JP2012041075A - Vessel with roll shrink label and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a roll shrink label for tearing off an adhesive material by hand without leaving paste, and easily tearing off the adhesive material from a base body by a heat alkaline aqueous solution without leaving the paste.SOLUTION: The vessel with the roll shrink label includes: the vessel; the roll shrink label wound on the outer periphery of the vessel; a first pressure sensitive adhesive layer formed on one end of the label, fixing the label and the vessel and made of a first hot melt pressure sensitive adhesive dispersing or dissolving in an 1.5 wt.% NaOH aqueous solution at 90°C; and a second pressure sensitive adhesive layer formed on the other end of the label, fixing the mutual labels and made of a second hot melt pressure sensitive adhesive undispersed or undissolved in the 1.5 wt.% NaOH aqueous solution at 90°C.

Description

  The present invention relates to a container with a roll shrink label and a method for producing the same. In particular, the present invention relates to glass bottles and PET (polyethylene terephthalate) bottles used in soft drinks, seasonings, detergents, shampoos, edible oils, cosmetics, pharmaceuticals, and the like with roll shrink labels.

  In recent years, the amount of PET bottles used for beverages has increased along with the amount of PET bottles produced. The used PET bottles are discharged as garbage, but a recycling system has been established by the Recycled Resource Utilization Promotion Law so that the amount of the garbage is not increased as much as possible and can be recycled as resources. In recycling PET bottles, the PET bottles collected after use are cut into 8mm square pellets, soaked in hot alkali (85-90 ° C 1.5% NaOH) aqueous solution for about 15 minutes, peeled off the label, washed with water and dried -Labels are removed by wind selection and PET pellets are recycled.

For this reason, PET bottle labels include stretch labels, shrink labels, roll labels using alkali-dispersed hot-melt adhesives (Patent Documents 1 and 2), and the like. Stretch labels use the principle of rubber bands that return to their original state when stretched and released. In other words, the body-shaped label is stretched and placed on the PET bottle to release it, and the label is returned to its original position and wrapped for use. However, stretch labels cannot be used for uneven PET bottles (atypical bottles) that have a small restoring force of the labels and emphasize design. The shrink label covers a PET bottle while cutting a cylindrical label with a labeler, and shrinks it with the heat of a heater or steam, thereby closely attaching the film to the container. However, this method has a problem in that the cost is high because the label needs to be processed into a cylindrical shape in advance. Moreover, in order to make it easy to cover a cylindrical label on a bottle, a certain amount of label thickness is required, and there is a problem of cost. Furthermore, when the temperature is 30 ° C. or higher, the shrink label is shrunk and wrinkles are generated and cannot be covered well, and it is necessary to adjust the humidity of the label. On the other hand, a roll label using an alkali-dispersed hot melt pressure-sensitive adhesive has a problem that it cannot be used for uneven PET bottles (atypical bottles) that emphasize design.

  Patent Document 3 proposes to use a UV (Ultraviolet) curable hot melt adhesive / or UV adhesive for the roll shrink label, but it is difficult to control the UV irradiation amount of the UV curable adhesive, It did not conform to the voluntary regulations of the PET bottle recycling promotion council because it was not dispersed in alkali. In addition, problems such as a more complicated structure of the labeler and an increase in the price of the labeler have occurred. Furthermore, UV curable hot-melt adhesives are irritating to the skin and attach to the skin of the worker, or because of hot melt, if the heated steam adheres to the skin, the sensitive person causes an allergic reaction. There was a problem with safety.

JP 2005-220244 A Japanese Patent No. 4278704 JP 2008-145498 A

An object of the present invention is to provide a container with a roll shrink label in which there is no redeposition of the label or hot melt adhesive to the PET bottle after the label is peeled off.
Furthermore, an object of the present invention is to provide a roll shrink label excellent in recyclability, which can peel off the adhesive without leaving adhesive residue, and can easily peel off the adhesive from the substrate with a hot alkaline aqueous solution without adhesive residue. Is to provide.

  In order to recycle PET bottles, the PET Bottle Recycling Promotion Council has been working with related organizations and ministries to develop various laws and guidelines for PET bottles. For PET bottle labels, we have created “independent design guidelines for designated PET bottles” and are self-regulating. In this voluntary regulation, either a stretch label or shrink label, or a film or paper label such as an OPP (stretched polypropylene) film, PE (polyethylene) film, or PET film, and either hot water peeling or hot alkali peeling The label had to be peeled off.

  The method for peeling the label from the PET bottle is based on the “designated PET bottle self-regulation guidelines” issued by the PET Bottle Recycling Promotion Council. That is, in the hot alkali peeling test, a pellet made by cutting a bottle with a label, printing, etc., was immersed in a 1.5% NaOH aqueous solution at 90 ° C. at a pellet concentration of 10% (weight ratio) and slowly slowed for 15 minutes. Stir. Subsequently, it filters with a filter and visually observes a pellet. When the label peels off and printing ink, adhesive, etc. do not remain in the bottle, it is judged that there is a hot alkali peelability.

  The present invention is a hot melt pressure-sensitive adhesive for PET bottle paper and OPP trunk-wrap labels suitable for “independent design guidelines for designated PET bottles” issued by the PET Bottle Recycling Promotion Council, such as soft drinks and seasonings. The label does not peel off even if it is placed in water when cooling it in use, but if the bottle is pelletized after being collected and immersed in a hot alkaline aqueous solution, the label is easily peeled off from the PET bottle and does not adhere to the PET bottle again. The present invention provides a roll shrink label that can also be used for uneven PET bottles (atypical bottles).

  Moreover, this invention provides the container which adhere | attached the roll-wrap label using the roll shrink label which has the said characteristic further.

The present invention relates to the following contents.
[1] Container; Roll shrink label wound around the outer periphery of the container; Dispersed or dissolved in a 1.5 wt% NaOH aqueous solution at 90 ° C. that is formed at one end of the label and fixes the label and the container A first adhesive layer made of a first hot-melt adhesive; and a second non-dispersed and dissolved in a 1.5 wt% NaOH aqueous solution at 90 ° C. that is formed on the other end of the label and fixes the labels to each other A container with a roll shrink label, comprising a second adhesive layer made of a hot melt adhesive.
[2] The container with a roll shrink label according to [1], wherein the first hot melt pressure-sensitive adhesive has a viscosity measured by a rheometer at 100 ° C. of 20,000 mPa · s or less.
[3] The second hot-melt pressure-sensitive adhesive has a viscosity measured with a rheometer at 100 ° C. of 20,000 mPa · s or less and a viscosity measured with a rheometer at 90 ° C. of 30,000 mPa · s or more. ] The container with a roll shrink label as described in].
[4] The container with a roll shrink label according to [1], wherein the roll shrink label is a MD direction uniaxially stretched film.
[5] A first pressure-sensitive adhesive layer made of a first pressure-sensitive adhesive dispersed or dissolved in a hot alkaline aqueous solution is formed at one end of the roll shrink label, and a second pressure-sensitive adhesive not dispersed and dissolved in the hot alkaline aqueous solution is formed at the other end. A step of forming a second pressure-sensitive adhesive layer; a step of winding the label obtained in the previous step around a container, fixing the label and the container with the first pressure-sensitive adhesive layer, and fixing the labels with the second pressure-sensitive adhesive layer And a method for producing a container with a roll shrink label, comprising the step of shrinking the label by heating.
[6] A label for roll shrink which is a uniaxially stretched film in the MD direction.
[7] A hot-melt pressure-sensitive adhesive for roll shrink labels that does not disperse and dissolve in a 1.5 wt% NaOH aqueous solution at 90 ° C.
[8] A roll shrink label; a first adhesive layer formed on one end of the label and made of a first adhesive dispersed or dissolved by a hot alkaline aqueous solution; and formed on the other end of the label, A roll shrink label with an adhesive layer comprising a second adhesive layer made of a second adhesive that does not disperse and dissolve.

