WO2023171098A1 - Coated glass container and method for producing same - Google Patents

Coated glass container and method for producing same Download PDF

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Publication number
WO2023171098A1
WO2023171098A1 PCT/JP2022/048498 JP2022048498W WO2023171098A1 WO 2023171098 A1 WO2023171098 A1 WO 2023171098A1 JP 2022048498 W JP2022048498 W JP 2022048498W WO 2023171098 A1 WO2023171098 A1 WO 2023171098A1
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WO
WIPO (PCT)
Prior art keywords
glass container
coating
coated glass
coating agent
label
Prior art date
Application number
PCT/JP2022/048498
Other languages
French (fr)
Japanese (ja)
Inventor
靖弘 五郡
杜友 山代
Original Assignee
東洋ガラス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋ガラス株式会社 filed Critical 東洋ガラス株式会社
Publication of WO2023171098A1 publication Critical patent/WO2023171098A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Definitions

  • coating has been performed in which a coating agent is applied to the outer surface of a glass container near the exit of a lehr (so-called cold end).
  • a coating agent is made by adding a surfactant to a solid lubricant such as polyethylene, polyethylene wax, modified polyethylene wax, or carnauba wax to disperse these fine particles in water to form an emulsion.
  • hot end coating is often performed as a pretreatment. This is done by applying a tin compound (mainly tin tetrachloride) or a titanium compound (mainly titanium tetrachloride) to the outer surface of the high-temperature glass container immediately after forming, near the entrance of the lehr, and applying tin oxide to the outer surface of the glass container. Alternatively, a film of titanium oxide or the like is formed. Hot-end coating improves the adhesion of the cold-end coating film to the glass surface. Glass containers such as glass bottles are often coated with both the above-mentioned hot-end coating and cold-end coating and then labeled.
  • a tin compound mainly tin tetrachloride
  • titanium compound mainly titanium tetrachloride
  • Patent Document 1 discloses an aqueous composition characterized by containing an emulsified polyethylene wax having an acid value of 10 to 25 mg-KOH/g and a silane coupling agent having an amino group, and which has a label.
  • An invention related to a coating composition for forming an easily peelable glass surface is disclosed.
  • the mixed liquid may change over time, and the stability of the coating composition is low.
  • Patent Document 2 describes the steps of applying a first coating agent containing a solid lubricant to the outer surface of a glass container, and applying a second coating agent containing an easily peelable substance (such as a silane coupling agent).
  • a coating method is disclosed, which is characterized in that the coating method comprises:
  • An object of the present invention is to provide a glass container coated with a coating that has a label that is difficult to peel off during normal use and does not remain on the glass container when the label is peeled off, and a method for manufacturing the same. is the purpose. Another object is to provide a coating method that can maintain the stability of the cold-end coating agent.
  • the present inventors have discovered that in the cold-end coating process, a first coating agent containing an adhesive substance is applied, and then a second coating agent containing a solid lubricant is applied and then glued.
  • a first coating agent containing an adhesive substance is applied, and then a second coating agent containing a solid lubricant is applied and then glued.
  • the label has a level of adhesion that makes it difficult to peel off during normal use, and when the label is removed after use, it does not remain on the surface of the glass container.
  • the present invention is as follows.
  • the present invention includes the following.
  • Method of manufacturing glass containers [2] The method for producing a coated glass container according to [1], wherein the adhesive substance contains an amino group silane coupling agent.
  • [4] The method for manufacturing a coated glass container according to any one of [1] to [3], wherein the second coating agent contains a surfactant.
  • [5] The method for manufacturing a coated glass container according to any one of [1] to [4], wherein the first coating agent is applied to the glass surface of the glass container body.
  • [6] The coated glass according to any one of [1] to [5], wherein the step of applying the second coating agent is performed after the first coating agent has dried after applying the first coating.
  • Method of manufacturing containers [7] A method for producing a labeled glass container, comprising the step of attaching a glued label to the coated glass container according to any one of [1] to [6].
  • a coated glass container A glass container body, an adhesive layer disposed on the glass container body; A coated glass container comprising a lubricity and scratch resistance imparting layer disposed on the adhesive layer.
  • coated glass containers of the present invention are coated with a specific cold-end coating, so the label has a degree of adhesion that is difficult to peel off during normal use, and when it is peeled off, a portion of the label remains on the surface of the glass container.
  • FIG. 1 is a flowchart showing an example of a method for manufacturing a coated glass container of the present invention.
  • FIG. 2 is an explanatory diagram of cold-end coating using a spray nozzle in the method for manufacturing a coated glass container of the present invention (view from above).
  • FIG. 3 is an explanatory diagram of cold-end coating using a spray nozzle in the method for manufacturing a coated glass container of the present invention (view from the side).
  • FIG. 1 is a cross-sectional view of a labeled glass container that has been coated according to the present invention.
  • FIG. 2 is a cross-sectional view of the surface state of a labeled glass container that has been subjected to a conventional coating treatment.
  • FIG. 2 is a cross-sectional view of the surface state of a labeled glass container that has been subjected to the coating treatment of the present invention. It is a photograph showing the state in which the mixed coating agent was stored for 10 days.
  • the present invention includes a step of applying a first coating agent containing an adhesive substance to a slowly cooled glass container body to form a first coated glass container, and a step of applying a solid lubricant to the first coated glass container. , and forming a second coated glass container by applying a second coating agent that imparts lubricity and scratch resistance.
  • FIG. 1 is a flowchart showing an example of a conventional method for manufacturing a glass container.
  • glass cullet and the like which are glass materials, are melted in a melting furnace A.
  • the temperature of the molten glass is adjusted, and the glass gob obtained from the melting furnace A is molded into a glass container in the bottle making machine B.
  • the formed glass container is transported to an annealing furnace C to remove any remaining strain.
  • the glass container from which the strain has been removed in the slow cooling furnace C is inspected by an inspection machine D, subjected to packaging treatment E, and then shipped F.
  • a label with glue is attached at the place of purchase of the glass container after the glass container is shipped from a manufacturing factory (not shown).
  • hot end coating In order to impart lubricity and scratch resistance to the outer surface of the glass of the glass container and to adjust the adhesive strength of the label, hot end coating (HEC) is applied as necessary before entering the lehr C, and then After leaving the lehr C and before entering the inspection machine D, cold end coating is performed.
  • hot-end coating involves gasifying tin chloride and spraying it onto a hot glass container
  • cold-end coating involves spraying an aqueous solution containing polyethylene wax or the like.
  • the present invention is characterized in that cold end coating is performed in two steps.
  • a step of applying a first coating agent containing an adhesive substance and a step of applying a second coating agent containing a solid lubricant and imparting lubricity and scratch resistance are performed.
  • the step of applying the first coating agent is characterized in that the step of applying the first coating agent is performed before the step of applying the second coating agent.
  • the temperature of the glass container body manufactured by bottle making machine B is 400 to 600°C, and the temperature of the glass container after passing through the slow cooling furnace is 70 to 120°C. .
  • the first coating agent is sprayed laterally and downwardly onto the glass container whose temperature has been lowered and the strain has been released using an upstream spray nozzle to apply the first coating agent to almost the entire outer surface of the glass container (excluding the mouth and bottom). Further, the step of applying the second coating agent is performed using a downstream spray nozzle in the same application area as the first coating.
  • FIGS. 2 and 3 are explanatory diagrams of coating using a spray nozzle (coating in the cold-end coating step) in the method for manufacturing a coated glass container of the present invention.
  • the glass container body 1 from which the strain has been removed is placed on a moving conveyor 5, which is a moving means, and advances from the outlet of the lehr 8 toward the inspection machine (FIG. 2).
  • the upstream spray nozzle 6 and the downstream spray nozzle 7 move between the rows of glass containers in a direction perpendicular to the traveling direction of the glass container body 1 and perform spraying (FIG. 3).
  • the first coating agent is sprayed laterally and downwardly using the upstream spray nozzle 6 to cover almost the entire outer surface of the glass container main body 1 (excluding the mouth and bottom). Apply a first coating agent. After a drying time of 5 seconds to 10 minutes, the second coating agent is sprayed laterally and downward again using the downstream spray nozzle 7, and the second coating agent is applied on top of the first coating, thereby forming the coating of the present invention.
  • the treated glass container is completed.
  • a glass container refers to a container made of glass and used to contain drinks, food, and the like. Specific examples include glass bottles and glass containers for food storage, and the cross-sectional view of the body thereof may have a circular or polygonal shape.
  • the glass container body refers to a glass container that has not been coated or has been hot-end coated and has not been cold-end coated
  • a coated glass container refers to a glass container that has been coated with a cold-end coating according to the present invention. Refers to the glass container before it is attached.
  • a labeled glass container refers to a glass container with a label pasted on it, regardless of whether it is coated or not; however, the labeled glass container produced by the manufacturing method of the present invention is a glass container that has a label pasted on it after being coated. It is a glass container.
  • the first coating agent includes an adhesive substance.
  • adhesive substance as used herein means a substance that has the property of adhering an inorganic material such as glass to a solid lubricant contained in a second coating agent that is subsequently applied.
  • the adhesive substance of the first coating agent is not particularly limited as long as it can bond the inorganic material and the solid lubricant.
  • a specific example of the adhesive substance is a silane coupling agent.
  • a specific example of the silane coupling agent is represented by the general formula YSi(CH 3 ) 3 -nXn, where X is a halogen such as chlorine, OR (alkoxy group), or hydrogen, and Y is an organic compound that can react with organic compounds such as polymers. Residues such as vinyl, methacrylic, epoxy, amino, and mercapto groups.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
  • the concentration of the adhesive substance is preferably 0.01 to 1 mass%. If it is less than 0.01 mass%, the adhesive effect will be small, and if it is more than 1 mass%, the adhesive force will be increased more than necessary, the force that attracts the label glue through the second coating will be strong, and the label will not be easily peeled off. It becomes difficult.
  • the first coating agent can contain materials other than the adhesive substance to the extent that the effects of the present invention are not impaired, but it is preferable that it does not contain anything other than water, which is a solvent (excluding impurities, etc.). That is, the first coating agent is preferably an aqueous solution of an adhesive substance.
  • the second coating agent that imparts lubricity and scratch resistance includes a solid lubricant.
