JP2019031408A - Glass container and its production method - Google Patents

Abstract

To provide improved lubricity to a resin member in a glass container and a production method of a glass container having high lubricity to the resin member.SOLUTION: A glass container includes a coating on a surface, in which the coating includes a metal oxide layer bonded to the surface; a silane coupling agent bonded to the surface; and a nonionic surfactant bonded to at least one of the silane coupling agent and the metal oxide layer. A method of producing a glass container having the coating on the surface includes: a first step of forming the metal oxide layer on the surface; and, after the first step, a second step of coating an aqueous solution containing the silane coupling agent and the nonionic surfactant on the surface.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass container and a manufacturing method thereof.

  Some glass containers have a surface coated with polyethylene wax to suppress surface scratches, thereby increasing the surface slipperiness (for example, Patent Document 1). The coating of the glass container according to Patent Document 1 includes a silane coupling agent having an amino group in order to firmly bond polyethylene wax to the glass container surface. Thereby, even when the glass container is exposed to a high-temperature liquid in the pasteriser, the peeling of the polyethylene wax can be suppressed.

JP 2002-241145 A

  In recent years, the processing capacity per unit time of a filling device for filling a glass container with a liquid such as a beverage has increased, and the conveyance speed of the glass container in the filling device has increased. In the filling device, a guide member that is in sliding contact with the side surface of the glass container is used to transport the glass container along a predetermined transport path. This guide member is often formed of a resin material. Therefore, in order to smoothly transport the glass container along the transport path, the glass container is required to have sufficient sliding properties with respect to the resin guide member. A glass container provided with a coating containing polyethylene wax has relatively high slipperiness with respect to other glass containers, but is not sufficiently slippery with respect to resins such as polypropylene, polyethylene, nylon, and polyacetal.

  This invention makes it a subject to improve the lubricity with respect to the resin member in a glass container in view of the above background. Moreover, it aims at providing the manufacturing method of a glass container with high slipperiness | lubricity with respect to a resin member.

  In order to solve the above problems, a first aspect of the present invention is a glass container having a coating on a surface, the coating comprising a metal oxide layer bonded to the surface and a silane cup bonded to the surface. It has a ring agent and a nonionic surfactant bonded to at least one of the silane coupling agent and the metal oxide layer.

  According to this aspect, the slipperiness with respect to the resin member of a glass container can be improved. The coating containing a nonionic surfactant has higher lubricity with respect to the resin member than the coating containing polyethylene wax. Since the nonionic surfactant is bonded to the silane coupling agent that is covalently bonded to the surface of the glass container, the nonionic surfactant is retained on the surface even after the glass container is washed with water. Therefore, the glass container of this aspect can be used also in the filling apparatus containing a water washing apparatus and a paste riser. The metal oxide layer can increase the hardness of the surface of the glass container and prevent scratches. Further, the metal oxide layer can interact with the nonionic surfactant and prevent the nonionic surfactant from peeling off. Nonionic surfactants are safer and less burdensome on the environment than anionic surfactants and cationic surfactants. Therefore, a glass container having a coating containing a nonionic surfactant is suitable as a container for food or beverages.

  In the first aspect, the nonionic surfactant is selected from the group consisting of an ether type nonionic surfactant, an ester type nonionic surfactant, and an ester ether type nonionic surfactant. It is good to be 1 or more types. The nonionic surfactant may contain at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether.

  In the first aspect, the silane coupling agent may include at least one of an amino group, a vinyl group, a methacryl group, an epoxy group, a ureido group, and an isocyanate group. In the first aspect, the metal oxide layer may be a tin oxide layer. In the first aspect, it is preferable that the coating does not substantially contain polyethylene wax.

  The second aspect of the present invention is a method for producing a glass container having a coating on the surface, the first step of forming a metal oxide layer on the surface, and the silane coupling after the first step. A second step of applying an aqueous solution containing an agent to the surface; and a third step of applying an aqueous solution containing a nonionic surfactant to the surface after the second step.