According to the present invention, after the roll shrink label is peeled off, it does not reattach to the container.
In addition, the roll shrink label of the present invention can be used for uneven (atypical) bottles, and the label does not peel off when the container is used. By simply stirring in a 1.5% NaOH aqueous solution at 15 ° C. for 15 minutes, the label peels off from the PET bottle, and the label or hot melt adhesive does not reattach to the PET bottle.

Furthermore, the roll-shrink label of the present invention is a requirement to peel off the label with hot alkaline water in the “Self-regulation Guidelines for Designated PET Bottles” issued by the PET Bottle Recycling Promotion Council, and to be able to peel off without adhesive residue by manual peeling. Since it satisfy | fills, it can utilize preferably as a label for PET bottles.
Furthermore, when the roll shrink label is peeled off from the PET bottle, the alkali-dispersed hot melt adhesive does not remain in the PET bottle.

  Hereinafter, the roll shrink label of the present invention will be described in more detail.

  The container with a shrink label of the present invention is a container; a roll shrink label wound around the outer periphery of the container; 1.5 wt% NaOH at 90 ° C. formed at one end of the label and fixing the label and the container A first adhesive layer comprising a first hot melt adhesive that is dispersed or dissolved in an aqueous solution; and dispersed in a 1.5 wt% NaOH aqueous solution at 90 ° C. that is formed on the other end of the label and fixes the labels together. And a second adhesive layer made of a second hot melt adhesive that does not dissolve.

  Said roll shrink label is formed from a base film. Examples of the base film include a stretched polyester film, a stretched polystyrene film, a stretched polyolefin film, a polylactic acid film, a foamed polyolefin film, a stretched polyester-polystyrene coextruded film, and a foamed polystyrene film. Or the laminated film of a nonwoven fabric and the said film may be sufficient. The stretched film may be uniaxially stretched or biaxially stretched, and in the case of a uniaxially stretched film, it may be longitudinally uniaxially stretched or laterally uniaxially stretched. However, the shrink uniaxially stretched film is suitable for the shrink label in which the shrink label is formed in a cylindrical shape and attached to the container and then subjected to heat shrinkage treatment, whereas the roll shrink label of the present invention is used as the shrink label. Even if it is a case, it is not limited to a laterally uniaxially stretched film, Any of laterally uniaxially stretched, longitudinally uniaxially stretched, and a biaxially stretched film can be used conveniently.

It is preferable that the thermal contraction rate of the base film with respect to the stretching direction is 5 to 85% so that the label of the present invention has an effect as a roll shrink label. In addition, the heat shrinkage rate in this invention is a heat shrinkage rate by 100 degreeC hot water, Comprising: The heat shrinkage rate of an extending | stretching direction shall follow a following formula. Therefore, in the case of a longitudinally uniaxially stretched film, since the shrinking direction is the film flow direction, the thermal shrinkage rate in the flow direction is 5 to 85%, and in the case of a laterally uniaxially stretched film, the film shrinks in the film width direction. The heat shrinkage ratio in the film width direction is 5 to 85%. In the case of a biaxially stretched film, the thermal shrinkage rate is preferably within the above range with respect to any stretching method.
Thermal contraction rate (%) = (dimension before heating−dimension after heating) / (dimension before heating) × 100
The thickness of the base film layer is not particularly limited, but is appropriately selected within a range not impairing heat resistance, rigidity, mechanical suitability, appearance, etc., preferably about 5 to 250 μm, and more preferably 10 to 50 μm. The roll shrink label can be used even if the label is thin. Therefore, in consideration of economy, the roll shrink label is particularly preferably 10 to 50 μm.

    Furthermore, various additives such as a lubricant, a filler, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, and a colorant are added to the base film as necessary. Also good. Further, the surface of the base film layer may be subjected to conventional surface treatment such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc. in order to improve printability.

    The base film is not limited to a single layer of the film, and may be a laminated film of two or more types of films. Further, a vapor deposition film of silicon oxide, aluminum oxide, aluminum, or the like is provided on these films. It may be provided. As thickness of a laminated film, what is formed in about 10-300 micrometers is preferable.

  The container of the present invention includes glass containers such as glass bottles used for soft drinks, seasonings, detergents, shampoos, edible oils, cosmetics and pharmaceuticals, and plastic containers and paper containers such as PET (polyethylene terephthalate) bottles. Etc. The label of the present invention is preferably used for PET bottle containers from the viewpoint of bottle recycling, but can also be used for other plastic containers, glass containers, and paper.

Moreover, the 1st hot-melt adhesive in this invention will not be specifically limited if it disperse | distributes or melt | dissolves in 1.5 weight% NaOH aqueous solution of 90 degreeC.
Specifically, the first hot-melt pressure-sensitive adhesive preferably has a viscosity of 20,000 mPa · s or less measured with a rheometer at 100 ° C. Within this viscosity range, the first hot melt adhesive is dispersed or dissolved in the NaOH aqueous solution.
More specifically, the first hot-melt pressure-sensitive adhesive preferably contains a thermoplastic elastomer (A) and a rosin-based tackifier (B) having an acid value of 100 mgKOH / g to 300 mgKOH / g, Terpene phenol resin (C), synthetic oil (D), polypropylene wax (E), wax (F) having a penetration of 10 ° C. or less at 25 ° C., polyethylene glycol (G) having a number average molecular weight of 1,000 or more And a component selected from polybutene (H).
It is desirable that the pressure-sensitive adhesive does not remain on the container side when the roll shrink label is peeled by hand. Therefore, as a preferred embodiment, the alkali-dispersed hot-melt pressure-sensitive adhesive is a thermoplastic elastomer (A), and the acid value is 100 mgKOH / g. The rosin-based tackifier (B), the terpene phenol resin (C), the synthetic oil (D), and the polypropylene wax (E) obtained by graft polymerization of maleic anhydride, which are 300 mgKOH / g or less, may be included.
Alternatively, as another preferred embodiment, the thermoplastic elastomer (A), the rosin-based tackifier (B) having an acid value of 100 mgKOH / g to 300 mgKOH / g, the synthetic oil (D), and the penetration at 25 ° C. Wax (F) which is 10 dmm or less and polyethylene glycol (G) having a number average molecular weight of 1,000 or more may be included.
Alternatively, as another preferred embodiment, the alkali-dispersed hot-melt pressure-sensitive adhesive is a thermoplastic elastomer (A), a rosin-based tackifier (B) having an acid value of 100 mgKOH / g to 300 mgKOH / g, and a synthetic oil (D ) Or / and polybutene (H) and wax (F) having a penetration at 25 ° C. of 10 dmm or less.