  • Glass containers may get scratches or other small scratches due to collisions between pieces of glass or contact with conveyance devices, and containers that are not slippery may be difficult to convey on conveyors or the like. For this reason, coating agents containing solid lubricants have traditionally been applied to glass containers.
  • a second coating agent containing a solid lubricant is applied.
  • the lubricity and scratch resistance imparting layer formed by applying the second coating agent is on the surface, at least a portion of the solid lubricant is exposed on the surface, making it easy to label.
  • releasability refers to the property that paper or synthetic resin coated with an adhesive, such as a pasted label, tack label, or sticker, can be easily peeled off from a glass container.
  • solid lubricants can be used, and examples thereof include polyethylene, polyethylene wax, modified polyethylene wax, carnauba wax, and the like.
  • the solid lubricant may be used as a mixture of two or more of these, or different types of solid lubricants may be applied in a layered manner.
  • a surfactant may be added to the second coating agent in order to disperse fine particles of the solid lubricant in water and form an emulsion state.
  • conventional surfactants such as potassium oleate can be used.
  • other additives such as solid plasticizers may be added, similar to conventional solid lubricant coatings.
  • the concentration of the solid lubricant in the second coating agent is preferably 0.01 to 10 mass%. If the concentration of the solid lubricant is less than 0.01 mass%, the effect of imparting lubricity and scratch resistance to the glass surface will be reduced, and if it exceeds 10 mass%, the viscosity of the coating agent will become too high, making it difficult to apply it to the glass surface. becomes difficult.
  • the solvent for the second coating agent is not particularly limited, but water is preferred.
  • a surfactant When a surfactant is used in the second coating agent, its concentration is preferably 0.01 mass% or more and 1.0 mass% or less based on the total amount of the second coating agent. If the concentration of the surfactant exceeds 1.0 mass%, the water resistance of the coating may be affected. Moreover, when the concentration of the surfactant is less than 0.01 mass%, the dispersibility of polyethylene may be affected.
  • the glass container body may or may not be coated with a hot end coating, but in the present invention, since the first coating agent can impart appropriate adhesion, the hot end coating It is preferable to apply the first coating agent directly to the surface of the glass container body that is not coated with the coating.
  • the coating agents used may be those conventionally used, such as tin compounds such as tin oxide and tin tetrachloride, titanium compounds such as titanium oxide and titanium tetrachloride, zirconium dioxide, etc. Examples include zirconium compounds such as zirconium chloride. Therefore, by applying these, a metal oxide layer containing at least one selected from tin oxide, titanium oxide, and zirconia oxide layer is formed.
  • Hot-end coating is carried out by applying a hot-end coating agent to the outer surface of a hot (400° C. to 600° C.) glass container immediately after molding, after the bottle making process and before the slow cooling process.
  • label glue such as a label, tack label, or sticker
  • a labeled glass container can be produced.
  • Adhesive components of the label glue include vinyl adhesives, acrylic adhesives, casein adhesives, starch pastes, etc.
  • vinyl adhesives Tokiwanol Z22H and the like can be used.
  • Materials for the label include high-quality paper, art paper, glossy paper, and the like.
  • the present invention is a coated glass container, which includes a glass container body, an adhesive layer formed by applying a first coating agent on the outer surface of the glass container body, and an adhesive layer (first coating layer). and a lubricity and scratch resistance imparting layer formed by applying a second coating agent.
  • the present invention is a labeled glass container in which a label is attached to the coated glass container.
  • FIG. 4 is a sectional view of a labeled glass container B in which a label 4 to which label glue 9 is attached is attached to a coated glass container of the present invention.
  • an adhesive layer 3 is disposed on almost the entire outer surface of the glass container body 1 (excluding the bottle mouth and bottom).
  • the adhesive layer 3 contains an adhesive substance.
  • the adhesive substance is derived from an adhesive substance contained in the first coating agent.
  • a lubricity and scratch resistance imparting layer 2 is disposed on the adhesive layer 3.
  • the lubricity and scratch resistance imparting layer 2 contains a solid lubricant.
  • the solid lubricant is the same as that contained in the second coating agent.
  • a label 4 to which label glue 9 is attached is pasted onto the slippery and scratch-resistant layer 2.
  • the label glue 9 is placed on the slipperiness and scratch resistance imparting layer 2, and the label 4 is placed on the label glue 9.
  • a substance derived from the hot end coating may be provided between the adhesive layer 3 and the outer surface of the glass container body 1 if necessary.
  • a hot end coating layer (hot end coating layer) can be provided on the glass surface.
  • the hot end coating layer is preferably a layer containing at least one of a tin compound, a titanium compound, and a zirconia compound, and the thickness of the layer is 2 nm to 50 nm, preferably 5 nm to 20 nm (expressed in units of CTU (Coating Thickness Units)). and 20 CTU to 80 CTU are preferred).
  • FIG. 5 shows a label 4 with label glue 9 attached to a conventional coated glass container (hot-end coated and then coated with a mixed coating agent containing a silane coupling agent and a solid lubricant).
  • FIG. 2 is a cross-sectional view of the surface state of a labeled glass container.
  • a hot end coating layer 10 is formed by hot coating on the surface 1a of the glass container body 1, and then a coating containing a silane coupling agent and a solid lubricant is applied.
  • a silane coupling agent-containing lubricity and scratch resistance imparting layer 22 made of particles 22a of a silane coupling agent-containing solid lubricant is formed.
  • the label may be difficult to remove from the glass container because the hot end coating has the property of attracting organic substances such as label glue.
  • the hot end coating has the property of attracting organic substances such as label glue.
  • a mixed coating agent containing a silane coupling agent and a solid lubricant is used, floating substances are generated due to long-term storage, as seen in the comparative examples described in the specification of this application. I can't.
  • an adhesive layer 3 containing an adhesive substance is formed on the surface 1a of the glass container body 1, and a coating containing solid lubricant particles 2a is applied thereon. By performing this step, the lubricity and scratch resistance imparting layer 2 is formed.
  • the amino-based silane coupling agent used when forming the adhesive layer 3 functions as an adhesive substance in the present invention, and can adhere the solid lubricant particles 2a and the surface 1a of the glass container body 1.
  • the label 4 to which the label glue 9 has been attached is pasted on the lubricity and scratch resistance imparting layer 2 made of solid lubricant.
  • the gap between the lubricity and scratch resistance imparting layer 2 and the label 4 becomes easy to peel off.
  • the lubricity and scratch resistance imparting layer 2 is described as being composed of granular solid lubricant particles, but the lubricity and scratch resistance imparting layer 2 is not granular but has an uneven structure. It may be a coating film without.
  • the thicknesses of the adhesive layer 3 and the lubricity and scratch resistance imparting layer 2 are not particularly limited, and may be the same thickness or different thicknesses.
  • Labeled glass containers manufactured using the coated glass containers of the present invention have labels that are difficult to peel off when used with normal glass containers, and when the labels are removed at the time of disposal, they can be removed cleanly without leaving any residue on the glass. It is possible. Also, the glass container is at a low temperature (for example, 7°C). It is characterized by being easy to peel at both room temperature (15-25°C) and high temperature (40°C).
  • Label removability evaluation material breakage rate
  • the corner of the label of the labeled glass bottle was peeled off with a fingernail, and the label was peeled off by picking it with fingers, and the label material breakage rate was calculated from the point at which the label broke.
  • the wood breakage rate was evaluated as " ⁇ ” if it was less than 5%, " ⁇ ” if it was 5% or more and less than 80%, and "x” if it was 80% or more.
  • the label material breakage rate was measured after the glass bottles were stored in a refrigerator at 7° C. and 35% humidity for one week after the label was pasted. This item is described as "easy peelability" in Table 1.
  • Examples 1 to 3 Apply a first coating agent containing an amino-based silane coupling agent (A0439 manufactured by Tokyo Kasei Co., Ltd.) to the surfaces of 50 ml glass bottles (20 bottles) without hot-end coating (surface temperature approximately 100°C) using an upstream spray device. do.
  • the first coating agent is a mixture of 0.2% by weight of an amino group silane coupling agent and 99.8% by weight of water.
  • a second coating containing a solid lubricant is applied by a downstream spray device.
  • the second coating agent is a mixture of 0.32% polyethylene wax, 0.08% by weight of an anionic surfactant (potassium oleate), and 99.6% by weight of water.
  • Labeled glass bottles were obtained by pasting vaporized paper with a length of 100 mm and a width of 60 mm as a label on the coated glass bottles (10 bottles) obtained by the method described above using glue (Tokiwanol Z22H). (Example 1).
  • both the first coating agent and the second coating agent were stored at room temperature for 10 days, and an experiment was conducted to confirm the condition, but no particular change was observed.
  • Examples 4-6 In FIG. 1, labeled glass bottles were obtained in the same manner as in Examples 1 to 3, except that before entering the lehr C, SnCl 4 was gasified and applied (hot end coating) to form a tin oxide film. Ta.
  • Comparative examples 1-2 Labeled glass bottles were obtained in the same manner as in Examples 4 to 6, except that the first coating containing silane was not performed in the cold end coating.
  • Comparative examples 3-4 Labeled glass bottles were obtained in the same manner as in Examples 1 to 3, except that hot end coating and cold end coating were not performed.
  • Comparative example 5 Labeled glass bottles were obtained in the same manner as in Comparative Examples 3 to 4, except that only hot end coating was performed by the method described in Examples 4 to 6.
  • Comparative examples 6-7 As a cold end coating, an aqueous solution mixture of 0.2% by weight of an amino-based silane coupling agent, 0.32% of polyethylene wax, 0.08% by weight of an anionic surfactant (potassium oleate), and water was used. Labeled glass bottles were obtained in the same manner as in Examples 1 to 3 except for coating. An experiment was also conducted in which the mixture was stored at room temperature for 10 days and the state of the mixture was confirmed. The photograph is shown in Figure 7. As you can see from the photo, floating particles were observed, indicating that it may be difficult to apply the coating solution evenly. In Table 1, those in which floating matter was observed were evaluated as "x" for storage stability.
  • Comparative examples 8-9 As a cold end coating, an aqueous solution mixture of 0.2% by weight of an amino-based silane coupling agent, 0.32% of polyethylene wax, 0.08% by weight of an anionic surfactant (potassium oleate), and water was applied. Labeled glass bottles were obtained in the same manner as in Examples 4-6.
  • the label has enough adhesive strength to be difficult to peel off during normal use, and can be removed cleanly without tearing.