  According to this aspect, after the silane coupling agent layer is formed on the surface of the glass container, the nonionic surfactant layer is formed on the silane coupling agent layer. It is possible to efficiently retain the nonionic surfactant.

  The third aspect of the present invention is a method for manufacturing a glass container having a coating on the surface, the first step of forming a metal oxide layer on the surface, and the silane coupling after the first step. And a second step of applying an aqueous solution containing an agent and a nonionic surfactant to the surface. In the third aspect, the aqueous solution applied in the second step preferably does not contain polyethylene wax.

  According to this aspect, the silane coupling agent and the nonionic surfactant can be held on the surface of the glass container by one application, and the manufacturing process can be simplified.

  In the second and third aspects, the nonionic surfactant comprises an ether type nonionic surfactant, an ester type nonionic surfactant, and an ester ether type nonionic surfactant. It is good in it being 1 or more types selected from a group. In the second and third aspects, the nonionic surfactant may include at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether.

  In the second and third aspects, the concentration of the nonionic surfactant in the aqueous solution containing the nonionic surfactant may be 0.05% by weight or more and 0.50% by weight or less.

  According to this aspect, the nonionic surfactant can be sufficiently retained on the surface of the glass container, and the lubricity with respect to the resin member can be improved.

  In the third aspect, the nonionic surfactant contains at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether, and in an aqueous solution containing the nonionic surfactant. The concentration of the nonionic surfactant is preferably 0.05% by weight or more and 0.20% by weight or less.

  According to this aspect, the layer of the nonionic surfactant can be uniformly formed on the surface of the glass container. Moreover, adhesion of the nonionic surfactant precipitate to the surface of the glass container is suppressed, and the appearance (appearance) of the surface of the glass container can be improved.

  In the second and third aspects, the silane coupling agent may include at least one of an amino group, a vinyl group, an epoxy group, a ureido group, and an isocyanate group. In the second and third aspects, the concentration of the silane coupling agent in the aqueous solution containing the silane coupling agent is preferably 0.05% by weight or more and 0.30% by weight or less. In the second and third aspects, the metal oxide layer may be a tin oxide layer.

  ADVANTAGE OF THE INVENTION According to this invention, the lubricity with respect to the resin member can be improved in a glass container. Moreover, the manufacturing method of a glass container with high lubricity with respect to a resin member can be provided.

Explanatory drawing which shows the coupling | bonding structure of a silane coupling agent and the surface of a glass container (A) Structural formula of polyoxyethylene (20) sorbitan monooleate, (B) Structural formula of polyoxyethylene alkyl ether (A), (B) Explanatory drawing of slipping angle test of glass container against glass container (A: front view, B: side view), explanatory drawing of slipping angle test of glass container against resin member (C: front view) , D: Side view) (A), (B) Explanatory drawing of a scratch test (A: front view, B: plan view) Table showing the results of the sliding angle test of each sample manufactured by the first manufacturing method (recoating method) Table showing the results of the scratch test of each sample manufactured by the first manufacturing method (multiple coating method) Table showing the results of the appearance observation of each sample manufactured by the first manufacturing method (multiple coating method) Table showing results of lubricity angle test of each sample manufactured by the second manufacturing method (mixed coating method) Table showing results of scratch test of each sample manufactured by the second manufacturing method (mixed coating method) Table showing results of appearance observation of each sample manufactured by the second manufacturing method (mixed coating method)

(Glass container)
Hereinafter, embodiments of the present invention will be described. The glass container according to the present embodiment is soda-lime glass, and contains silicon, sodium, and calcium as main components. The glass also contains aluminum, potassium, magnesium, and sulfur. Further, the glass may contain chromium, nickel, iron and the like as a colorant.