  Examples of the thermoplastic elastomer (A) include styrenic polymers. The styrenic thermoplastic elastomer generally has a polystyrene block and a rubber intermediate block, and the polystyrene portion forms a physical crosslink (domain) to become a bridging point, and the intermediate rubber block gives rubber elasticity to the product. The intermediate soft segment includes polybutadiene (B), polyisoprene (I), and polyolefin elastomer (ethylene propylene, EB). Depending on the arrangement of the hard segment with polystyrene (S), linear (linear type) And radial (radical type). Among the preferable styrene elastomers described above, in the present invention, a styrene / butadiene block copolymer (SB, diblock), (SBSS, triblock, styrene / isoprene block copolymer (SI) are used. , Diblock), (S-I-S, triblock), and styrene / butadiene-isoprene block copolymers (SB-I, diblock), (SB / IB, triblock) and Hydrogenated products of these block copolymers, for example, hydrogenated products of styrene / butadiene / styrene block copolymers (SBS), hydrogenated products of styrene / isoprene / styrene block copolymers (SEPS), and carboxylic acids Modified styrenic elastomers as described above, and in addition to styrene in the styrene block, styrene and α-methylstyrene, etc. A copolymer of an aromatic vinyl compound is also exemplified, and a styrene-ethylene / butylene-styrene block polymer (SEBS) is more preferable from the viewpoint of thermal stability (difficult to thermally decompose).

  The rosin tackifier (B) having an acid value of 100 mgKOH / g or more and 300 mgKOH / g or less is not particularly limited, but is preferably a rosin tackifier having a acid value of 170 mgKOH / g or more and 250 mgKOH / g or less. Rosin is an amber, amorphous natural resin obtained from pine, and can be divided into gum rosin, wood rosin and tall oil rosin depending on the production. The main component is a mixture of abietic acid having three ring structures, a conjugated double bond, and a carboxyl group and its isomer, and has a bulky structure rich in reactivity. Due to its high reactivity, thermal stability is poor, and rosin is generally hydrogenated to improve stability. Examples of the rosin-based tackifier having an acid value of 100 mgKOH / g or more and 300 mgKOH / g or less include raw rosin having the acid value (unmodified rosin), hydrogenated rosin, (meth) acrylic acid modified rosin, water Examples thereof include a (meth) acrylic acid modified rosin, a maleic acid modified rosin, a hydrogenated maleic acid modified rosin, a fumaric acid modified rosin, and a hydrogenated fumaric acid modified rosin. From the viewpoint of compatibility with the thermoplastic elastomer, preferably a hydrogenated rosin or a (hydrogenated) acrylic acid modified rosin or the like, more preferably the acid-modified and / or hydrogenated one, more preferably Is a hydrogenated rosin tackifier. When the acid value is 100 mgKOH / g or more, the alkali dispersibility is excellent. On the other hand, when the acid value is 300 mgKOH / g or less, the viscosity of the hot melt composition is suppressed and the softening point does not become too high.

  The terpene phenol resin (C) is obtained by copolymerizing a cyclic terpene monomer and phenols, for example, in the presence of a Friedel-Crafts type catalyst in an organic solvent. In the present invention, a hydrogenated terpene phenol resin obtained by hydrogenating the obtained terpene phenol resin may be used. The terpene monomer may be a monocyclic terpene monomer or a bicyclic terpene monomer. Examples of these terpene monomers include pinene, limonene, isolimonene, camphene, terpinene, terpinolene, ferrandlene, bornylene, and mixtures thereof, α-pinene, β-pinene-based gum turpentine oil, pine oil, and d-limonene-based. And cyclic monoterpenes such as dipentene. Examples of the phenols include alkyl-substituted phenols such as phenol, cresol, xylenol, t-butylphenol, octylphenol, nonylphenol, and phenylphenol, and alkoxy-substituted phenols such as methoxyphenol, polyphenols such as catechol, resorcinol, hydroquinone, and pyrogallol. Examples thereof include halogenated phenols such as chlorophenol and bromophenol, naphthol, dioxynaphthalene, bisphenol A and the like. From the viewpoint of adhesive strength, preferred phenols include terpene phenol and cresol. The terpene phenol resin is easily available because various grades are commercially available from Yasuhara Chemical Co., Ltd. under the trade names “YS Polyster” and “Mighty Ace”. In addition, Arakawa Chemical Industry Co., Ltd. is also available under the trade name “Tamanor”. From the viewpoint of low-temperature tackiness and high-temperature adhesiveness, those having a softening point of 20 to 160 ° C are preferred.

  Synthetic oil (D) is an oil generally used as a plasticizer such as rubber and thermoplastic elastomer, a process oil produced in so-called petroleum refining and the like, paraffinic process oil, naphthenic process oil, aromatic It is broadly classified as a family process oil. Process oil is a mixture of aromatic rings, naphthene rings, and paraffin chains. Generally, the aromatic carbon in the total carbon is 30 wt% or more, and the aromatic oil is 35 to 45 wt% in the naphthenic ring carbon. Naphthenics and those with 50% by weight or more of paraffin chain carbon are classified as paraffinic. Paraffinic crude oil is separated into paraffinic oil and aromatic oil by distillation, hydrogenation reforming, solvent extraction, and solvent dewaxing. Naphthenic crude oil is also separated into naphthenic and aromatic oils by distillation and solvent extraction. In the present invention, the synthetic oil is preferably a naphthenic oil or a paraffinic oil from the viewpoint of adhesive residue when peeling off by hand. There are various commercial products under the trade names such as “Diana Fresia” and “Diana Process Oil” from Idemitsu Kosan Co., Ltd., and “Fukor New Flex” and “Fukor Flex” from Fuji Kosan Co., Ltd. Grades are commercially available. Synthetic oil is used in the present invention so as not to lower the adhesive strength at low temperatures.

  Any polypropylene wax (E) obtained by graft polymerization of maleic anhydride may be used as long as maleic anhydride is graft-polymerized on polypropylene wax. The polypropylene wax grafted with maleic anhydride can be produced, for example, by mixing polypropylene wax, maleic anhydride and peroxide with an extruder or the like and graft-polymerizing maleic anhydride onto the polypropylene wax. The polypropylene wax used as a raw material may be any conventionally known wax and is not particularly limited. The production of the polypropylene wax is carried out by a method of producing by decomposing a polymer or a method of producing by polymerizing monomers. In the decomposition method, the polymer chain is cut by shear stress in a state where the polymer is melted by heat. On the other hand, the polymerization method is produced, for example, by anionic polymerization of a polypropylene monomer.

  The polypropylene wax (E) obtained by graft polymerization of maleic anhydride has an acid value of 30 to 100 mgKOH / g from the viewpoint of alkali dispersibility or solubility, and a DSC melting point of 60 from the viewpoint of adhesive residue when peeled by hand. The thing of -150 degreeC is preferable. The DSC melting point is measured by the following measuring method. That is, Perkin Elmer Pyris 1 manufactured by Perkin Elmer was used as a measuring device, and the measurement was first held at 0 ° C. for 5 minutes, then heated to 170 ° C. at a speed of 10 ° C./minute, and then maintained at 170 ° C. for 1 minute. Then, the temperature was lowered to 0 ° C. at a speed of 40 ° C./min. After holding at 0 ° C. for 1 minute, the measured melting point when the temperature was raised again to 170 ° C. at a speed of 10 ° C./min was defined as DSC melting point ( same as below).