  • the amount of water contained in the glue decreases, and the breaking strength increases, and instead of the glue being destroyed, the label is torn, and paper is more likely to remain in the glass container.
  • the coated glass container of the present invention minimized label tearing even after being stored in a refrigerator or the like, and could be peeled off cleanly regardless of the temperature of the glass container.
  • an aqueous solution mixture of an amino group silane coupling agent, polyethylene wax, anionic surfactant, and water generates suspended matter when stored for a long period of time. If this floating matter adheres to a glass container, it becomes a glass product with foreign matter adhering to it, which is undesirable. Additionally, floating objects may clog the spray nozzle. Furthermore, in a comparative example using a coating agent of this aqueous solution mixture, easy peelability was observed because the mixture was used immediately after preparation, but if suspended matter floated due to long-term storage, the coating formation became unstable. It is presumed that as a result, the effect of easy peelability cannot be obtained.
  • a glass container coated with a coating that has a degree of adhesion that is difficult to peel off during normal use and does not remain easily when removed and a method for manufacturing the same.
  • a highly stable coating agent can be provided.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The purpose of the present invention is to provide a glass container coated so as to have adhesiveness to resist detachment during normal use and to leave no residue when detached, and a method for the production thereof. Disclosed is a method for producing a coated glass container that includes a step for applying a first coating agent that contains an adhesive substance to an annealed glass container body and forming a first-coated glass container and a step for applying a second coating agent that contains a solid lubricant and imparts lubricity and scratch resistance to the first-coated glass container and forming a second-coated glass container.

Description

コーティング処理済ガラス容器およびその製造方法Coated glass container and its manufacturing method
　従来から徐冷炉の出口付近（いわゆるコールドエンド）でガラス容器の外面にコーティング剤を塗布するコーティング（いわゆるコールドエンドコーティング）が行われている。このようなコーティングを行うことで、ガラス容器に滑性や耐スクラッチ性などが付与され、ガラス容器の強度の低下を抑止する。コーティング剤はポリエチレン、ポリエチレンワックス、変性ポリエチレンワックス、カルナウバワックスなどの固体滑剤に界面活性剤を加えることによってこれらの微粒子を水中に分散させ、エマルジョン状態としたものである。 Conventionally, coating (so-called cold-end coating) has been performed in which a coating agent is applied to the outer surface of a glass container near the exit of a lehr (so-called cold end). By applying such a coating, lubricity and scratch resistance are imparted to the glass container, thereby preventing a decrease in the strength of the glass container. The coating agent is made by adding a surfactant to a solid lubricant such as polyethylene, polyethylene wax, modified polyethylene wax, or carnauba wax to disperse these fine particles in water to form an emulsion.
　上記のコールドエンドコーティングを行う場合、その前処理としていわゆるホットエンドコーティングを行う場合が多い。これは、徐冷炉の入り口付近において、成形直後の高温のガラス容器の外面にスズ化合物（主に四塩化スズ）又はチタン化合物（主に四塩化チタン）などを作用させ、ガラス容器の外面に酸化スズ又は酸化チタンなどの被膜を形成するものである。ホットエンドコーティングを行うことにより、コールドエンドコーティング被膜のガラス面への接着性が向上する。ガラスびんなどのガラス容器は、上記のホットエンドコーティング及びコールドエンドコーティングの両方を行った上にラベルを貼付する場合が多い。 When performing the above-mentioned cold end coating, so-called hot end coating is often performed as a pretreatment. This is done by applying a tin compound (mainly tin tetrachloride) or a titanium compound (mainly titanium tetrachloride) to the outer surface of the high-temperature glass container immediately after forming, near the entrance of the lehr, and applying tin oxide to the outer surface of the glass container. Alternatively, a film of titanium oxide or the like is formed. Hot-end coating improves the adhesion of the cold-end coating film to the glass surface. Glass containers such as glass bottles are often coated with both the above-mentioned hot-end coating and cold-end coating and then labeled.
　しかしながら、ラベルの接着度が高すぎると、使用済のガラス容器をリサイクルするため、貼付されたラベルを剥がす際にラベル自体が切れて残ってしまう問題がある。特に、冷蔵保管されたガラス容器の場合、ラベルとガラス容器本体とを接着する糊に含まれる水分量が少なくなるため、糊自体の引っ張り強度が常温時よりも高くなり、相対的に強度が弱いラベル自体（特に紙材料のラベル）が破れ、ラベルの一部がガラス容器本体に残ってしまう。ラベルの一部が残ったガラス容器を再利用のため粉砕した際は、このラベルの残りが混入してガラス屑（カレット）の品質に影響を及ぼす問題がある。このため、ラベルの易剥離性（きれいに剥がしやすくする特性）を向上するためガラスの表面処理に関する技術が多く開発されている。 However, if the degree of adhesion of the label is too high, there is a problem that the label itself will be cut and left behind when the attached label is peeled off in order to recycle used glass containers. In particular, in the case of refrigerated glass containers, the amount of water contained in the glue that bonds the label and the glass container body is reduced, so the tensile strength of the glue itself is higher than at room temperature, making it relatively weak. The label itself (especially a label made of paper material) is torn and a portion of the label remains on the body of the glass container. When a glass container with a portion of the label remaining is crushed for reuse, there is a problem in that the remaining label gets mixed in and affects the quality of the glass waste (cullet). For this reason, many techniques related to surface treatment of glass have been developed in order to improve the easy peelability of labels (characteristics that make them easy to peel off cleanly).
　特許文献１には、酸価が１０～２５ｍｇ－ＫＯＨ／ｇである乳化された状態のポリエチレンワックスとアミノ基を有するシランカップリング剤とを含有することを特徴とする水性組成物であり、ラベル易剥離性ガラス表面形成用コーティング組成物に関する発明が開示されている。しかし、特許文献１に開示されているコーティング組成物は、混合液が時間経過で変化する恐れがあり、コーティング組成物の安定性が低い。 Patent Document 1 discloses an aqueous composition characterized by containing an emulsified polyethylene wax having an acid value of 10 to 25 mg-KOH/g and a silane coupling agent having an amino group, and which has a label. An invention related to a coating composition for forming an easily peelable glass surface is disclosed. However, in the coating composition disclosed in Patent Document 1, the mixed liquid may change over time, and the stability of the coating composition is low.
　特許文献２には、ガラス容器の外面に固体滑剤を含む第一のコーティング剤を塗布するステップと、易剥離性物質（シランカップリング剤など）を含む第二のコーティング剤を塗布するステップとを有することを特徴とするコーティング方法が開示されている。当該技術は、易剥離性を向上させたものではあるが、昨今のリサイクルの効率を促進するためには、さらなる易剥離性の向上が求められている。
　特に、ホットエンドコーティングは有機物を強く引き付けるので、ラベル糊も強く引き付けられてしまい、ラベルが剥がれにくくなる。一方、ホットエンドコーティングを行わないと、滑性を付与するための酸化ポリエチレン系コールドエンドコーティングの付着が弱くなるという問題がある。 Patent Document 2 describes the steps of applying a first coating agent containing a solid lubricant to the outer surface of a glass container, and applying a second coating agent containing an easily peelable substance (such as a silane coupling agent). A coating method is disclosed, which is characterized in that the coating method comprises: Although this technology has improved easy peelability, further improvement in easy peelability is required in order to promote recycling efficiency these days.
In particular, since the hot end coating strongly attracts organic matter, the label adhesive is also strongly attracted, making it difficult for the label to peel off. On the other hand, if hot end coating is not performed, there is a problem in that the adhesion of the oxidized polyethylene cold end coating for imparting lubricity becomes weak.
特開２００４－１６１９９３号公報Japanese Patent Application Publication No. 2004-161993 特開２００４－３１５２８５号公報Japanese Patent Application Publication No. 2004-315285
　本発明の課題は、ラベルが通常の使用では剥がれにくい程度の付着性を有し、剥がそうとしたときにラベルがガラス容器に残りにくいコーティング処理を施したガラス容器及びその製造方法を提供することが目的である。また、コールドエンドコーティング剤の安定性を保つことができるコーティング方法を提供することが目的である。 An object of the present invention is to provide a glass container coated with a coating that has a label that is difficult to peel off during normal use and does not remain on the glass container when the label is peeled off, and a method for manufacturing the same. is the purpose. Another object is to provide a coating method that can maintain the stability of the cold-end coating agent.
　本発明者らは、鋭意研究を重ねた結果、コールドエンドコーティングの工程において、接着性物質を含む第一コーティング剤を塗布し、その後、固体滑剤を含む第二コーティング剤を塗布した上で糊付ラベルを貼り付けることにより、ホットエンドコーティングがなくても、通常の使用ではラベルが剥がれにくい程度の付着性を有し、かつ、使用後にラベルを剥がす際には、ガラス容器表面にラベルが残りにくくなることを見出し、本発明に至った。すなわち、本発明は、以下の通りである。 As a result of extensive research, the present inventors have discovered that in the cold-end coating process, a first coating agent containing an adhesive substance is applied, and then a second coating agent containing a solid lubricant is applied and then glued. By pasting the label, even without a hot-end coating, the label has a level of adhesion that makes it difficult to peel off during normal use, and when the label is removed after use, it does not remain on the surface of the glass container. We have discovered that this is the case, and have arrived at the present invention. That is, the present invention is as follows.
　すなわち、本発明は、以下を包含する。
［１］　徐冷済ガラス容器本体に接着性物質を含む第一コーティング剤を塗布し、第一コーティング処理済ガラス容器を形成する工程と、
　前記第一コーティング処理済ガラス容器に、固体滑剤を含み、滑性及び耐スクラッチ性を付与する第二コーティング剤を塗布し、第二コーティング処理済ガラス容器を形成する工程とを含む、コーティング処理済ガラス容器の製造方法。
［２］　前記接着性物質がアミノ基シランカップリング剤を含む、［１］に記載のコーティング処理済ガラス容器の製造方法。
［３］　前記固体滑剤はポリエチレンワックスを含む、［１］又は［２］に記載のコーティング処理済ガラス容器の製造方法。
［４］　前記第二コーティング剤は界面活性剤を含む、［１］乃至［３］のいずれか一項に記載のコーティング処理済ガラス容器の製造方法。
［５］　ガラス容器本体のガラス表面に前記第一コーティング剤を塗布する、［１］乃至［４］のいずれか一項に記載のコーティング処理済ガラス容器の製造方法。
［６］　第一コーティング塗布後前記第一コーティング剤が乾燥してから、前記第二コーティング剤を塗布する工程を行う、［１］乃至［５］のいずれか一項に記載のコーティング処理済ガラス容器の製造方法。
［７］　［１］乃至［６］のいずれか一項に記載のコーティング処理済ガラス容器に、糊付ラベルを貼り付ける工程を含む、ラベル付ガラス容器の製造方法。
［８］　コーティング処理済ガラス容器であって、
　ガラス容器本体と、
　前記ガラス容器本体に配置される接着層と、
　前記接着層の上に配置される滑性及び耐スクラッチ性付与層とを含む、コーティング処理済ガラス容器。
［９］　［８］に記載のコーティング処理済ガラス容器の前記滑性及び耐スクラッチ性付与層の表面に糊付ラベルを直接貼り付けた、ラベル付ガラス容器。 That is, the present invention includes the following.