In the glass of the present embodiment, silicon is 65 to 75% by weight in terms of SiO _{2 with} respect to the total weight of the glass, sodium is 12 to 14% by weight in terms of Na ₂ O, and calcium is 10 to 10% in terms of CaO. 12 wt%, aluminum is 1.5 to 3.0 wt% in terms of Al ₂ O ₃ , potassium is 0.0 to 1.5 wt% in terms of K ₂ O, and magnesium is in terms of MgO. It is 0.0 to 1.5% by weight, and sulfur is 0.03 to 0.40% by weight in terms of SO ₃ .

  The glass container according to the present embodiment is formed in the form of a bottle (bottle). In other embodiments, the glass container may be in the form of a cup, glass, pot, tray or the like.

  The glass container has a coating on its surface. The coating has a silane coupling agent bonded to the surface of the glass container, a metal oxide layer bonded to the surface, and a nonionic surfactant bonded to at least one of the silane coupling agent and the metal oxide layer. .

  The metal oxide layer includes at least one selected from the group consisting of tin oxide, titanium oxide, and zirconia (zirconium dioxide). The metal oxide layer is included in the hot end coating (HC). Hot end coating is performed immediately after the glass container forming step (hot end), and is formed by a hot end coating process that forms a film on the surface of the glass container at a high temperature (400 ° C. to 700 ° C.) before the slow cooling step. Is done.

  The thickness of the metal oxide layer is 2 nm to 50 nm, preferably 5 nm to 20 nm. When other units are used, the thickness of the metal oxide layer is 20 CTU or more and 80 CTU or less. CTU (Coating Thickness Units) is a value measured by a hot coating meter manufactured by American Glass Research, and has a correlation with the film thickness of the coating. One CTU corresponds to 0.1 to 0.4 nm.

  The silane coupling agent includes at least one selected from the group consisting of an amino group, a vinyl group, a methacryl group, an epoxy group, a ureido group, and an isocyanate group. Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, and 3 -It may be at least one selected from the group consisting of isocyanatepropyltriethoxysilane.

  As shown in FIG. 1, a silane coupling agent produces | generates a silanol group by the hydrolysis reaction of an alkoxy group. The silanol group forms a covalent bond by a dehydration condensation reaction with a hydroxyl group present on the surface of the glass container. Thereby, a silane coupling agent couple | bonds with the surface of a glass container. At the same time, silane coupling agents form siloxane bonds by dehydration condensation of silanol groups. The silane coupling agent is bonded in layers to the surface of the glass container.

  The nonionic surfactant is at least one selected from the group consisting of an ether type nonionic surfactant, an ester type nonionic surfactant, and an ester ether type nonionic surfactant. The nonionic surfactant may include, for example, at least one of polyoxyethylene (20) sorbitan monooleate (see FIG. 2A) and polyoxyethylene alkyl ether (see FIG. 2B).

  The nonionic surfactant is bonded to at least one of the functional group of the silane coupling agent and the metal oxide layer. The nonionic surfactant preferably forms a covalent bond with the functional group of the silane coupling agent. The nonionic surfactant preferably forms a coordinate bond and an ionic bond with a metal atom contained in the metal oxide layer.

  Silane coupling agents and nonionic surfactants are included in the cold end coating. The cold end coating is formed by a cold end coating process in which a film is formed on the surface of a glass container at a low temperature (70 ° C. to 150 ° C.) after the glass container is slowly cooled (cold end).

  The cold end coating in this embodiment contains a silane coupling agent and a nonionic surfactant as main components. That is, the cold end coating is substantially free of other lubricants such as polyethylene wax, polyethylene, modified polyethylene wax, and carnauba wax. Also, if the cold end coating contains other lubricants such as polyethylene wax, polyethylene, modified polyethylene wax, and carnauba wax, these weight concentrations are negligible relative to the weight concentration of the nonionic surfactant. Low enough. That is, the cold end coating does not contain other lubricants such as polyethylene wax, polyethylene, modified polyethylene wax, and carnauba wax to an extent that affects the slipperiness.