  Polypropylene wax (E) obtained by graft polymerization of maleic anhydride is a maleic anhydride-modified polypropylene wax having a trade name of Ricosen PPMA from Clariant Japan, and a trade name of X-10016 from Baker Petrolite. Is commercially available.

  Examples of the wax (F) having a penetration at 25 ° C. of 10 dmm or less include polyethylene wax, polypropylene wax, Fischer Tropu wax, paraffin wax, and microcrystalline wax. From the viewpoint of leaving no adhesive residue when manually peeling off, paraffin wax, polyethylene wax, and Fischer-Tropsch wax having an oil content of 0.2% by weight or less are preferable. Paraffin wax is a kind of petroleum wax. Petroleum wax (paraffin wax (solid wax at normal temperature separated and refined from vacuum distillation oil), microcrystalline wax (vacuum distilled bottom or wax solid at normal temperature separated and purified from heavy spilled oil), petrolatum (vacuum reduced pressure) Semi-solid wax at room temperature separated and purified from the distillation bottom). Since the paraffin wax is separated from the vacuum distillation fraction, it has a carbon number distribution of about 20 to 40 and a molecular weight of about 300 to 500 hydrocarbons. This can be confirmed by gas chromatography analysis. Usually, about 90% by weight is normal paraffin, so the crystals are large. Oil refers to 1 g of sample dissolved in 15 ml of methyl ethyl ketone, cooled to −32 ° C., the precipitated wax is filtered, the solvent in the filtrate is evaporated, and the mass of residual oil is measured. (JIS K 2235-5.6). For example, paraffin wax having an oil content of 0.01% by weight to 0.2% by weight is also commercially available from Nippon Seiwa Co., Ltd. under the trade name of paraffin wax “HNP series”. The melting point is preferably 64 ° C. or higher and 80 ° C. or lower, more preferably 75 ° C. or higher and 77 ° C. or lower, from the viewpoint that no glue remains when peeling off by hand.

  The polyethylene wax has, for example, a molecular weight of 100 to 5,000 and a viscosity at 150 ° C. (based on JIS K 6862-1984 A method) of 500 mPa · s from the viewpoint that no glue remains when peeling off by hand. The following polyethylene is used. There are three typical methods for synthesizing polyethylene. (1) High pressure method: The most representative is ICI method, and other BASF, du Pont method, Union Carbide method, etc. (2) Medium pressure method: Philips method, Standard (Indiana) method, etc. (3) Low pressure method: For example, the Ziegler method. It is commercially available under the trade names of “POLYWAX” from Baker Petrolite, “Neowax” from Yashara Chemical Co., Ltd., and “AC polyethylene” from Allied Signal. Preferably, the melting point is 70 ° C. or higher and 100 ° C. or lower, more preferably 85 ° C. or higher and 95 ° C. or lower, from the viewpoint of adhesive strength at high temperature, adhesive strength that does not leave adhesive when peeled by hand, and no adhesive residue when peeled by hand.

Fischer-Tropsch wax is a by-product wax produced when synthetic petroleum is produced from coal by a hydrocarbon synthesis method. The chemical structure is a long saturated linear hydrocarbon with a few methyl branches and an isoparaffin content of about 10%. Compared to ordinary paraffin wax, it has a longer linear structure, and it has fewer side chains than microwax and is a linear molecule. The crystal structure is a plate-like crystal represented by a general chemical formula as C _n H _{2n + 2} , and particularly those having a carbon number distribution of C ₁₅ to C ₁₂₀ are suitably used for the roll shrink label of the present invention.
As the Fischer-Tropsch wax, for example, “Sazol Wax H1”, “Sazol Wax C80”, “Sazol Wax C105” and “Sazol Wax H2” manufactured by Sazol are also commercially available. . The melting point is preferably 70 ° C. or higher and 110 ° C. or lower, and more preferably 90 ° C. or higher and 105 ° C. or lower, from the viewpoint of leaving no adhesive residue by manual peeling.

The polyethylene glycol (G) having a number average molecular weight of 1,000 or more is obtained by ring-opening polymerization of ethylene oxide, has a hydroxyl group at the terminal, and may be linear or branched. The number average molecular weight is 1,000 or more, preferably 60,000 or less. Those of 3,000 or more and 20,000 or less are more preferable. If it is 1,000 or more, the cohesive force is not reduced, and when the label is peeled off, the hot melt pressure-sensitive adhesive composition does not remain in the PET bottle. Moreover, compatibility is good in a number average molecular weight being 60,000 or less.
The number average molecular weight was measured by a high temperature Gel Permeation Chromatography (GPC) method. The measurement conditions were a temperature of 40 ° C., the solvent was THF (the column used was Polymer Laboratories PLgel 5 μm MIXD-D), and the standard polymer was used in a polystyrene conversion method.
Examples of polyethylene glycol (G) having a number average molecular weight of 1,000 or more include PEG1000, PEG15000, PEG2000, PEG4000, PEG4000S, Sanyo Kasei Co., Ltd., polyethylene glycol 1000, polyethylene glycol 1500, 2000, polyethylene glycol 4000, manufactured by NOF Corporation. The product name such as is also commercially available.

  A typical example of polybutene (H) is a copolymer having a molecular structure of a long-chain hydrocarbon in which normal butene is partially reacted mainly with isobutene. Although it is a low polymer mainly composed of isobutylene, unlike the low molecular weight polyisobutylene using purified isobutylene as a raw material, the remaining fraction obtained by extracting butadiene from the C4 fraction produced by naphtha decomposition can be used as it is. It is a liquid polymer in which some butene 1 is copolymerized. Polybutene is also marketed under the trade names such as “Nisseki Polybutene” from Nippon Oil Corporation, “Toughmer BL” from Mitsui Chemicals, and “Idemitsu Polybutene” from Idemitsu Kosan Co., Ltd.

The penetration of the present invention is a measurement method for determining the hardness of petroleum wax, a load of 100 g is applied to the needle at a measurement temperature with a penetration meter, and the number of millimeters to penetrate into the sample in 5 seconds is determined. The value was expressed by a value (dmm) 10 times this value (JIS K 2235-5.4).
The softening point of the present invention was based on the softening point test method by the ring and ball method according to JIS K 6863-1994.
The melting point of the present invention is based on the melting point measurement method according to JIS K 2235-5.3.
The above components (A) and (B) are mixed with components (C) to (H) as necessary to produce a first hot melt pressure-sensitive adhesive. The order of mixing is, for example, terpene phenol resin (C), synthetic oil (D), polypropylene wax (E), wax (F), polyethylene glycol (G), and polybutene (H) by heating and mixing to completely dissolve. Thereafter, the thermoplastic elastomer (A) may be added and completely dissolved, and finally the rosin tackifier (B) may be added and dissolved. As a preferred easy-to-use trial production method, a 500 cc stainless beaker is placed in a mantle heater, terpene phenol resin (C), synthetic oil (D), polypropylene wax (E), wax (F), polyethylene glycol (G), polybutene (H ) And mix by heating. The stirrer may be prepared by adding a small amount of the thermoplastic elastomer (A) while rotating at a stirring speed of 200 to 1000 rpm using a propeller type, and finally adding the rosin-based tackifier (B).
When the total amount of the first hot-melt pressure-sensitive adhesive is 100 parts by weight, the blending ratio (% by weight) of each component is as follows: thermoplastic elastomer (A): rosin-based tackifier (B): terpene phenol resin (C): synthesis Oil (D): Polypropylene wax (E): Wax (F): Polyethylene glycol (G): Polybutene (H) = 5-40: 20-60: 0-0-20: 0-50: 0-20-20-20 : 0 to 20: 0 to 50 is preferable, and more preferably 10 to 30:30 to 50: 0 to 10: 0 to 40: 0 to 10: 0 to 10: 0 to 10: 0 to 40.

