no melting point. UniCid 350: Manufactured by NuCera, fatty acid, melting point: 92°C UniCid 550: Manufactured by NuCera, fatty acid, melting point: 102℃ UniCid 700: Manufactured by NuCera, fatty acid, melting point: 110°C Unilyn 425: Manufactured by NuCera, a higher alcohol with an average of 30 carbon atoms, melting point: 91°C Unitox 490: Manufactured by NuCera, ethoxylated alcohol, melting point: 71°C Unitox 750: Manufactured by NuCera, ethoxylated alcohol, melting point: 106°C

[0083] [Antioxidant] IRG1010: Irganox 1010, manufactured by BASF, pentaerythritol-tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]

[0084] <Manufacturing of hot melt adhesive compositions> (Manufacturing method HM-1) The hot melt adhesive composition was prepared by the following method: 20 parts of a plasticizer (castor hydrogenated oil), 18 parts of a thermoplastic elastomer (G1652), 62 parts of a tackifier (RHR-301), and 0.5 parts of an antioxidant (IRG1010) were added to a stainless steel beaker equipped with a stirrer. The contents were carefully heated to a temperature of 130-150°C. While maintaining the temperature of 130-150°C for approximately 1 hour, the mixture was stirred until the plasticizer and tackifier dissolved, and then completely melted into a homogeneous mixture. The mixture was then cooled to produce the hot melt adhesive composition.

[0085] (Manufacturing methods HM-2~18 and HM'-2) Production examples HM-2 to HM-18 and HM'-2 were manufactured in the same manner as production example HM-1, using the mixing ratios shown in Tables 2 and 3.

[0086] (Manufacturing method HM'-1) Hot melt adhesive composition HM'-1 was manufactured by the following method: 40 parts of thermoplastic elastomer: D1118, 60 parts of tackifier: Alcon M-90, and 0.5 parts of antioxidant: IRG1010 were placed in a stainless steel beaker equipped with a stirrer, and the contents were carefully heated to 130-150°C. While maintaining the temperature of 130-150°C for about 1 hour, the mixture was stirred until the plasticizer and tackifier dissolved, and then completely melted into a homogeneous mixture. The mixture was then cooled to produce hot melt adhesive composition HM'-1.

[0087] [Table 2]

[0088] [Table 3]

[0089] [Example 1] The mixed resin (F-1) was extruded using an extruder (a co-rotating twin-screw extruder PMT32-40.5 manufactured by IKG Corporation) under the conditions of screw rotation speed: 50 rpm and supply speed: 5 kg / hr, and a mixed resin film with a thickness of 80 μm was obtained on the release layer (silene treatment) of PET using a T-die. The obtained mixed resin film was cut to 15 cm x 30 cm, folded to enclose 500 g of hot melt adhesive composition (HM-1), and the three open sides were heat-sealed to obtain the lump (X) of Example 1.

[0090] [Examples 2-22, Comparative Examples 1-4] Using the mixing ratios shown in Tables 4 to 6, the aggregates (X) of Examples 2 to 22 and the aggregates (X') of Comparative Examples 1 to 4 were produced in the same manner as in Example 1.

[0091] (Bag breakability) Forty pieces of lump (X) and lump (X') were placed in a cardboard box measuring 50cm (length) x 38cm (width) x 30cm (height), and left in a 40°C oven for 24 hours. The state of the molten bags was visually inspected and evaluated. ◎, ○, and △ were considered pass, and × was considered fail. [Evaluation Criteria] ◎: No rupture of the melted bag. Excellent. ○: There are ruptures in the molten bags, but the lumps are not adhered to each other. Good. △: The melting bag is torn, and the lumps are stuck together, but they can be easily separated. No practical problems. ×: The melting bag is torn, and the lumps are stuck together and cannot be separated. Unusable.