  As described above, the glass container has on its surface a hot end coating including a metal oxide layer and a cold end coating including a silane coupling agent and a nonionic surfactant.

(Production method of glass container: 1)
A first manufacturing method of a glass container having a coating on the surface includes a first step of forming a metal oxide layer, and a second step of applying an aqueous solution containing a silane coupling agent to the surface after the first step. And a third step of applying an aqueous solution containing a nonionic surfactant on the surface after the second step. Thus, the 1st manufacturing method which made application | coating of a silane coupling agent (2nd process) and application | coating of a nonionic surfactant (3rd process) mutually independent is called an overcoating method.

The first step is performed by a hot end coating process immediately after the molding step. A hot end coating process is performed by the chemical vapor deposition method (CVD) with respect to the surface of a glass container of high temperature (400 degreeC-700 degreeC). When the tin oxide layer (SnO ₂ ) is formed on the upper surface of the glass container, tin tetrachloride (SnCl ₄ ) may be used as a raw material. When the titanium oxide layer (TiO ₂ ) is formed on the upper surface of the glass container, titanium tetrachloride (TiCl ₄ ) may be used as a raw material.

  The second step and the third step are performed by a cold end coating process after the slow cooling step. The cold end coating treatment is performed by applying an aqueous solution containing at least one of a silane coupling agent or a nonionic surfactant to the surface of a low temperature (70 ° C. to 150 ° C.) glass container. The application may be performed by spray application or dip application.

  In the second step, the concentration of the silane coupling agent in the aqueous solution containing the silane coupling agent is 0.05 wt% or more and 0.30 wt% or less, preferably 0.15 wt% or more and 0.30 wt% or less. Good. When the concentration of the silane coupling agent is lower than 0.05% by weight, the adhesion of the nonionic surfactant is lowered. Therefore, the nonionic surfactant easily flows out by washing with water. On the other hand, even if the concentration of the silane coupling agent is higher than 0.30% by weight, the adhesiveness of the nonionic surfactant hardly changes. When the concentration of the silane coupling agent is in the range of 0.05% by weight or more and 0.30% by weight or less, the adhesion of the nonionic surfactant increases as the concentration increases.

  In the third step, the concentration of the nonionic surfactant in the aqueous solution containing the nonionic surfactant is preferably 0.05% by weight or more and 0.50% by weight or less. When the concentration of the nonionic surfactant is lower than 0.05% by weight, appropriate slipperiness cannot be imparted to the surface of the glass container. On the other hand, even if the concentration of the nonionic surfactant is higher than 0.50% by weight, the slipperiness of the surface of the glass container is hardly changed.

(Manufacturing method of glass container: 2)
A second manufacturing method of a glass container having a coating on the surface includes a first step of forming a metal oxide layer on the surface, and an aqueous solution containing a silane coupling agent and a nonionic surfactant after the first step. And a second step of applying to the surface. Thus, the 2nd manufacturing method using the aqueous solution containing a silane coupling agent and a nonionic surfactant is called mixed coating method.

  The first step in the second manufacturing method is the same as the first step in the first manufacturing method described above.

  The second step is performed by a cold end coating process after the slow cooling step. The cold end coating treatment is performed by applying an aqueous solution containing a silane coupling agent and a nonionic surfactant to the surface of a glass container at a low temperature (70 ° C. to 150 ° C.). The application may be performed by spray application or dip application.

  In the second step, in the aqueous solution containing the silane coupling agent and the nonionic surfactant, the concentration of the silane coupling agent is 0.05% by weight or more and 0.30% by weight or less, preferably 0.15% by weight or more. It is good that it is 0.30% by weight or less. The concentration of the nonionic surfactant is 0.05% by weight or more and 0.50% by weight or less, preferably 0.05% by weight or more and 0.20% by weight or less.