The first hot melt pressure-sensitive adhesive is used to form the first adhesive layer at one end on the base film, which becomes the joint between the base film and the container, and the second adhesive layer at the other end is formed. By using the second hot melt pressure-sensitive adhesive, the following effects can be obtained.
That is, after using a labeled container, when separating the pelletized PET bottle substrate and the label in the recycling facility, if the pellet is put in a 90 ° C. 1.5 wt% NaOH aqueous solution, the PET bottle substrate and the roll shrink label are The first hot melt adhesive is separated because it is dispersed in the solution. On the other hand, in this solution, the second hot melt pressure-sensitive adhesive continues to maintain adhesion between the base films and does not separate. Therefore, the separated label is not reattached to the PET bottle base by the second adhesive layer.

The second hot melt pressure-sensitive adhesive is not particularly limited as long as it is a pressure-sensitive adhesive that is not dispersed and dissolved in a 1.5 wt% NaOH aqueous solution at 90 ° C.
Specifically, the second hot melt pressure-sensitive adhesive has a viscosity measured with a rheometer at 100 ° C. of 20,000 mPa · s or less and a viscosity measured with a rheometer at 90 ° C. of 30,000 mPa · s or more. Is preferred. Within this viscosity range, the hot melt pressure-sensitive adhesive is neither dispersed nor dissolved in the NaOH aqueous solution.
More specifically, the second hot melt pressure-sensitive adhesive preferably contains a thermoplastic elastomer (J) and a tackifier (K), and further includes a synthetic oil (D), a wax (L), and a polybutene (H ) May be included.
The thermoplastic elastomer (J) is preferably a styrene elastomer. Styrenic elastomers include styrene / butadiene block copolymers (SB, diblock), (SBSS, triblock, styrene / isoprene block copolymers (SI, diblock), (S -IS, triblock), and styrene / butadiene-isoprene block copolymers (SB, I, diblock), (SB / IB, triblock) and water of these block copolymers Additives, for example, hydrogenated styrene / butadiene / styrene block copolymer (SBS), hydrogenated styrene / isoprene / styrene block copolymer (SEPS), and styrene-based styrenic compounds described above modified with carboxylic acid Elastomers, and copolymers of styrene and aromatic vinyl compounds such as α-methylstyrene in addition to styrene in the styrene block Are also illustrated.

  The thermoplastic elastomer (J) may be used alone or in combination of two or more, and diblock and triblock may be contained, but the contained diblock is a thermoplastic elastomer ( J) 70% by weight or less, preferably 40% by weight or less, out of 100% by weight based on the total. When it is 70% by weight or less, it is difficult to peel off when the roll shrink labels (that is, the base films) are bonded to each other.

  The ratio of styrene contained in these thermoplastic elastomers (J) is 10 to 40% by weight, preferably 15 to 35% by weight. If it is 10% by weight or more, the cohesive strength of the adhesive is high. When it is 40% by weight or less, fluidity is good.

  As the tackifier (K), hydrogenated aliphatic, alicyclic, and aromatic petroleum resins and terpene resins are preferable because of excellent weather resistance. Specific examples of a more preferable solid tackifying resin include, for example, a hydrogenated alicyclic petroleum resin manufactured by Arakawa Chemical Co., Ltd., trade name: Archon, and a terpene resin, Yashara Chemical Co., Ltd., trade name: Clearon. Etc. These may be used independently and 2 or more types may be used together.

  The softening point of the tackifier (K) is preferably 90 to 140 ° C. More preferably, it is 100-135 degreeC. When it is 90 ° C. or higher, the elastic modulus does not rapidly decrease in a high temperature range. When the temperature is 140 ° C. or lower, tack does not disappear in a low temperature range, and the adhesiveness to the roll shrink label is excellent.

  About synthetic oil (D) and polybutene (H), it is as having demonstrated the 1st hot melt adhesive.

  Wax (L) is a substance that has a viscosity of 5,000 mPa · s or less at 150 ° C. and solids and crystallizes at 20 ° C., for example, natural wax: animal wax (eg, beeswax, whale wax), plant Wax (wood wax, rice bran wax, etc.), mineral wax (montan wax, ozokerite, etc.), petroleum wax (paraffin wax, microcrystalline wax, etc.), synthetic wax: Fischer-Tropsch wax, polyethylene wax, etc. In particular, polyethylene wax and paraffin wax are preferable.

The above-mentioned (J), (K), (D), (L) and (H) components are mixed to prepare a second hot melt adhesive. For example, the mixing order is as follows. First, (D), (L), (H), about half of the amount (J) is added and dissolved, (J) is added and completely dissolved, and the remaining (J) is finally added. You may throw it in. The instrument used is a 500 cc metal can heated by a mantle heater, and the stirrer is preferably a propeller type stirring blade and the rotational speed is preferably 200 to 500 rpm.
When the total amount of the second hot-melt pressure-sensitive adhesive is 100, the blending ratio (% by weight) of each component is as follows: thermoplastic elastomer (J): tackifier (K): terpene phenol (C): synthetic oil (D) : Wax (L): Polybutene (H) = 5-30: 30-80: 0-30: 0-40: 0-20: 0-50, more preferably 5-25: 20-70: 0 It is 10: 0 to 40: 0 to 10: 0 to 30. Within this range, the cohesive force is maintained, the adhesiveness is good, and the roll shrink label is not peeled off when thermally contracted.

Next, the manufacturing method of the container with a roll shrink label is demonstrated.
First, a first pressure-sensitive adhesive layer made of a first hot melt pressure-sensitive adhesive is formed on one end of a roll shrink label, and a second pressure-sensitive adhesive layer made of a second hot-melt pressure-sensitive adhesive is formed on the other end. It shall be a roll shrink label with. As a method for forming each adhesive layer, an adhesive may be directly applied to form an adhesive layer, or an adhesive layer may be transferred and indirectly applied.
Examples of the direct coating method include slit coating, curtain spray, spiral spray, dot or bead coating, and slit coating is preferable.
In the case of contact coating, slit coating is used, and the coating temperature is preferably 90 ° C. or higher and 110 ° C. or lower. If it is in said temperature range, even if it is higher than the shrink temperature of a roll shrink label, since the time for which a shrink label is heated is short, it can coat without shrinking.
In the curtain spray, spiral spray, dot or bead method, there is a distance from the nozzle to the base film, so each adhesive will cool down before reaching the roll shrink label, so the roll shrink label will shrink before mounting. Can be prevented.
Examples of the method of indirectly applying include a method using a roll. In the method using a roll, for example, a hot melt adhesive is applied to a release paper using a hand applicator, and then the coated product is cut to a required size and transferred to a roll shrink label. According to this method, there is no possibility that the roll shrink label contracts on the base film of the roll shrink label due to the temperature of the pressure-sensitive adhesive during coating.