[1] A step of applying a first coating agent containing an adhesive substance to the annealed glass container body to form a first coated glass container;
applying a second coating agent containing a solid lubricant and imparting lubricity and scratch resistance to the first coated glass container to form a second coated glass container. Method of manufacturing glass containers.
[2] The method for producing a coated glass container according to [1], wherein the adhesive substance contains an amino group silane coupling agent.
[3] The method for producing a coated glass container according to [1] or [2], wherein the solid lubricant contains polyethylene wax.
[4] The method for manufacturing a coated glass container according to any one of [1] to [3], wherein the second coating agent contains a surfactant.
[5] The method for manufacturing a coated glass container according to any one of [1] to [4], wherein the first coating agent is applied to the glass surface of the glass container body.
[6] The coated glass according to any one of [1] to [5], wherein the step of applying the second coating agent is performed after the first coating agent has dried after applying the first coating. Method of manufacturing containers.
[7] A method for producing a labeled glass container, comprising the step of attaching a glued label to the coated glass container according to any one of [1] to [6].
[8] A coated glass container,
A glass container body,
an adhesive layer disposed on the glass container body;
A coated glass container comprising a lubricity and scratch resistance imparting layer disposed on the adhesive layer.
[9] A labeled glass container, wherein a glued label is directly attached to the surface of the lubricity and scratch resistance imparting layer of the coated glass container according to [8].
　本発明のコーティング処理済ガラス容器は、特定のコールドエンドコーティングを施しているため、通常の使用ではラベルは剥がれにくい程度の付着性を有し、かつ剥がしたときにガラス容器表面にラベルの一部が残りにくい（きれいに剥がせる）ラベル付きのガラス容器を提供することができる。また、当該コーティングに使用するコーティング剤及びコーティング方法を用いることにより、コーティング液を安定に保存でき、コーティングにムラが発生しないという特徴も有する。 The coated glass containers of the present invention are coated with a specific cold-end coating, so the label has a degree of adhesion that is difficult to peel off during normal use, and when it is peeled off, a portion of the label remains on the surface of the glass container. We can provide glass containers with labels that do not leave any residue (and can be removed cleanly). Furthermore, by using the coating agent and coating method used in the coating, the coating solution can be stored stably and the coating does not become uneven.
本発明のコーティング処理済ガラス容器の製造方法の一例を示すフローチャートである。1 is a flowchart showing an example of a method for manufacturing a coated glass container of the present invention. 本発明のコーティング処理済ガラス容器の製造方法におけるスプレーノズルによるコールドエンドコーティングの説明図である（上方向から見た図）。FIG. 2 is an explanatory diagram of cold-end coating using a spray nozzle in the method for manufacturing a coated glass container of the present invention (view from above). 本発明のコーティング処理済ガラス容器の製造方法におけるスプレーノズルによるコールドエンドコーティングの説明図である（横方向から見た図）。FIG. 3 is an explanatory diagram of cold-end coating using a spray nozzle in the method for manufacturing a coated glass container of the present invention (view from the side). 本発明のコーティング処理をしたラベル付ガラス容器の断面図である。FIG. 1 is a cross-sectional view of a labeled glass container that has been coated according to the present invention. 従来のコーティング処理をしたラベル付ガラス容器の表面状態の断面図である。FIG. 2 is a cross-sectional view of the surface state of a labeled glass container that has been subjected to a conventional coating treatment. 本発明のコーティング処理をしたラベル付ガラス容器の表面状態の断面図である。FIG. 2 is a cross-sectional view of the surface state of a labeled glass container that has been subjected to the coating treatment of the present invention. 混合したコーティング剤を１０日間保管した状態を示す写真である。It is a photograph showing the state in which the mixed coating agent was stored for 10 days.
　以下、本発明について、より詳細に説明するが、本発明の技術思想の範囲内で適宜修正できるものである。 The present invention will be described in more detail below, but it can be modified as appropriate within the scope of the technical idea of the present invention.
＜コーティング処理済ガラス容器及びラベル付ガラス容器の製造方法＞
　本発明は、徐冷済ガラス容器本体に接着性物質を含む第一コーティング剤を塗布し、第一コーティング処理済ガラス容器を形成する工程と、第一コーティング処理済ガラス容器に、固体滑剤を含み、滑性及び耐スクラッチ性を付与する第二コーティング剤を塗布し、第二コーティング処理済ガラス容器を形成する工程とを有することを特徴とする、コーティング処理済ガラス容器の製造方法である。 <Method for manufacturing coated glass containers and labeled glass containers>
The present invention includes a step of applying a first coating agent containing an adhesive substance to a slowly cooled glass container body to form a first coated glass container, and a step of applying a solid lubricant to the first coated glass container. , and forming a second coated glass container by applying a second coating agent that imparts lubricity and scratch resistance.
　図１は、従来から実施されているガラス容器の製造方法の一例を示すフローチャートである。まず、ガラスの材料となるガラスカレット等を熔融炉Ａにおいて熔融する。熔融したガラスの温度調整を行い、熔融炉Ａから得られたガラスゴブを製びん機Ｂにおいてガラス容器を成形する。成形されたガラス容器は残存するひずみを抜くため、徐冷炉Ｃに運ばれる。徐冷炉Ｃにおいて、ひずみが抜かれたガラス容器は、検査機Ｄにおいて検査され、包装処理Ｅが行われた後、出荷Ｆされる。ガラス容器にラベルを貼り付ける場合は、ガラス容器の製造工場の出荷Ｆ後にガラス容器の購入先で糊が付着されたラベルを貼り付ける（図示しない）。 FIG. 1 is a flowchart showing an example of a conventional method for manufacturing a glass container. First, glass cullet and the like, which are glass materials, are melted in a melting furnace A. The temperature of the molten glass is adjusted, and the glass gob obtained from the melting furnace A is molded into a glass container in the bottle making machine B. The formed glass container is transported to an annealing furnace C to remove any remaining strain. The glass container from which the strain has been removed in the slow cooling furnace C is inspected by an inspection machine D, subjected to packaging treatment E, and then shipped F. When a label is attached to a glass container, a label with glue is attached at the place of purchase of the glass container after the glass container is shipped from a manufacturing factory (not shown).
　ガラス容器のガラスの外面に滑性及び耐スクラッチ性が付与するため、および、ラベルの接着力を調整するために、必要に応じ徐冷炉Ｃに入る前にホットエンドコーティング（ＨＥＣ）を実施し、その後、徐冷炉Ｃから出た後、検査機Ｄに入る前までにコールドエンドコーティングを実施する。
　従来技術としては、ホットエンドコーティングは、塩化スズをガス化して、高温のガラス容器に吹きかけるものであり、コールドエンドコーティングは、ポリエチレンワックス等を含む水溶液をスプレー等で吹きかけるものである。
　本発明においては、コールドエンドコーティングを２回に分けて実施することが特徴である。具体的には、コールドエンドコーティング工程において、接着性物質を含む第一コーティング剤を塗布する工程と、固体滑剤を含み、滑性及び耐スクラッチ性を付与する第二コーティング剤を塗布する工程とを実施し、第一コーティング剤を塗布する工程は、第二コーティング剤を塗布する工程よりも前に実施することが特徴である。このようにすることにより、糊付ラベルは、固体滑剤の少なくとも一部が表面に出ている状態で貼り付けることにより、ラベルに付着している糊との接着力を高くなりすぎないようにすることができ、廃棄時等にラベルを剥がしやすくする。 In order to impart lubricity and scratch resistance to the outer surface of the glass of the glass container and to adjust the adhesive strength of the label, hot end coating (HEC) is applied as necessary before entering the lehr C, and then After leaving the lehr C and before entering the inspection machine D, cold end coating is performed.
As conventional techniques, hot-end coating involves gasifying tin chloride and spraying it onto a hot glass container, and cold-end coating involves spraying an aqueous solution containing polyethylene wax or the like.
The present invention is characterized in that cold end coating is performed in two steps. Specifically, in the cold-end coating process, a step of applying a first coating agent containing an adhesive substance and a step of applying a second coating agent containing a solid lubricant and imparting lubricity and scratch resistance are performed. The step of applying the first coating agent is characterized in that the step of applying the first coating agent is performed before the step of applying the second coating agent. By doing this, the adhesive label is pasted with at least a portion of the solid lubricant exposed on the surface, thereby preventing the adhesive force with the adhesive attached to the label from becoming too high. This makes it easier to remove the label when disposing of the product.
　本発明のコーティング処理済ガラス容器の製造方法においては、製びん機Ｂにより製造されたガラス容器本体は温度が４００～６００℃であり、その後徐冷炉を経たガラス容器の温度は７０～１２０℃となる。温度が下がりひずみが抜かれたガラス容器に上流スプレーノズルにより横方向及び下方向に向かってスプレーし、ガラス容器の外面のほぼ全体（口部、底部を除く）に第一コーティング剤を塗布する。また、第二コーティング剤を塗布する工程は、下流スプレーノズルにより、第一コーティングと同じ塗布範囲で行う。 In the method for manufacturing coated glass containers of the present invention, the temperature of the glass container body manufactured by bottle making machine B is 400 to 600°C, and the temperature of the glass container after passing through the slow cooling furnace is 70 to 120°C. . The first coating agent is sprayed laterally and downwardly onto the glass container whose temperature has been lowered and the strain has been released using an upstream spray nozzle to apply the first coating agent to almost the entire outer surface of the glass container (excluding the mouth and bottom). Further, the step of applying the second coating agent is performed using a downstream spray nozzle in the same application area as the first coating.