  When the concentration of the silane coupling agent is lower than 0.05% by weight, the adhesion of the nonionic surfactant is lowered. Therefore, the nonionic surfactant easily flows out by washing with water. On the other hand, even if the concentration of the silane coupling agent is higher than 0.30% by weight, the adhesiveness of the nonionic surfactant hardly changes. When the concentration of the silane coupling agent is in the range of 0.05% by weight or more and 0.30% by weight or less, the adhesion of the nonionic surfactant increases as the concentration increases.

  When the concentration of the nonionic surfactant is lower than 0.05% by weight, appropriate slipperiness cannot be imparted to the surface of the glass container. On the other hand, even if the concentration of the nonionic surfactant is higher than 0.30% by weight, the slipperiness of the surface of the glass container is hardly changed. When the concentration of the nonionic surfactant is in the range of 0.30% by weight or more and 0.50% by weight, the appearance of the surface improves as the concentration decreases. This is considered to be due to the fact that as the concentration increases, excess nonionic surfactant is deposited on the surface.

  According to the above aspect, the lubricity with respect to the resin member of a glass container can be improved. The coating containing a nonionic surfactant has higher lubricity with respect to the resin member than the coating containing polyethylene wax. Since the nonionic surfactant is bonded to the silane coupling agent that is covalently bonded to the surface of the glass container, the nonionic surfactant is retained on the surface even after the glass container is washed with water. Therefore, the glass container of this aspect can be used also in the filling apparatus containing a water washing apparatus and a paste riser.

  The metal oxide layer can increase the hardness of the surface of the glass container and prevent scratches. Further, the metal oxide layer can interact with the nonionic surfactant and prevent the nonionic surfactant from peeling off.

  Nonionic surfactants are safer and less burdensome on the environment than anionic surfactants and cationic surfactants. Therefore, a glass container having a coating containing a nonionic surfactant is suitable as a container for food or beverages.

  Examples of the above embodiment will be described below.

  Each sample which concerns on an Example was manufactured based on said 1st manufacturing method (overpainting method) and 2nd manufacturing method (mixed coating method).

  In the first production method (overcoating method), as a first step, a tin oxide layer was formed on the surface of the molded glass container by hot end coating treatment. The hot end coating treatment was performed by CVD using tin tetrachloride in a glass container at 600 ° C., and the thickness of the tin oxide layer was 60 CTU.

  Next, as a second step, an aqueous solution containing 3-aminopropyltriethoxysilane at a predetermined concentration (0.07 wt%, 0.20 wt%) was applied to the surface of the glass container by spraying. At this time, the glass container was previously heated to 120 ° C. by an oven and rotated at 2 rps using a potter's wheel. Application by spraying was performed at a spray angle of 110 degrees and a flow rate of 35 to 40 mL / min for 1 second.

  Immediately after the second step, as a third step, an aqueous solution containing 0.4% by weight of polyoxyethylene (20) sorbitan monooleate or polyoxyethylene alkyl ether was applied to the surface of the glass container by spraying. At this time, the glass container was about 120 ° C. and was rotated at 2 rps using a potter's wheel. Application by spraying was performed at a spray angle of 110 degrees and a flow rate of 35 to 40 mL / min for 1 second. Thus, the sample (Examples 1-4) which concerns on an Example was adjusted.

  In the samples according to the comparative examples (Comparative Examples 1 to 8), the first step and the second step were omitted with respect to the first manufacturing method.

  In the second production method (mixed coating method), as a first step, a tin oxide layer was formed on the surface of the molded glass container by hot end coating treatment. The hot end coating treatment was performed by CVD using tin tetrachloride in a glass container at 600 ° C., and the thickness of the tin oxide layer was 60 CTU.