  The width of the first adhesive layer formed at one end of the roll shrink label is preferably 2 mm or more, more preferably 5 mm or more from the viewpoint of temporary fixing. The width of the second adhesive layer formed on the other end of the roll shrink label is preferably 3 mm or more, more preferably 10 mm or more, and further preferably 20 mm or more. When the width of the second adhesive layer is 3 mm or more, when the roll shrink label is heated with steam or the like, the strength of the adhesive layer is insufficient and the label is not peeled off or displaced. The “adhesive layer width” here is the length of the adhesive layer in the label winding direction.

Next, the shrink label with an adhesive is wound around the container, the label and the container are fixed by the first adhesive layer, and the labels are fixed by the second adhesive layer.
Next, the roll shrink label wound around the container is shrunk with steam or hot water, and fixed around an uneven (atypical) bottle. The shrink temperature is preferably 70 to 90 ° C.

  In addition, when shrinking a shrink label, the first hot melt pressure-sensitive adhesive used for bonding the container and the label may be partially peeled off from the bottle or adhered, or when the container is used or at 90 ° C. 1.5 wt. There is no problem in peeling with a% NaOH aqueous solution. This is because, once shrinking, the label is fixed on the container mainly by the shrinkage stress of the film.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
In the examples, “parts” simply means “parts by weight” and “%” means “% by weight”. “WT%” means “% by weight”.

  The components used in the first and second hot melt adhesives are as follows.

Thermoplastic elastomer (A)
Kraton G1650 (manufactured by Kraton Polymer Co., Ltd.) (hereinafter abbreviated as “G1650”)
Styrene-ethylene-butylene-styrene block polymer (SEBS)
Diblock amount: 0%
Melt viscosity ^{* 1} : 8,000 mPa · s
Clayton G1652 (manufactured by Clayton Polymer) (hereinafter abbreviated as “G1652”)
Styrene-ethylene-butylene-styrene block polymer (SEBS)
Diblock amount: 0%
Melt viscosity ^{* 1} ; 1,350 mPa · s
Clayton G1726 (manufactured by Clayton Polymer) (hereinafter abbreviated as “G1726”)
Styrene-ethylene-butylene-styrene block polymer (SEBS)
Diblock amount: 70%
Melt viscosity ^{* 1} : 200 mPa · s
The melt viscosity ^{* 1} is a melt viscosity at 25 ° C. of a toluene solution having a thermoplastic elastomer concentration of 25% by weight. The melt viscosity was measured using a B-type viscometer RB80L (manufactured by Toki Sangyo Co., Ltd.). 3 was carried out at a suitable rotational speed.

Rosin tackifier (B) having an acid value of 100 mgKOH / g or more and 300 mgKOH / g or less
・ Licarodin F (manufactured by Harima Chemicals)
Hydrogenated rosin Acid value: 175 mgKOH / g
Softening point: 72 ° C
・ KE-604 (Arakawa Chemical Co., Ltd.)
Hydrogenated acrylic acid modified rosin Acid value: 240 mgKOH / g
Softening point: 125 ° C

Terpene phenol resin (C)
・ YS Polystar T30 (manufactured by Yasuhara Chemical Co., Ltd.) (hereinafter abbreviated as “T30”)
Terpene phenol resin Softening point: 30 ° C
Synthetic oil (D)
Diana Fresia N-90 (made by Idemitsu Kosan Co., Ltd.) (hereinafter abbreviated as “N90”)
Paraffin-based process oil / Diana process PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) (hereinafter abbreviated as “PW90”)
Paraffin-based process oil / Diana process PW-380 (manufactured by Idemitsu Kosan Co., Ltd.) (hereinafter abbreviated as “PW380”)
Paraffinic process oil / process oil 100R (manufactured by Idemitsu Kosan Co., Ltd.) (hereinafter abbreviated as “100R”)
Naphthenic process oil
Polypropylene wax grafted with maleic anhydride (E)
・ Ricosen PPMA6252 (manufactured by Client Japan) (hereinafter abbreviated as “PPMA6252”)
Maleic anhydride-modified polypropylene wax Acid value: 40 mgKOH / g
DSC melting point: 127 ° C
・ Ricosen PPMA1462 (manufactured by Client Japan) (hereinafter abbreviated as "PPMA1462")
Maleic anhydride-modified polypropylene wax Acid value: 50 mgKOH / g
DSC melting point: 66 ° C
・ X-10016 (manufactured by Baker Petrolite)
Maleic anhydride-modified polypropylene wax Acid value: 60 mgKOH / g
DSC melting point: 117 ° C
Wax (F) having a penetration of 25 ° C. of 10 dmm or less
・ HNP-9 (Nippon Seiwa Co., Ltd.)
Paraffin wax penetration: 7dmm
Melting point: 76 ° C
Oil content: 0.1WT%
POLYWAX 655 (manufactured by Baker Petrolite) (hereinafter abbreviated as “PW655”)
Polyethylene wax penetration: 2dmm
Melting point: 90 ° C
Oil content: 0.1 WT% or less, Sasol wax C80 (manufactured by Sasol) (hereinafter abbreviated as “C80”)
Fischer Trop push wax penetration: 8dmm
Melting point: 77 ° C
Oil content: 0.1WT% or less
Polyethylene glycol (G) having a number average molecular weight of 1,000 or more
Polyethylene glycol PEG-1000 (manufactured by Sanyo Chemical Co., Ltd.) (hereinafter abbreviated as “PEG-1000”)
Polyethylene glycol Number average molecular weight: 1,000
Polyethylene glycol PEG-2000 (manufactured by Sanyo Chemical Co., Ltd.) (hereinafter abbreviated as “PEG-2000”)
Polyethylene glycol Number average molecular weight: 2,000
Polyethylene glycol PEG-6000 (manufactured by Sanyo Chemical Co., Ltd.) (hereinafter abbreviated as “PEG-6000”)
Polyethylene glycol Number average molecular weight: 6,000
Polyethylene glycol PEG-20000 (manufactured by Sanyo Kasei Co., Ltd.) (hereinafter abbreviated as “PEG-20000”)
Polyethylene glycol Number average molecular weight: 20,000
Polybutene (H)
• Idemitsu Polybutene 100R (manufactured by Idemitsu Kosan Co., Ltd.) (hereinafter abbreviated as “Polybutene 100R”)
Polybutene hydrogenated grade
Thermoplastic elastomer (J)
Kraton G1726 (manufactured by Kraton Polymer Co., Ltd.) (hereinafter abbreviated as “G1726”)
Styrene-ethylene-butylene-styrene block polymer (SEBS)
Diblock amount: 70%, styrene ratio 30% by weight
Melt viscosity ^{* 1} : 200 mPa · s
Clayton G1652 (manufactured by Clayton Polymer) (hereinafter abbreviated as “G1652”)
Styrene-ethylene-butylene-styrene block polymer (SEBS)
Diblock amount: 0%
Melt viscosity ^{* 1} ; 1,350 mPa · s
Kraton G1643 (manufactured by Kraton Polymer Co., Ltd.) (hereinafter abbreviated as “G1643”)
Styrene-ethylene-butylene-styrene block polymer (SEBS)
Diblock amount: 18%
Melt viscosity ^{* 1} ; 200 mPa · s
・ Septon 2104 (Kuraray)
Polystyrene-poly (ethylene / propylene) block-polystyrene (SEPS)
Styrene content 30% by weight
Melt viscosity ^{* 2} : 23 mPa · s
The melt viscosity ^{* 1} is a melt viscosity at 25 ° C. of a toluene solution having a thermoplastic elastomer concentration of 25% by weight. The melt viscosity was measured using a B-type viscometer RB80L (manufactured by Toki Sangyo Co., Ltd.). 3 was carried out at a suitable rotational speed. The melt viscosity ^{* 2} is a melt viscosity at 25 ° C. of a toluene solution having a thermoplastic elastomer concentration of 15% by weight. The melt viscosity was measured using a B-type viscometer RB80L (manufactured by Toki Sangyo Co., Ltd.). 3 was carried out at a suitable rotational speed.
Tackifier (K)
・ Arcon P-100 (Arakawa Chemical Co., Ltd.)
Hydrogenated petroleum-based tackifier Softening point: 100 ° C
・ Arcon P-90 (Arakawa Chemical Co., Ltd.)
Hydrogenated petroleum-based tackifier Softening point: 90 ° C
・ KE-604 (Arakawa Chemical Co., Ltd.)
Hydrogenated acrylic acid modified rosin Acid value: 240 mgKOH / g
Softening point: 125 ° C