　図２、図３は、本発明のコーティング処理済ガラス容器の製造方法におけるスプレーノズルによるコーティング（コールドエンドコーティング工程におけるコーティング）の説明図である。
　ひずみが抜かれたガラス容器本体１は、移動手段である移動するコンベア５の上に配置され、徐冷炉８の出口から検査機に向けて進行する（図２）。上流スプレーノズル６と下流スプレーノズル７はガラス容器本体１の進行方向と垂直する方向でガラス容器列間を移動しスプレーを行う（図３）。ガラス容器本体１の口付近の位置から、上流スプレーノズル６で第一コーティング剤を横方向及び下方向に向かってスプレーし、ガラス容器本体１の外面のほぼ全体（口部、底部を除く）に第一コーティング剤を塗布する。５秒～１０分の乾燥時間を経て、再び下流スプレーノズル７で第二コーティング剤を横方向及び下方に向かってスプレーし、第一コーティングの上に第二コーティング剤を塗布し、本発明のコーティング処理済ガラス容器が完成する。 FIGS. 2 and 3 are explanatory diagrams of coating using a spray nozzle (coating in the cold-end coating step) in the method for manufacturing a coated glass container of the present invention.
The glass container body 1 from which the strain has been removed is placed on a moving conveyor 5, which is a moving means, and advances from the outlet of the lehr 8 toward the inspection machine (FIG. 2). The upstream spray nozzle 6 and the downstream spray nozzle 7 move between the rows of glass containers in a direction perpendicular to the traveling direction of the glass container body 1 and perform spraying (FIG. 3). From a position near the mouth of the glass container main body 1, the first coating agent is sprayed laterally and downwardly using the upstream spray nozzle 6 to cover almost the entire outer surface of the glass container main body 1 (excluding the mouth and bottom). Apply a first coating agent. After a drying time of 5 seconds to 10 minutes, the second coating agent is sprayed laterally and downward again using the downstream spray nozzle 7, and the second coating agent is applied on top of the first coating, thereby forming the coating of the present invention. The treated glass container is completed.
　なお、本明細書において、ガラス容器とは、ガラスを材料として成形され、飲料や食料などを入れるものをいう。具体例としては、例えば、ガラスびんや食品保存用ガラス容器などであり、それらの胴部横断面図が円形、多角形などの形状がある。
　ガラス容器本体とは、コーティング未処理、又はホットエンドコーティング済であって、コールドエンドコーティング未処理のガラス容器をいい、コーティング処理済ガラス容器とは、本発明のコールドエンドコーティングを施したラベルを貼り付ける前のガラス容器をいう。
　ラベル付ガラス容器とは、コーティング処理をする、コーティング処理しないにかかわらずラベルを貼り付けたガラス容器を意味するが、本発明の製造方法によるラベル付ガラス容器は、コーティング処理をした後にラベルを貼り付けたガラス容器である。 Note that in this specification, a glass container refers to a container made of glass and used to contain drinks, food, and the like. Specific examples include glass bottles and glass containers for food storage, and the cross-sectional view of the body thereof may have a circular or polygonal shape.
The glass container body refers to a glass container that has not been coated or has been hot-end coated and has not been cold-end coated, and a coated glass container refers to a glass container that has been coated with a cold-end coating according to the present invention. Refers to the glass container before it is attached.
A labeled glass container refers to a glass container with a label pasted on it, regardless of whether it is coated or not; however, the labeled glass container produced by the manufacturing method of the present invention is a glass container that has a label pasted on it after being coated. It is a glass container.
［第一コーティング剤］
　本発明において、第一コーティング剤は、接着性物質を含む。ここでいう接着性物質とは、ガラス等の無機材料と、そのあとに塗布する第二コーティング剤に含まれる固体滑剤とを接着する特性を有する物質を意味する。
　第一コーティング剤の接着性物質は、無機材料と固体滑剤とを接着することができるものであれば、特に限定されるものではない。 [First coating agent]
In the present invention, the first coating agent includes an adhesive substance. The term "adhesive substance" as used herein means a substance that has the property of adhering an inorganic material such as glass to a solid lubricant contained in a second coating agent that is subsequently applied.
The adhesive substance of the first coating agent is not particularly limited as long as it can bond the inorganic material and the solid lubricant.
　接着性物質の具体例として、シランカップリング剤が挙げられる。シランカップリング剤の具体例は一般式ＹＳｉ（ＣＨ３）３－ｎＸｎで表され、Ｘは塩素などハロゲン、ＯＲ（アルコキシ基）又は水素であり、Ｙは高分子など有機化合物と反応しうる有機残基で、ビニル、メタクリル、エポキシ、アミノ、メルカプト基などである。シランカップリング剤としては、例えばビニルトリメトキシシラン、ビニルトリエトキシシラン、２－（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルメチルジメトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルトリメトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１、３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩、特殊アミノシラン、３－ウレイドプロピルトリエトキシシラン、３－クロロプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシランが挙げられる。 A specific example of the adhesive substance is a silane coupling agent. A specific example of the silane coupling agent is represented by the general formula YSi(CH 3 ) 3 -nXn, where X is a halogen such as chlorine, OR (alkoxy group), or hydrogen, and Y is an organic compound that can react with organic compounds such as polymers. Residues such as vinyl, methacrylic, epoxy, amino, and mercapto groups. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Ethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2( aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl -3-Aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane , 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatepropyltriethoxysilane.
　接着性物質の濃度は０．０１～１ｍａｓｓ％が好ましい。０．０１ｍａｓｓ％よりも少ないと接着性効果が小さく、１ｍａｓｓ％よりも多くすると必要以上に接着力が高まり、第２コーティングを介してラベル糊を引きつける力が強くなり、ラベルを容易に剥がすことが難しくなる。 The concentration of the adhesive substance is preferably 0.01 to 1 mass%. If it is less than 0.01 mass%, the adhesive effect will be small, and if it is more than 1 mass%, the adhesive force will be increased more than necessary, the force that attracts the label glue through the second coating will be strong, and the label will not be easily peeled off. It becomes difficult.
　第一コーティング剤は、本発明の効果を損なわない程度に接着性物質以外の材料を含むことができるが、溶媒である水以外を含まない（不純物等を除く）ことが好ましい。すなわち、第一コーティング剤は、接着性物質の水溶液であることが好ましい。 The first coating agent can contain materials other than the adhesive substance to the extent that the effects of the present invention are not impaired, but it is preferable that it does not contain anything other than water, which is a solvent (excluding impurities, etc.). That is, the first coating agent is preferably an aqueous solution of an adhesive substance.
［第二コーティング剤］
　滑性及び耐スクラッチ性を付与する第二コーティング剤は、固体滑剤を含む。ガラス容器は、ガラス同士の衝突や搬送装置などとの接触によりスクラッチなどの細かな傷が入る場合があり、また、滑りが悪い容器はコンベアなどでの搬送などが困難になる場合がある。そのため、従来から固体滑剤を含むコーティング剤をガラス容器に塗布することが行われてきた。
　本発明においては、第一コーティング剤を塗布した後で、固体滑剤を含む第二コーティング剤を塗布する。なお、本発明においては、第二コーティング剤に塗布され形成される滑性及び耐スクラッチ性付与層が表面にあることにより、固体滑剤の少なくとも一部が表面に出ている状態により、ラベルを容易に剥離させる剥離性の機能を付与することができる。なお、本明細書において剥離性とは、貼り付けられたラベル、タックラベル、シール等粘着剤が塗布された紙や合成樹脂がガラス容器から容易に剥がせる性質をいう。 [Second coating agent]
The second coating agent that imparts lubricity and scratch resistance includes a solid lubricant. Glass containers may get scratches or other small scratches due to collisions between pieces of glass or contact with conveyance devices, and containers that are not slippery may be difficult to convey on conveyors or the like. For this reason, coating agents containing solid lubricants have traditionally been applied to glass containers.
In the present invention, after applying the first coating agent, a second coating agent containing a solid lubricant is applied. In addition, in the present invention, since the lubricity and scratch resistance imparting layer formed by applying the second coating agent is on the surface, at least a portion of the solid lubricant is exposed on the surface, making it easy to label. It is possible to impart a releasability function that allows the material to be peeled off. In this specification, the term "releasability" refers to the property that paper or synthetic resin coated with an adhesive, such as a pasted label, tack label, or sticker, can be easily peeled off from a glass container.
　固体滑剤は、従来周知のものを使用でき、例えば、ポリエチレン、ポリエチレンワックス、変性ポリエチレンワックス、カルナウバワックスなどが挙げられる。固体滑剤は、これら２種以上を混合して用いてもよいし、異種の固体滑剤を積層するように塗布させてもよい。 Conventionally known solid lubricants can be used, and examples thereof include polyethylene, polyethylene wax, modified polyethylene wax, carnauba wax, and the like. The solid lubricant may be used as a mixture of two or more of these, or different types of solid lubricants may be applied in a layered manner.
　本発明においては、固体滑剤の微粒子を水中に分散させ、エマルジョン状態とするために界面活性剤を第二コーティング剤に添加してもよい。界面活性剤としては、例えばオレイン酸カリウムなどの従来と同様のものを用いることができる。さらに、従来の固体滑剤コーティング剤と同様に、固体可塑剤などの他の添加剤を加えてもよい。 In the present invention, a surfactant may be added to the second coating agent in order to disperse fine particles of the solid lubricant in water and form an emulsion state. As the surfactant, conventional surfactants such as potassium oleate can be used. Additionally, other additives such as solid plasticizers may be added, similar to conventional solid lubricant coatings.
　第二コーティング剤の固体滑剤の濃度は０．０１～１０ｍａｓｓ％であることが好ましい。固体滑剤の濃度が０．０１ｍａｓｓ％よりも少ないと、ガラス面に滑性、耐スクラッチ性を付与する効果が小さくなり、１０ｍａｓｓ％を越えるとコーティング剤の粘性が大きくなりすぎ、ガラス面に塗布するのが困難となる。
　第二コーティング剤の溶媒は、特に限定されるものではないが、水が好ましい。 The concentration of the solid lubricant in the second coating agent is preferably 0.01 to 10 mass%. If the concentration of the solid lubricant is less than 0.01 mass%, the effect of imparting lubricity and scratch resistance to the glass surface will be reduced, and if it exceeds 10 mass%, the viscosity of the coating agent will become too high, making it difficult to apply it to the glass surface. becomes difficult.