  Next, as a second step, any one of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, and vinyltriethoxysilane is added at a predetermined concentration (0.07 wt%, 0.20). The surface of the glass container is sprayed with an aqueous solution containing polyoxyethylene (20) sorbitan monooleate or polyoxyethylene alkyl ether at a predetermined concentration (0.1 wt%, 0.4 wt%). It was applied to. At this time, the glass container was previously heated to 120 ° C. by an oven. Application | coating was performed for 0.2 second at the flow volume of 30 mL / min using the spray gun which drive | works with respect to a glass container. Thus, the sample (Examples 11-22) which concerns on an Example was adjusted.

  Each Example and Comparative Example were evaluated by a lubricity angle test, a scratch test, and an appearance observation.

  The slip angle test was performed using the slip angle tester 1 shown in FIG. The lubricity angle tester 1 has a base 2 and a support plate 3 provided so as to be rotatable with respect to the base 2. The support plate 3 can be rotated in the vertical direction from the initial position where the support surface is horizontal.

  The glass container used for the lubricity angle test is formed in a cylindrical shape. In the slip angle test, the slipperiness between glass containers and the slipperiness between the glass container and the resin member were measured. Moreover, the lubricity angle test was performed in a state where the glass container was dried (dry state) and a state where the glass container was wet (wet state). The wet state was prepared by immersing the glass container in pure water before the measurement and attaching water to the surface.

  As shown in FIGS. 3A and 3B, three samples were used in the slip test between glass containers. The first and second samples 4A and 4B were fixed on the support plate 3 so as to be parallel to and in contact with each other. At this time, the axes of the first and second samples 4A and 4B were arranged so as to be orthogonal to the rotation axis of the support plate 3 in plan view. The third sample 4C was disposed between and above each of the first and second samples 4A and 4B in parallel. In this state, the third sample 4C comes into contact with and is supported by the first and second samples 4A and 4B. In this state, the angle of the support plate 3 was increased, and the angle when the third sample 4C slipped with respect to the first and second samples 4A and 4B was read as the slip angle [deg]. The slip angle indicates that the smaller the value, the higher the slipperiness.

  As shown in FIGS. 3C and 3D, a pedestal 5 formed from a resin material to be measured was used in the lubricity test between the glass container and the resin member. The pedestal 5 was fixed to the upper surface of the support plate 3. A groove extending in a direction orthogonal to the rotation axis of the support plate 3 in plan view is formed on the upper surface of the pedestal. The groove has a triangular cross section and two inclined wall surfaces. A cylindrical sample 4D of the glass container was placed in parallel in the groove. In this state, the sample 4D comes into contact with the two inclined surfaces of the groove on the outer peripheral surface. In this state, the angle of the support plate 3 was increased, and the angle when the sample 4D slipped against the pedestal 5 was read as the slip angle [deg].

  The material of the base 5 is polyethylene (PE), ultrahigh molecular weight polyethylene 1 (UHPE1, manufactured by Sakushin Kogyo Co., Ltd., product name Newlite, μs = 0.25), ultrahigh molecular weight polyethylene 2 (UHPE2, Sakushin Kogyo Co., Ltd.) Product name NL-Supermu LF, μs = 0.11), polypropylene (PP), 6 nylon (PA6), and polyacetal (POM).

  The scratch test was performed using the scratch tester 10. The scratch testing machine 10 uses two cylindrical samples 11A and 11B of glass containers. The scratch testing machine 10 includes a first holder 12A that supports the first sample 11A so that the axis is horizontal, and a second holder that supports the second sample 11B above the first sample 11A so that the axis is horizontal. 12B. The first and second holders 12A and 12B support the first and second samples 11B so that they cross each other at 90 degrees in plan view and abut against each other vertically. A weight can be placed on the second holder 12B, and the contact load between the first sample 11A and the second sample 11B can be adjusted. In the test, the first holder 12A is slid in the horizontal direction at a speed of 8 cm / min with respect to the axis of the first sample 11A, and it is confirmed whether either the first sample 11A or the second sample 11B is damaged. did. In the test, the load applied to the second sample 11B was increased stepwise, and the load when a scratch occurred was defined as the scratch generation load [kg]. The scratch generation load indicates that the larger the value, the harder the scratch is generated. The scratch test was conducted in a dry state and a wet state in the same manner as the slip angle test.