[0092] (Solubility) For HM-1 to HM-18 and HM'-1 and HM'-2, white hot-melt adhesive compositions were prepared by adding 1% by mass of titanium dioxide to the total mass of the hot-melt adhesive composition. The resulting mixed resin film was cut to 15 cm x 30 cm, folded to enclose 500 g of the white hot-melt adhesive composition, and the three open sides were heat-sealed to obtain a mass (Y) containing the white hot-melt adhesive composition. The mass (Y) was placed in a beaker, heated to 150°C, and then stirred for 1 minute at a stirring speed of 500 rpm using a stirring blade (IKA Japan, stirring blade R1381). After that, the molten material was dropped onto black paper and the color unevenness was visually evaluated. ◎, ○, and △ were considered pass, and × was considered fail. [Evaluation Criteria] ◎: No uneven coloring, excellent quality. ○: Some uneven coloring is visible, but overall good. △: Although there is some overall color unevenness, there is no unmelted residue in the molten bag, and there are no practical problems. ×: Color inconsistencies are visible throughout, and the melted bag remains; unusable.

[0093] (Stringy) The solid material was placed in the melting tank of a hot melt gun and heated to 150°C. Intermittent coating was then performed 600 times horizontally on a substrate 30 cm away from the tip of the hot melt gun. The mass of the falling material between the hot melt gun and the substrate was measured to evaluate stringing properties. The test conditions were as follows, and the test was performed three times, with the average value being examined. Discharge temperature: 140℃ Discharge amount: 0.2g / time Discharge time: 0.2 seconds Discharge interval: 0.2 seconds ◎, ○, and △ are considered passing grades, while × is considered a failing grade. [Evaluation Criteria] ◎: Less than 200mg, excellent. ○: More than 200mg but less than 500mg is good. △: More than 500mg but less than 1g; no practical problems. ×: If the amount exceeds 1g, or if the dissolved lumps clog the nozzle, it cannot be applied. Not practical.

[0094] [Table 4]

[0095] [Table 5]

[0096] [Table 6]

[0097] Tables 4 and 5 show that the mass X containing a hot-melt adhesive in a molten bag made of a mixed resin film exhibits excellent solubility and bag-breaking properties, as well as good stringing properties during labeling. On the other hand, the comparative mass X' in Table 6 failed to satisfy any of the following criteria: solubility, bag-breaking properties, or good stringing properties during labeling.

Claims

1. A mass containing a hot melt adhesive composition in a molten bag, The molten bag has a density of 923-930 kg / m³. ３ It consists of a mixed resin film containing low-density polyethylene resin (A) and ethylene-vinyl acetate copolymer resin (B), A hot melt adhesive composition in the form of a lump containing a plasticizer (C) and having a viscosity of 500 to 2500 mPa·s at 140°C.

2. The mass according to claim 1, characterized in that the plasticizer (C) contains a plasticizer having a melting point of 35 to 120°C.

3. The mass according to claim 1, wherein the content of ethylene-vinyl acetate copolymer resin (B) in 100% by mass of the mixed resin film is 10 to 50% by mass.

4. The aggregate according to claim 1, wherein the vinyl acetate content of the ethylene-vinyl acetate copolymer resin (B) is 5 to 30% by mass.

5. Low-density polyethylene resin (A) at 190°C, 2.16 kgf / cm² ２ The aggregate according to claim 1, characterized in that the melt mass flow rate is 1 to 25 g / 10 min.

6. The mass according to claim 1, characterized in that the film thickness of the molten bag is 10 to 500 μm.

7. The aggregate according to claim 1, characterized in that the plasticizer (C) contains at least one selected from fatty acids and their derivatives.

8. The lump according to claim 1, characterized in that the hot melt adhesive composition is an alkali-dispersed hot melt adhesive composition.

9. A container to which a label is attached using the mass described in any one of claims 1 to 8.

10. The container according to claim 9, characterized in that the material of the container is polyethylene terephthalate or glass.

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