Wax (L)
PW2000 (manufactured by Baker Petrolite) (hereinafter abbreviated as “PW2000”)
Main component: Polyethylene Softening point: 126 ° C
PW1000 (manufactured by Baker Petrolite) (hereinafter abbreviated as “PW1000”)
Main component: Polyethylene Softening point: 113 ° C
PW655 (manufactured by Baker Petrolite) (hereinafter abbreviated as “PW655”)
Main component: Polyethylene Softening point: 99 ° C
HNP-9 (Nippon Seiwa Co., Ltd.) (hereinafter abbreviated as “HNP-9”)
Paraffin wax Softening point: 75 ° C
PW500 (manufactured by Baker Petrolite) (hereinafter abbreviated as “PW500”)
Main component: Polyethylene Softening point: 90 ° C

<The preparation method of the 1st hot melt adhesive>
Production Example A-1
In a stainless beaker equipped with a stirrer, 31 parts by weight of synthetic oil (D); N90, polypropylene wax (E): 4 parts by weight of PPMA1462, and 10 parts by weight of terpene phenol resin (C): T-30 are heated. And melted. Heating was performed with care so that the contents would not be below 130 ° C and above 150 ° C. After melting, stirring is performed to obtain a homogeneous molten solution, and while maintaining the temperature below 150 ° C. and continuing stirring, 16 parts by weight of thermoplastic elastomer (A); G1650 is gradually added to the melt, and the addition is completed. Then, 39 parts by weight of rosin-based tackifier (B), licarrodin F, was added to obtain a molten homogeneous mixture and cooled to obtain a first hot melt pressure-sensitive adhesive composition.

Production Examples A-2 to 6
The thermoplastic elastomer (A), rosin tackifier (B), terpene phenol resin (C), synthetic oil (D) and polypropylene wax (E) obtained by graft polymerization of maleic anhydride are listed in Table 1 below. Ingredients were added, and first hot melt pressure-sensitive adhesives of Production Examples A-2 to A-6 were produced in the same manner as Production Example A-1.

Production Example A-7
A stainless beaker equipped with a stirrer is charged with synthetic oil (D); 32 parts by weight of PW90 and 7 parts by weight of wax (F): HNP-9 having a penetration of 10 ° C. or less at 25 ° C. and heated to melt. did. Heating was performed with care so that the contents would not be below 130 ° C and above 150 ° C. After melting, stirring is performed to obtain a uniform molten solution, and while maintaining the temperature below 150 ° C. and continuing stirring, 10 parts by weight of thermoplastic elastomer (A); G1650 is gradually added to the melt, and the addition is completed. Thereafter, 51 parts by weight of licarodine F was added to the rosin-based tackifier (B) to form a molten homogeneous mixture and cooled to prepare a first hot melt pressure-sensitive adhesive composition.

Production Example A-8-14
The thermoplastic elastomer (A), rosin-based tackifier (B), synthetic oil (D), wax (F) having a penetration at 25 ° C. of 10 dmm or less, and polybutene (H) are listed in Table 1 below. Ingredients were added and the first hot melt adhesives of Production Examples A-8 to 14 were produced in the same manner as Production Example A-7.

Production Example A-15
In a stainless beaker equipped with a stirrer, synthetic oil (D): 32 parts by weight of PW90 and a wax having a penetration of 10 dmm or less at 25 ° C .: 10 parts by weight or less: 7 parts by weight of HNP-9, polyethylene glycol (G): 6 parts by weight of PEG-1000 was charged and heated to melt. Heating was performed with care so that the contents would not be below 130 ° C and above 150 ° C. After melting, stirring is performed to obtain a uniform molten solution, and while maintaining the temperature below 150 ° C. and continuing stirring, 10 parts by weight of thermoplastic elastomer (A); G1650 is gradually added to the melt, and the addition is completed. Thereafter, 45 parts by weight of licarodine F was added to the rosin-based tackifier (B) to form a molten homogeneous mixture and cooled to prepare a first hot melt adhesive.

Production Example A-16-20
Table 1 below shows thermoplastic elastomer (A), rosin-based tackifier (B), synthetic oil (D), wax (F) and polyethylene glycol (G) having a penetration of 10 ° C. or less at 25 ° C. The first hot melt pressure-sensitive adhesive of Production Examples A-16 to 20 was produced in the same manner as in Production Example A-15.

<Measurement method of viscosity>
About the obtained 1st hot melt adhesive, the viscosity measurement was performed at 100 degreeC using the plate-type rheometer. The measurement method and measurement conditions are as follows. The measurement results are shown in Table 1.
・ Measuring device: Dynamic viscosity viscoelasticity measuring device Rheosol-G3000 (manufactured by UBM Co., Ltd. ・ Measurement mode: temperature dependence ・ Chuck: parallel plate ・ Waveform: sine wave ・ Parallel diameter: 19.99 mm
・ Cap: 1mm
Measurement start temperature: 180 Measurement end temperature: 30
・ Cooling rate: 2 ℃ / min ・ Rotation width: 2Hz, 3deg

<Method for producing second hot melt pressure-sensitive adhesive>
Production Example B-1
In a stainless steel beaker equipped with a stirrer, 33 parts by weight of the added tackifier (K): Alcon P-100 and 27 parts by weight of polybutene (H): 100R were charged and heated to a molten state. 7 parts by weight of thermoplastic elastomer (J): G1726 was added and stirred at 150 ° C. for 1 hour, the remaining tackifier (K): 33 parts by weight of Alcon P-100 was added and stirred at 150 ° C. for 1 hour, A second hot melt adhesive was obtained.

Production Example B-2
Add 35 parts by weight of synthetic oil (D): N90 to be added to a stainless steel beaker equipped with a stirrer, heat, add 20 parts by weight of thermoplastic elastomer (J): G1652 and stir at 150 ° C. for 1 hour to adhere. Giving agent (K): 30 parts by weight of Alcon P-90 and 10 parts by weight of KE-604 are charged, heated, and when it is in a molten state, 5 parts by weight of wax (L): HNP-9 are gradually added. And a second hot melt pressure-sensitive adhesive was obtained by stirring at 150 ° C. for 1 hour.