  Appearance observation confirmed the glass container of the dry state and the wet state by visual observation, and confirmed the white deposit | attachment (stain) on the surface of the glass container. The deposit is caused by precipitation of at least one of a silane coupling agent and a nonionic surfactant.

  As shown in the lubricity test results (overcoating method) in FIG. 5, Examples 1 to 4 are glass containers (dry), polyethylene resins (dry and wet), polypropylene (dry), and polyacetal (dry and wet). It was confirmed that good slipperiness was exhibited. Moreover, in Examples 1 and 2 using polyoxyethylene alkyl ether as a nonionic surfactant, it was confirmed that good slipperiness was exhibited with respect to 6 nylon (dry).

  When paying attention to the slipperiness with the glass container (wet), it was confirmed that the slipperiness was improved by the presence of the silane coupling agent. It was also confirmed that the lubricity was further improved by increasing the concentration of the silane coupling agent from 0.07 wt% to 0.20 wt%. This is presumably because the presence of the silane coupling agent does not elute the nonionic surfactant even in an environment where water is present, and is maintained on the surface of the glass container.

  As shown in the scratch test result (overcoat method) in FIG. 6, Examples 1 to 4 having a tin oxide layer have scratch resistance compared to Comparative Examples 3, 4, 7, and 8 having no tin oxide layer. It was confirmed to improve.

  As shown in the appearance test results (overcoating method) in FIG. 7, Examples 1 to 4 having a silane coupling agent and a nonionic surfactant all show a good appearance in a dry state and a wet state. Was confirmed. The reason why the wet state shows better appearance than the dry state is considered to be due to the excess nonionic surfactant being eluted by water. Moreover, it was confirmed that the case where polyoxyethylene (20) sorbitan monooleate is used exhibits a better appearance than the polyoxyethylene alkyl ether.

  As shown in the lubricity test results (mixed coating method) in FIG. 8, Examples 11 to 22 have good lubricity with respect to glass containers (dry), polyethylene resins (dry and wet), and polyacetal (dry). It was confirmed that In addition, Examples 11 to 14 using 3-aminopropyltriethoxysilane as the silane coupling agent were further confirmed to exhibit good lubricity against polypropylene (dry). In addition, Examples 15 to 18 using 3-glycidoxypropyltriethoxysilane as a silane coupling agent were confirmed to show good lubricity with respect to polypropylene (dry) and 6 nylon (dry).

  Paying attention to the slipperiness with the glass container (wet), Examples 11 to 14 using 3-aminopropyltriethoxysilane as the silane coupling agent are Examples 15 using 3-glycidoxypropyltriethoxysilane. It was confirmed that the slipperiness was higher than that of Examples 19 to 22 using ˜18 and vinyltriethoxysilane. Moreover, when paying attention to lubricity with PE, Examples 15 to 18 using 3-glycidoxypropyltriethoxysilane as silane coupling agents are examples 11 to 14 using 3-aminopropyltriethoxysilane. And it was confirmed that the slipperiness was higher than those of Examples 19 to 22 using vinyltriethoxysilane.

  In addition, from Examples 11 to 22, it was confirmed that the concentration of the silane coupling agent was higher at 0.20% by weight than at 0.07% by weight. This is presumably because the presence of the silane coupling agent does not elute the nonionic surfactant even in an environment where water is present, and is maintained on the surface of the glass container.

  As shown in the scratch test result (mixed coating method) in FIG. 9, it was confirmed that Examples 11 to 22 having a tin oxide layer exhibit good scratch resistance. It was confirmed that the scratch resistance was higher when the concentration of the silane coupling agent was 0.20% by weight than 0.07% by weight.