The solvent for the second coating agent is not particularly limited, but water is preferred.
　第二コーティング剤に界面活性剤を用いる場合、その濃度は、第二コーティング剤全量に対して好ましくは０．０１ｍａｓｓ％以上であり、１．０ｍａｓｓ％以下である。界面活性剤の濃度が１．０ｍａｓｓ％を超える場合、コーティングの耐水性に影響がある場合がある。また、界面活性剤の濃度が０．０１ｍａｓｓ％未満である場合、ポリエチレンの分散性に影響がある場合がある。 When a surfactant is used in the second coating agent, its concentration is preferably 0.01 mass% or more and 1.0 mass% or less based on the total amount of the second coating agent. If the concentration of the surfactant exceeds 1.0 mass%, the water resistance of the coating may be affected. Moreover, when the concentration of the surfactant is less than 0.01 mass%, the dispersibility of polyethylene may be affected.
　本発明において、ガラス容器本体はホットエンドコーティングを施したものでもよいし、施さないものでもよいが、本発明においては、第一コーティング剤が適度な接着性付与することができるため、ホットエンドコーティングを施さないガラス容器本体の表面に直接に前記第一コーティング剤を塗布することが好ましい。
　ホットエンドコーティングをする場合は、用いられるコーティング剤は従来から用いられているものでよく、例えば、酸化スズや四塩化スズ等のスズ化合物、酸化チタンや四塩化チタン等のチタン化合物、二酸化ジルコニウムや塩化ジルコニウム等のジルコニウム化合物が挙げられる。
　したがって、これらを塗布することにより、酸化スズ、酸化チタン、酸化ジルコニア層から選択される少なくとも一種を含む金属酸化物層を形成することになる。
　ホットエンドコーティングは、製びん工程の後、徐冷工程の前において、成形直後の高温（４００℃～６００℃）のガラス容器の外面にホットエンドコーティングのコーティング剤を塗布することにより実施する。 In the present invention, the glass container body may or may not be coated with a hot end coating, but in the present invention, since the first coating agent can impart appropriate adhesion, the hot end coating It is preferable to apply the first coating agent directly to the surface of the glass container body that is not coated with the coating.
In the case of hot-end coating, the coating agents used may be those conventionally used, such as tin compounds such as tin oxide and tin tetrachloride, titanium compounds such as titanium oxide and titanium tetrachloride, zirconium dioxide, etc. Examples include zirconium compounds such as zirconium chloride.
Therefore, by applying these, a metal oxide layer containing at least one selected from tin oxide, titanium oxide, and zirconia oxide layer is formed.
Hot-end coating is carried out by applying a hot-end coating agent to the outer surface of a hot (400° C. to 600° C.) glass container immediately after molding, after the bottle making process and before the slow cooling process.
　本発明のコーティング処理済ガラス容器の製造方法により製造されたコーティング処理済ガラス容器にさらにラベル、タックラベル、シールなど粘着性の有する材料（ラベル糊など）を塗布した紙や樹脂を貼り付けることにより、ラベル付ガラス容器を製造することができる。
　ラベル糊の粘着成分としては、ビニル系接着剤、アクリル系接着剤、カゼイン系接着剤、でんぷん糊などが挙げられ、例えば、ビニル系接着剤ではトキワノールＺ２２Ｈなどを使用することができる。
　また、ラベルの材料としては、上質紙、アート紙、光沢紙などが挙げられる。 By further pasting paper or resin coated with an adhesive material (label glue, etc.) such as a label, tack label, or sticker to the coated glass container manufactured by the method for manufacturing a coated glass container of the present invention. , a labeled glass container can be produced.
Adhesive components of the label glue include vinyl adhesives, acrylic adhesives, casein adhesives, starch pastes, etc. For example, as vinyl adhesives, Tokiwanol Z22H and the like can be used.
Materials for the label include high-quality paper, art paper, glossy paper, and the like.
＜コーティング処理済ガラス容器及びラベル付ガラス容器＞
　本発明は、コーティング処理済ガラス容器であって、ガラス容器本体と、ガラス容器本体の外側の表面に配置される第一コーティング剤塗布によって形成される接着層と、接着層（第一コーティング層）の上に配置され、第二コーティング剤塗布によって形成される滑性及び耐スクラッチ性付与層とを含む、コーティング処理済ガラス容器である。そして、本発明は上記コーティング処理済ガラス容器にラベルを貼り付けたラベル付ガラス容器である。 <Coated glass containers and labeled glass containers>
The present invention is a coated glass container, which includes a glass container body, an adhesive layer formed by applying a first coating agent on the outer surface of the glass container body, and an adhesive layer (first coating layer). and a lubricity and scratch resistance imparting layer formed by applying a second coating agent. The present invention is a labeled glass container in which a label is attached to the coated glass container.
　図４は、本発明のコーティング処理済ガラス容器に、ラベル糊９が付着したラベル４を貼り付けたラベル付ガラス容器Ｂの断面図である。図４に示すように、ガラス容器本体１の外面のほぼ全体（瓶口、底部を除く）に接着層３が配置されている。接着層３は、接着性物質を含むものである。接着性物質は、第一コーティング剤に含まれる接着性物質由来のものである。また、接着層３の上に滑性及び耐スクラッチ性付与層２が配置されている。滑性及び耐スクラッチ性付与層２は、固体滑剤を含むものである。固体滑剤は、上記第二コーティング剤に含まれるものと同様である。滑性及び耐スクラッチ性付与層２の上にラベル糊９が付着したラベル４を貼り付けている。したがって、滑性及び耐スクラッチ性付与層２の上には、ラベル糊９が配置され、ラベル糊９の上にラベル４が配置されている。図４では図示しないが、必要によりホットエンドコーティング由来の物質が接着層３とガラス容器本体１の外側の表面との間に設けられていてもよい。 FIG. 4 is a sectional view of a labeled glass container B in which a label 4 to which label glue 9 is attached is attached to a coated glass container of the present invention. As shown in FIG. 4, an adhesive layer 3 is disposed on almost the entire outer surface of the glass container body 1 (excluding the bottle mouth and bottom). The adhesive layer 3 contains an adhesive substance. The adhesive substance is derived from an adhesive substance contained in the first coating agent. Furthermore, a lubricity and scratch resistance imparting layer 2 is disposed on the adhesive layer 3. The lubricity and scratch resistance imparting layer 2 contains a solid lubricant. The solid lubricant is the same as that contained in the second coating agent. A label 4 to which label glue 9 is attached is pasted onto the slippery and scratch-resistant layer 2. Therefore, the label glue 9 is placed on the slipperiness and scratch resistance imparting layer 2, and the label 4 is placed on the label glue 9. Although not shown in FIG. 4, a substance derived from the hot end coating may be provided between the adhesive layer 3 and the outer surface of the glass container body 1 if necessary.
　必須ではないが、ガラス表面にホットエンドコーティングによる層（ホットエンドコーティング層）を設けることができる。ホットエンドコーティング層は、スズ化合物、チタン化合物及びジルコニア化合物の少なくとも一種を含む層が好ましく、層の厚さは、２ｎｍ～５０ｎｍ、好ましいのは５ｎｍ～２０ｎｍ（ＣＴＵ（Ｃｏａｔｉｎｇ　Ｔｈｉｃｋｎｅｓｓ　Ｕｎｉｔｓ）の単位で表すと２０ＣＴＵ～８０ＣＴＵが好ましい）である。 Although not essential, a hot end coating layer (hot end coating layer) can be provided on the glass surface. The hot end coating layer is preferably a layer containing at least one of a tin compound, a titanium compound, and a zirconia compound, and the thickness of the layer is 2 nm to 50 nm, preferably 5 nm to 20 nm (expressed in units of CTU (Coating Thickness Units)). and 20 CTU to 80 CTU are preferred).
　図５は、従来のコーティング処理済ガラス容器（ホットエンドコーティングした上で、シランカップリング剤と固体滑剤とを含む混合コーティング剤を塗布したもの）にラベル糊９が付着したラベル４を貼り付けたラベル付ガラス容器の表面状態の断面図である。図５に示すように、従来のコーティング処理済ガラス容器は、ガラス容器本体１の表面１ａに、ホットコーティングによるホットエンドコーティング層１０をした上で、シランカップリング剤及び固体滑剤を含むコーティングを行うことによりシランカップリング剤含有固体滑剤の粒子２２ａからなるシランカップリング剤含有滑性及び耐スクラッチ性付与層２２を形成する。この態様のラベル付ガラス容器は、ホットエンドコーティングにラベル糊などの有機物を引き付ける性質があるので、ラベルがガラス容器から剥がしにくい場合がある。また、シランカップリング剤及び固体滑剤の混合コーティング剤を使用すると、本願明細書に記載の比較例に見られるように、長期間の保存により浮遊物が発生してしまい、実際にコーティングに使用することができない。
　一方、本発明のコーティング処理済ガラス容器は、図６に示すように、ガラス容器本体１の表面１ａに接着性物質を含む接着層３を形成し、その上に固体滑剤の粒子２ａを含むコーティングを行うことにより滑性及び耐スクラッチ性付与層２を形成するものである。接着層３を形成するときに用いられるアミノ系シランカップリング剤は、本発明では接着性物質として機能し、固体滑剤の粒子２ａとガラス容器本体１の表面１ａを接着させることができる。その後、ラベル糊９が付着したラベル４を、固体滑剤の滑性及び耐スクラッチ性付与層２の上に貼り付けることとなるが、滑性及び耐スクラッチ性付与層２の上にラベル糊９付きのラベル４（糊付ラベル）を貼付することで、滑性及び耐スクラッチ性付与層２とラベル４との間が剥がしやすくなる。なお、滑性及び耐スクラッチ性付与層２は、固体滑剤の粒子として粒状のものから構成されているように記載されているが、滑性及び耐スクラッチ性付与層２は、粒状でなく、凹凸のないコーティング膜であってよい。
　また、接着層３と、滑性及び耐スクラッチ性付与層２の厚さは特に限定されるものではなく、同じ厚さにしてもよいし、異なる厚さにしてもよい。 Figure 5 shows a label 4 with label glue 9 attached to a conventional coated glass container (hot-end coated and then coated with a mixed coating agent containing a silane coupling agent and a solid lubricant). FIG. 2 is a cross-sectional view of the surface state of a labeled glass container. As shown in FIG. 5, in the conventional coated glass container, a hot end coating layer 10 is formed by hot coating on the surface 1a of the glass container body 1, and then a coating containing a silane coupling agent and a solid lubricant is applied. As a result, a silane coupling agent-containing lubricity and scratch resistance imparting layer 22 made of particles 22a of a silane coupling agent-containing solid lubricant is formed. In this embodiment of labeled glass containers, the label may be difficult to remove from the glass container because the hot end coating has the property of attracting organic substances such as label glue. In addition, when a mixed coating agent containing a silane coupling agent and a solid lubricant is used, floating substances are generated due to long-term storage, as seen in the comparative examples described in the specification of this application. I can't.