Production Examples B-3 to 7
In the same manner as in Production Example B-2, in a stainless steel beaker equipped with a stirrer, the entire amount of synthetic oil (D): N90 to be added is charged and heated, and the entire amount of the thermoplastic elastomer (J) is added at 150 ° C. Stir for a period of time, add the entire amount of tackifier (K), heat, and gradually add the total amount of wax (L) when it is in a molten state, and stir at 150 ° C. for 1 hour to obtain the second hot melt adhesive An agent was obtained.
<Measurement method of viscosity>
About the obtained 2nd hot melt adhesive, the viscosity measurement was performed by the method similar to a 1st hot melt adhesive at 90 degreeC and 100 degreeC. The results are shown in Table 2.

<Production method of roll shrink label>
The first hot-melt pressure-sensitive adhesive and the second hot-melt pressure-sensitive adhesive prepared by the above method were applied to a release paper using a hand applicator heated to 150 ° C. so that the coating amount was 20 to 30 μm. . The coated product is cut to a required size, and the first hot melt pressure-sensitive adhesive coated material prepared by the above method is transferred to the end (I) of the base film shown below having a width of 60 mm and a length of 250 mm. A first adhesive layer was provided. In the same manner, the second hot-melt pressure-sensitive adhesive coated material was transferred to the other opposite end (II), and a second pressure-sensitive adhesive layer was provided to produce a roll shrink label. The widths of the ends (I) and (II) are shown in Table 3.

<Base film>
As the base film used, MD direction uniaxially stretched polyethylene terephthalate (Toyobo Co., Ltd.) having a thickness of 20 μm was used.

Examples 1-20
<Method for producing labeled container>
The roll shrink label produced above was wound around a barrel of a cylindrical PET bottle having a circumference of 200 mm. At that time, the first pressure-sensitive adhesive layer (I) is first adhered to the PET bottle, and then the roll shrink label is circled, and the second pressure-sensitive adhesive layer (II) is adhered to the roll shrink label. The first pressure-sensitive adhesive layer (II) was not adhered to the PET bottle, but was adhered only to the roll shrink label to produce a container. The prepared container was subjected to the following tests, and the results are shown in Table 3.
<Alkali peelability>
The labeled container was pulverized to about 8 × 8 mm square to form a PET bottle pellet with a label attached. In a 1,000 ml round flask, 360 g of a 1.5 wt% sodium hydroxide aqueous solution and 40 g of the pellets were placed, and stirred at 250 rpm (stirring blade: propeller). After 15 minutes, it is filtered through a filter, the pellet is visually observed, the label is peeled off, and the hot melt adhesive composition does not remain in the PET bottle: ○, the label remains in the PET bottle, or the hot melt adhesive composition is When remaining in PET bottle or reattached: x.

<Adhesive strength (vs. OPP)>
For strength measurement, the second hot-melt pressure-sensitive adhesive prepared by the above method was applied to a release paper to a thickness of 20 μm, transferred to the printing surface of the base film, and affixed to a PET bottle. Created.

<Adhesive strength (against PET)>
For strength measurement, the second hot-melt pressure-sensitive adhesive prepared by the above method is applied to a release paper (thickness 20 μm), transferred to the printing surface of the base film, and this is attached to a PET bottle. It was created.

The test container to which the label was attached was cut to a width of 15 mm, and the adhesive strength was measured by 180 ° square peeling (peeling speed: 300 mm / min) in a constant temperature and humidity chamber at a temperature of 23 ° C. and a relative humidity of 65%.
It should be noted that if the adhesive strength is 0.4 N / 15 mm or more for both OPP and PET, ○. If it is less than 0.4 N / 15 mm, it is x.

<Shrink aptitude test>
The labeled container produced by the above method was placed in a hot water bath heated to 90 ° C., and the roll shrink label was shrunk and evaluated. The evaluation when the roll shrink label contracted and the first adhesive layer or the second adhesive layer was peeled off or shifted was evaluated as x. The evaluation when there was no deviation or peeling was rated as “◯”.

<Adhesive residue>
The labeled container was placed in a 90 ° C. hot water bath, the roll shrink label was shrunk, and the label of the sample judged to have a shrinkability of ○ was peeled off. The evaluation when the first hot melt adhesive remained in the PET bottle was evaluated as x. The evaluation when no residue was left was rated as ○.
The above results are shown in Table 3.
According to the examples of the present invention, it was shown that all had sufficient adhesive strength and shrinkability, were excellent in alkali peelability, and had no adhesive residue.
Comparative Examples 1-5
The pressure-sensitive adhesive for fixing the label and the container was blended with the components shown in Table 4, and the pressure-sensitive adhesive was prepared and the viscosity was measured in the same manner as in Production Example A-1 (Production Example A′-1). 2).
Moreover, the adhesive for fixing labels was mix | blended the component of Table 5, and it produced similarly to manufacture example B-1, and measured the viscosity (manufacture example B'-1-3).
Next, the components shown in Table 6 including any of these pressure-sensitive adhesives were blended, and similarly to Example 1, a labeled container was prepared and each test was performed. The test results are shown in Table 6.

Claims (8)

container,
A roll shrink label wound around the outer periphery of the container,
A first adhesive layer made of a first hot melt adhesive dispersed or dissolved in a 1.5 wt% NaOH aqueous solution at 90 ° C., which is formed at one end of the label and fixes the label and the container; and With a roll shrink label provided with a second adhesive layer made of a second hot melt adhesive that is not dispersed or dissolved in a 1.5 wt% NaOH aqueous solution at 90 ° C., which is formed at the other end of the label and fixes the labels together container.   The container with a roll shrink label according to claim 1, wherein the first hot melt adhesive has a viscosity measured by a rheometer at 100 ° C of 20,000 mPa · s or less.   The second hot melt pressure-sensitive adhesive has a viscosity measured with a rheometer at 100 ° C of 20,000 mPa · s or less and a viscosity measured with a rheometer at 90 ° C of 30,000 mPa · s or more. Container with roll shrink label.   The container with a roll shrink label according to claim 1, wherein the roll shrink label is a uniaxially stretched film in the MD direction. A first pressure-sensitive adhesive layer made of a first pressure-sensitive adhesive dispersed or dissolved in a hot alkaline aqueous solution is formed at one end of the roll shrink label, and a second pressure-sensitive adhesive made of a second pressure-sensitive adhesive not dispersed or dissolved in the hot alkaline aqueous solution at the other end. Forming an adhesive layer of
Winding the label obtained in the previous step around the container, fixing the label and the container with the first adhesive layer, fixing the labels with the second adhesive layer, and shrinking the label by heating The manufacturing method of the container with a roll shrink label provided.   A roll shrink label, which is a uniaxially stretched film in the MD direction.   A hot-melt pressure-sensitive adhesive for roll shrink labels that is not dispersed or dissolved in a 1.5 wt% NaOH aqueous solution at 90 ° C. Roll shrink label,
A first pressure-sensitive adhesive layer formed of a first pressure-sensitive adhesive formed on one end of the label and dispersed or dissolved by a hot alkaline aqueous solution; and a second pressure-sensitive adhesive layer formed on the other end of the label and not dispersed and dissolved in the hot alkaline aqueous solution. A roll shrink label with an adhesive layer comprising a second adhesive layer made of an adhesive.