  As shown in the appearance test results (mixed coating method) in FIG. 10, Examples 11 to 22 having a silane coupling agent and a nonionic surfactant all show a good appearance in a dry state and a wet state. Was confirmed. It is considered that the reason why the appearance in the wet state is better than that in the dry state is that excess nonionic surfactant is eluted with water.

  As for the concentration of the nonionic surfactant, it was confirmed that 0.1% by weight shows a better appearance in the dry state than when 0.4% by weight. This result is considered to be due to the fact that the nonionic surfactant having a lower concentration is less likely to be excessive on the surface of the glass container and is less likely to precipitate on the surface of the glass container.

  Although the description of the specific embodiment is finished as described above, the present invention is not limited to the above embodiment and can be widely modified.

1: Sliding angle tester 2: Base 3: Support plates 4A to 4D: Sample 5: Base 10: Scratch tester 11A, 11B Sample 12A: First holder 12B: Second holder

Claims (17)

A glass container having a coating on its surface,
The coating includes a metal oxide layer bonded to the surface, a silane coupling agent bonded to the surface, and a nonionic surfactant bonded to at least one of the silane coupling agent and the metal oxide layer. A glass container characterized by comprising:   The nonionic surfactant is at least one selected from the group consisting of an ether type nonionic surfactant, an ester type nonionic surfactant, and an ester ether type nonionic surfactant. The glass container according to claim 1.   The glass container according to claim 1, wherein the nonionic surfactant contains at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether.   The said silane coupling agent contains at least 1 of an amino group, a vinyl group, a methacryl group, an epoxy group, a ureido group, and an isocyanate group in any one of Claims 1-3 characterized by the above-mentioned. The glass container described.   The glass container according to any one of claims 1 to 4, wherein the metal oxide layer is a tin oxide layer.   The glass container according to claim 1, wherein the coating is substantially free of polyethylene wax. A method for producing a glass container having a coating on its surface,
A first step of forming a metal oxide layer on the surface;
A second step of applying an aqueous solution containing a silane coupling agent to the surface after the first step;
And a third step of applying an aqueous solution containing a nonionic surfactant on the surface after the second step. A method for producing a glass container having a coating on its surface,
A first step of forming a metal oxide layer on the surface;
After the said 1st process, it has the 2nd process of apply | coating the aqueous solution containing a silane coupling agent and a nonionic surfactant on the said surface, The manufacturing method of the glass container characterized by the above-mentioned.   The method for producing a glass container according to claim 8, wherein the aqueous solution applied in the second step does not contain polyethylene wax.   The nonionic surfactant is at least one selected from the group consisting of an ether type nonionic surfactant, an ester type nonionic surfactant, and an ester ether type nonionic surfactant. The manufacturing method of the glass container as described in any one of Claims 7-9 characterized by these.   The nonionic surfactant includes at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether, according to any one of claims 7 to 10. Manufacturing method of glass container.   12. The glass container according to claim 11, wherein the concentration of the nonionic surfactant in the aqueous solution containing the nonionic surfactant is 0.05 wt% or more and 0.50 wt% or less. Production method. The nonionic surfactant includes at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether,
The concentration of the nonionic surfactant in the aqueous solution containing the nonionic surfactant is 0.05 wt% or more and 0.20 wt% or less. Manufacturing method of glass container.   The glass according to any one of claims 7 to 13, wherein the silane coupling agent includes at least one of an amino group, a vinyl group, an epoxy group, a ureido group, and an isocyanate group. Container manufacturing method.   The method for producing a glass container according to claim 14, wherein the concentration of the silane coupling agent in the aqueous solution containing the silane coupling agent is 0.05 wt% or more and 0.30 wt% or less.   The method for producing a glass container according to claim 15, wherein the concentration of the silane coupling agent in the aqueous solution containing the silane coupling agent is 0.15 wt% or more and 0.30 wt% or less.   The said metal oxide layer is a tin oxide layer, The manufacturing method of the glass container as described in any one of Claims 7-16 characterized by the above-mentioned.

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