On the other hand, in the coated glass container of the present invention, as shown in FIG. 6, an adhesive layer 3 containing an adhesive substance is formed on the surface 1a of the glass container body 1, and a coating containing solid lubricant particles 2a is applied thereon. By performing this step, the lubricity and scratch resistance imparting layer 2 is formed. The amino-based silane coupling agent used when forming the adhesive layer 3 functions as an adhesive substance in the present invention, and can adhere the solid lubricant particles 2a and the surface 1a of the glass container body 1. After that, the label 4 to which the label glue 9 has been attached is pasted on the lubricity and scratch resistance imparting layer 2 made of solid lubricant. By pasting the label 4 (adhesive label), the gap between the lubricity and scratch resistance imparting layer 2 and the label 4 becomes easy to peel off. Note that the lubricity and scratch resistance imparting layer 2 is described as being composed of granular solid lubricant particles, but the lubricity and scratch resistance imparting layer 2 is not granular but has an uneven structure. It may be a coating film without.
Further, the thicknesses of the adhesive layer 3 and the lubricity and scratch resistance imparting layer 2 are not particularly limited, and may be the same thickness or different thicknesses.
　本発明のコーティング処理済ガラス容器を用いて製造されたラベル付ガラス容器は、通常のガラス容器の使用ではラベルがはがれにくく、かつ、廃棄時にラベルを剥がす際は、ガラスに残らずきれいに剥がすことが可能である。また、ガラス容器が低温（例えば、７℃）。常温（１５～２５℃）、高温（４０℃）のいずれの温度でも剥がしやいという特徴を有する。 Labeled glass containers manufactured using the coated glass containers of the present invention have labels that are difficult to peel off when used with normal glass containers, and when the labels are removed at the time of disposal, they can be removed cleanly without leaving any residue on the glass. It is possible. Also, the glass container is at a low temperature (for example, 7°C). It is characterized by being easy to peel at both room temperature (15-25°C) and high temperature (40°C).
　以下、本発明を実施例により詳細に説明するが、これらの実施例は、本発明を好適に説明するための例示に過ぎず、なんら本発明を限定するものではない。
　なお、実施例及び比較例は各５本以上製造し、結果はその平均値とした。 EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but these examples are merely illustrative for suitably explaining the present invention, and do not limit the present invention in any way.
In addition, five or more each of Examples and Comparative Examples were manufactured, and the results were taken as the average value.
（引張試験）
　実施例、比較例のラベルを貼り付けたガラスびんを、冷蔵（７℃、３５％ＲＨ）、常温（２５℃、６５％ＲＨ）又は高温高湿（４０℃、８０％ＲＨ）の環境で一週間保管後に、ガラスびんの胴中央部のラベルの引張強度を測定した。引張試験機はデジタルフォースゲージを使用し、引張速度は２００ｍｍ／分であった。
　引張強度が３．０Ｎ以上の場合を「〇」、２．５Ｎより大きく３．０Ｎ未満の場合を「△」、２．５Ｎ未満の場合を「×」として評価した。なお、〇のものは接着力に問題なく、通常使用する際に自然にはがれたりすることはない。当該項目は表１では、「引張試験」と記載されている。 (Tensile test)
The glass bottles with the labels of Examples and Comparative Examples pasted were placed in a refrigerated (7°C, 35% RH), room temperature (25°C, 65% RH), or high temperature and high humidity (40°C, 80% RH) environment. After storage for a week, the tensile strength of the label at the center of the glass bottle was measured. A digital force gauge was used as the tensile tester, and the tensile speed was 200 mm/min.
When the tensile strength was 3.0N or more, it was evaluated as "○", when it was greater than 2.5N but less than 3.0N, it was evaluated as "Δ", and when it was less than 2.5N, it was evaluated as "x". In addition, those marked with ○ have no problems with adhesive strength and do not peel off naturally during normal use. This item is described as "Tensile test" in Table 1.
（ラベル剥離性評価（材破率））
　ラベル貼り付けガラスびんのラベルの角部を爪で剥がし、それを指で摘んでラベルを引き剥がし、ラベルが破断した時点をもってラベル材破率を計算した。材破率は、５％未満であれば「○」、５％以上８０％未満であれば「△」、８０％以上であれば「×」とした。なお、ラベル材破率は、ラベル貼付後、７℃、湿度３５％の冷蔵庫にて１週間ガラスびんを保管後に実施した。当該項目は表１では、「易剥離性」と記載されている。 (Label removability evaluation (material breakage rate))
The corner of the label of the labeled glass bottle was peeled off with a fingernail, and the label was peeled off by picking it with fingers, and the label material breakage rate was calculated from the point at which the label broke. The wood breakage rate was evaluated as "○" if it was less than 5%, "△" if it was 5% or more and less than 80%, and "x" if it was 80% or more. Note that the label material breakage rate was measured after the glass bottles were stored in a refrigerator at 7° C. and 35% humidity for one week after the label was pasted. This item is described as "easy peelability" in Table 1.
　実施例１～３
　ホットエンドコーティングを施さない５０ｍｌのガラスびん（２０本）の表面（表面温度約１００℃）に上流スプレー装置でアミノ基シランカップリング剤（東京化成株式会社製　Ａ０４３９）を含む第一コーティング剤を塗布する。第一コーティング剤は、アミノ基シランカップリング剤０．２重量％と水９９．８重量％とを混合したものである。３～５分ほどの乾燥時間を経過してから、下流スプレー装置で固体滑剤を含む第二コーティング剤を塗布する。第二コーティング剤は、ポリエチレンワックス０．３２％とアニオン系界面活性剤（オレイン酸カリウム）０．０８重量％と水９９．６重量％とを混合したものである。
　上記したように方法で得られたコーティング処理済ガラスびん（１０本）にラベルとして長さが１００ｍｍ、幅が６０ｍｍの蒸着紙を糊（トキワノールＺ２２Ｈ）で貼り付けることで、ラベル付ガラスびんを得た（実施例１）。
　なお、第一コーティング剤、第二コーティング剤のいずれも室温で１０日間保管し、その状態を確認する実験も行ったが、特に変化は見られなかった。 Examples 1 to 3
Apply a first coating agent containing an amino-based silane coupling agent (A0439 manufactured by Tokyo Kasei Co., Ltd.) to the surfaces of 50 ml glass bottles (20 bottles) without hot-end coating (surface temperature approximately 100°C) using an upstream spray device. do. The first coating agent is a mixture of 0.2% by weight of an amino group silane coupling agent and 99.8% by weight of water. After a drying period of about 3 to 5 minutes, a second coating containing a solid lubricant is applied by a downstream spray device. The second coating agent is a mixture of 0.32% polyethylene wax, 0.08% by weight of an anionic surfactant (potassium oleate), and 99.6% by weight of water.
Labeled glass bottles were obtained by pasting vaporized paper with a length of 100 mm and a width of 60 mm as a label on the coated glass bottles (10 bottles) obtained by the method described above using glue (Tokiwanol Z22H). (Example 1).
In addition, both the first coating agent and the second coating agent were stored at room temperature for 10 days, and an experiment was conducted to confirm the condition, but no particular change was observed.
実施例４～６
　図１において、徐冷炉Ｃに入る前に、ＳｎＣｌ４をガス化して塗布（ホットエンドコーティング）し、酸化スズ膜を形成した以外は、実施例１～３と同様の方法でラベル付ガラスびんを得た。 Examples 4-6
In FIG. 1, labeled glass bottles were obtained in the same manner as in Examples 1 to 3, except that before entering the lehr C, SnCl 4 was gasified and applied (hot end coating) to form a tin oxide film. Ta.
比較例１～２
　コールドエンドコーティングで、シランを含む第一コーティングを実施しないこと以外は、実施例４～６と同様の方法でラベル付ガラスびんを得た。 Comparative examples 1-2
Labeled glass bottles were obtained in the same manner as in Examples 4 to 6, except that the first coating containing silane was not performed in the cold end coating.
比較例３～４
　ホットエンドコーティング及びコールドエンドコーティングを実施しないことを除いて、実施例１～３と同様の方法でラベル付ガラスびんを得た。 Comparative examples 3-4
Labeled glass bottles were obtained in the same manner as in Examples 1 to 3, except that hot end coating and cold end coating were not performed.
比較例５
　実施例４～６に記載の方法によりホットエンドコーティングのみを実施して、比較例３～４と同様の方法でラベル付ガラスびんを得た。 Comparative example 5
Labeled glass bottles were obtained in the same manner as in Comparative Examples 3 to 4, except that only hot end coating was performed by the method described in Examples 4 to 6.
比較例６～７
　コールドエンドコーティングとして、アミノ基シランカップリング剤０．２重量％と、ポリエチレンワックス０．３２％と、アニオン系界面活性剤（オレイン酸カリウム）０．０８重量％と水とを混合した水溶液混合物を塗布した以外は実施例１～３と同様の方法でラベル付ガラスびんを得た。また、当該混合物を室温で１０日間保管し、その混合液の状態を確認する実験も行った。その写真を図７に示す。写真からわかるように浮遊物の発生が確認でき、コーティング液の均一な塗布が難しい可能性があることがわかった。表１においては、浮遊物が見られたものは、保存安定性に「×」と評価した。 Comparative examples 6-7
As a cold end coating, an aqueous solution mixture of 0.2% by weight of an amino-based silane coupling agent, 0.32% of polyethylene wax, 0.08% by weight of an anionic surfactant (potassium oleate), and water was used. Labeled glass bottles were obtained in the same manner as in Examples 1 to 3 except for coating. An experiment was also conducted in which the mixture was stored at room temperature for 10 days and the state of the mixture was confirmed. The photograph is shown in Figure 7. As you can see from the photo, floating particles were observed, indicating that it may be difficult to apply the coating solution evenly. In Table 1, those in which floating matter was observed were evaluated as "x" for storage stability.
比較例８～９
　コールドエンドコーティングとして、アミノ基シランカップリング剤０．２重量％、ポリエチレンワックス０．３２％とアニオン系界面活性剤（オレイン酸カリウム）０．０８重量％と水を混合した水溶液混合物を塗布した以外は実施例４～６と同様の方法でラベル付ガラスびんを得た。 Comparative examples 8-9
As a cold end coating, an aqueous solution mixture of 0.2% by weight of an amino-based silane coupling agent, 0.32% of polyethylene wax, 0.08% by weight of an anionic surfactant (potassium oleate), and water was applied. Labeled glass bottles were obtained in the same manner as in Examples 4-6.
　表１により、コーティング剤を２回分けて塗布することにより、ホットエンドコーティングの有無に関わらずラベルが通常の使用では剥がれにくい程度の接着力を有し、かつ、剥がすときに破れずきれいに剥がせることがわかった。また、一般的には、冷蔵庫等で保管したガラス容器は、糊に含まれる水分量が低下し、破壊強度が増加し、糊が破壊されない代わりにラベルが破れ、紙がガラス容器に残りやすくなるが、本発明のコーティング処理済ガラス容器は、冷蔵庫等で保管後であっても、ラベルの破れを最小限に抑え、ガラス容器の温度に関わらず、きれいに剥がすことができた。
　アミノ基シランカップリング剤、ポリエチレンワックス、アニオン系界面活性剤、及び水を混合した水溶液混合物は、長期間の保存により浮遊物が発生してしまうことがわかった。この浮遊物はガラス容器に付着すると、異物付着付きのガラス製品となり廃棄となるため好ましくない。また、浮遊物があるとスプレーノズルが詰まる恐れがある。さらに、この水溶液混合物のコーティング剤を用いた比較例は、混合物を調製してすぐに使用したため易剥離性が認められたが、長期の保管により浮遊物が浮いてしまうと、コーティング形成が不安定になり、その結果、易剥離性としての効果が得られなくなると推測される。 According to Table 1, by applying the coating agent twice, regardless of the presence or absence of hot end coating, the label has enough adhesive strength to be difficult to peel off during normal use, and can be removed cleanly without tearing. I understand. Additionally, in general, when glass containers are stored in a refrigerator, etc., the amount of water contained in the glue decreases, and the breaking strength increases, and instead of the glue being destroyed, the label is torn, and paper is more likely to remain in the glass container. However, the coated glass container of the present invention minimized label tearing even after being stored in a refrigerator or the like, and could be peeled off cleanly regardless of the temperature of the glass container.
It has been found that an aqueous solution mixture of an amino group silane coupling agent, polyethylene wax, anionic surfactant, and water generates suspended matter when stored for a long period of time. If this floating matter adheres to a glass container, it becomes a glass product with foreign matter adhering to it, which is undesirable. Additionally, floating objects may clog the spray nozzle. Furthermore, in a comparative example using a coating agent of this aqueous solution mixture, easy peelability was observed because the mixture was used immediately after preparation, but if suspended matter floated due to long-term storage, the coating formation became unstable. It is presumed that as a result, the effect of easy peelability cannot be obtained.
　本発明により、通常の使用でははがれにくい程度の付着性を有し、はがしたときに残りにくいコーティング処理を施したガラス容器及びその製造方法を提供することを実現することができる。安定性の高いコーティング剤を提供することができる。 According to the present invention, it is possible to provide a glass container coated with a coating that has a degree of adhesion that is difficult to peel off during normal use and does not remain easily when removed, and a method for manufacturing the same. A highly stable coating agent can be provided.
Ｂ　ラベル付ガラス容器全体
１　ガラス本体
２　滑性及び耐スクラッチ性付与層
２ａ　固体滑剤の粒子
３　接着層
４　ラベル
５　コンベア
６　上流スプレーノズル
７　下流スプレーノズル
８　徐冷炉
９　ラベル糊
１０　ホットエンドコーティング層

  B Entire labeled glass container 1 Glass body 2 Smoothness and scratch resistance imparting layer 2a Solid lubricant particles 3 Adhesive layer 4 Label 5 Conveyor 6 Upstream spray nozzle 7 Downstream spray nozzle 8 Annealing furnace 9 Label glue 10 Hot end coating layer

Claims (9)

  1. 　徐冷済ガラス容器本体に接着性物質を含む第一コーティング剤を塗布し、第一コーティング処理済ガラス容器を形成する工程と、
    　前記第一コーティング処理済ガラス容器に、固体滑剤を含み、滑性及び耐スクラッチ性を付与する第二コーティング剤を塗布し、第二コーティング処理済ガラス容器を形成する工程とを含む、コーティング処理済ガラス容器の製造方法。     a step of applying a first coating agent containing an adhesive substance to the slowly cooled glass container body to form a first coated glass container;
    applying a second coating agent containing a solid lubricant and imparting lubricity and scratch resistance to the first coated glass container to form a second coated glass container. Method of manufacturing glass containers.
  2. 　前記接着性物質がアミノ基シランカップリング剤を含む、請求項１に記載のコーティング処理済ガラス容器の製造方法。 The method for producing a coated glass container according to claim 1, wherein the adhesive substance contains an amino group silane coupling agent.
  3. 　前記固体滑剤はポリエチレンワックスを含む、請求項１又は２に記載のコーティング処理済ガラス容器の製造方法。 The method for manufacturing a coated glass container according to claim 1 or 2, wherein the solid lubricant includes polyethylene wax.
  4. 　前記第二コーティング剤は界面活性剤を含む、請求項１乃至３のいずれか一項に記載のコーティング処理済ガラス容器の製造方法。 The method for manufacturing a coated glass container according to any one of claims 1 to 3, wherein the second coating agent contains a surfactant.
  5. 　ガラス容器本体のガラス表面に前記第一コーティング剤を塗布する、請求項１乃至４のいずれか一項に記載のコーティング処理済ガラス容器の製造方法。 The method for manufacturing a coated glass container according to any one of claims 1 to 4, wherein the first coating agent is applied to the glass surface of the glass container body.
  6. 　第一コーティング塗布後前記第一コーティング剤が乾燥してから、前記第二コーティング剤を塗布する工程を行う、請求項１乃至５のいずれかの一項に記載のコーティング処理済ガラス容器の製造方法。 The method for manufacturing a coated glass container according to any one of claims 1 to 5, wherein the step of applying the second coating agent is performed after the first coating agent is dried after applying the first coating. .
  7. 　請求項１乃至６のいずれか一項に記載のコーティング処理済ガラス容器に、糊付ラベルを貼り付ける工程を含む、ラベル付ガラス容器の製造方法。 A method for producing a labeled glass container, the method comprising the step of attaching an adhesive label to the coated glass container according to any one of claims 1 to 6.
  8. 　コーティング処理済ガラス容器であって、
    　ガラス容器本体と、
    　前記ガラス容器本体に配置される接着層と、
    　前記接着層の上に配置される滑性及び耐スクラッチ性付与層とを含む、コーティング処理済ガラス容器。     A coated glass container,
    A glass container body,
    an adhesive layer disposed on the glass container body;
    A coated glass container comprising a lubricity and scratch resistance imparting layer disposed on the adhesive layer.
  9. 　請求項８に記載のコーティング処理済ガラス容器の前記滑性及び耐スクラッチ性付与層の表面に糊付ラベルを直接貼り付けた、ラベル付ガラス容器。

          A labeled glass container, wherein a glued label is directly attached to the surface of the lubricity and scratch resistance imparting layer of the coated glass container according to claim 8.
PCT/JP2022/048498 2022-03-07 2022-12-28 Coated glass container and method for producing same WO2023171098A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130677A (en) * 1977-10-21 1978-12-19 E. I. Du Pont De Nemours And Company Process for applying to glass an organic coating having controlled bond strength
JPS55100242A (en) * 1978-10-18 1980-07-31 Fr Deyuko Soc Covering of glass or ceramic article
WO1995010487A1 (en) * 1993-10-12 1995-04-20 Plm Ab Method of producing an article with a body of glass having protective coatings of polymeric material
JPH08500771A (en) * 1993-06-21 1996-01-30 エルフ アトケム ノース アメリカ インコーポレイテッド Brittle Oxide Support Reinforced by Crosslinkable Silane
JP2000512258A (en) * 1997-04-04 2000-09-19 ジヴェント ヒェミー ラインフェルデン ゲゼルシャフト ミット ベシュレンクテル ハフツング Method of manufacturing surface sealed hollow glass container
JP2001328613A (en) * 2000-05-19 2001-11-27 Toyo Glass Co Ltd Packaging container
JP2005177542A (en) * 2003-12-16 2005-07-07 Toyo Glass Co Ltd Method of coating glass container and the glass container
JP2009046348A (en) * 2007-08-20 2009-03-05 Nihon Yamamura Glass Co Ltd Glass product stuck with heat-sensitive label

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130677A (en) * 1977-10-21 1978-12-19 E. I. Du Pont De Nemours And Company Process for applying to glass an organic coating having controlled bond strength
JPS55100242A (en) * 1978-10-18 1980-07-31 Fr Deyuko Soc Covering of glass or ceramic article
JPH08500771A (en) * 1993-06-21 1996-01-30 エルフ アトケム ノース アメリカ インコーポレイテッド Brittle Oxide Support Reinforced by Crosslinkable Silane
WO1995010487A1 (en) * 1993-10-12 1995-04-20 Plm Ab Method of producing an article with a body of glass having protective coatings of polymeric material
JP2000512258A (en) * 1997-04-04 2000-09-19 ジヴェント ヒェミー ラインフェルデン ゲゼルシャフト ミット ベシュレンクテル ハフツング Method of manufacturing surface sealed hollow glass container
JP2001328613A (en) * 2000-05-19 2001-11-27 Toyo Glass Co Ltd Packaging container
JP2005177542A (en) * 2003-12-16 2005-07-07 Toyo Glass Co Ltd Method of coating glass container and the glass container
JP2009046348A (en) * 2007-08-20 2009-03-05 Nihon Yamamura Glass Co Ltd Glass product stuck with heat-sensitive label

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