JP6895339B2 - Glass container and its manufacturing method - Google Patents

Description

The present invention relates to a glass container and a method for producing the same.

In a glass container, in order to suppress scratches on the surface, the surface is coated with polyethylene wax to increase the slipperiness of the surface (for example, Patent Document 1). The coating of the glass container according to Patent Document 1 contains a silane coupling agent having an amino group in order to firmly bond the polyethylene wax to the surface of the glass container. This makes it possible to suppress the peeling of the polyethylene wax even when the glass container is exposed to a high-temperature liquid in the pastry.

Japanese Unexamined Patent Publication No. 2002-241145

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 transport 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 in order to convey the glass container along a predetermined transfer path. This guide member is often made 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 slipperiness with respect to the resin guide member. A glass container coated with polyethylene wax has relatively high slipperiness with respect to other glass containers, but the slipperiness is not sufficient with respect to resins such as polypropylene, polyethylene, nylon and polyacetal.

In view of the above background, it is an object of the present invention to improve the slipperiness of a glass container with respect to a resin member. Another object of the present invention is to provide a method for manufacturing a glass container having high slipperiness with respect to a resin member.

In order to solve the above problems, the first aspect of the present invention is a glass container having a coating on the surface, wherein the coating is a metal oxide layer bonded to the surface and a silane cup bonded to the surface. It is characterized by having 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 of the glass container with respect to the resin member can be improved. Coatings containing nonionic surfactants have higher slipperiness to resin members than coatings containing polyethylene wax. Since the nonionic surfactant binds to the silane coupling agent that is covalently bonded to the surface of the glass container, it is retained on the surface even after washing the glass container with water. Therefore, the glass container of this embodiment can also be used in a filling device including a water washing device and a pastorizer. 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. In addition, nonionic surfactants are safer and have a lower environmental load than anionic surfactants and cationic surfactants. Therefore, a glass container having a coating containing a nonionic surfactant is suitable as a container for foods, beverages, and the like.

Further, 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 preferable that there is at least one type of ester. Further, the nonionic surfactant may contain at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether.

Further, in the first aspect, the silane coupling agent may contain at least one of an amino group, a vinyl group, a methacryl group, an epoxy group, a ureido group, and an isocyanate group. Further, in the first aspect, the metal oxide layer may be a tin oxide layer. Further, in the first aspect, it is preferable that the coating is substantially free of polyethylene wax.

A second aspect of the present invention is a method for manufacturing a glass container having a coating on its surface, which comprises a first step of forming a metal oxide layer on the surface and a silane coupling after the first step. It is characterized by having 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 layer of the silane coupling agent is formed on the surface of the glass container, the layer of the nonionic surfactant is formed on the layer of the silane coupling agent, so that the layer of the nonionic surfactant is formed on the surface of the glass container. Can efficiently retain nonionic surfactants.

A third aspect of the present invention is a method for manufacturing a glass container having a coating on its surface, which comprises a first step of forming a metal oxide layer on the surface and a silane coupling after the first step. It is characterized by having a second step of applying an aqueous solution containing an agent and a nonionic surfactant to the surface. Further, in the third aspect, it is preferable that the aqueous solution applied in the second step does not contain polyethylene wax.

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

Further, 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 preferable that there is at least one species selected from the group. Further, in the second and third aspects, the nonionic surfactant may contain at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether.

Further, in the second and third aspects, 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.

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

Further, in the third aspect, the nonionic surfactant contains at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether, and is used 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, a layer of nonionic surfactant can be uniformly formed on the surface of the glass container. Further, the adhesion of the deposit of the nonionic surfactant to the surface of the glass container is suppressed, and the appearance (appearance) of the surface of the glass container can be improved.

Further, in the second and third aspects, the silane coupling agent may contain at least one of an amino group, a vinyl group, an epoxy group, a ureido group, and an isocyanate group. Further, 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. Further, in the second and third aspects, the metal oxide layer may be a tin oxide layer.

According to the present invention, it is possible to improve the slipperiness of a glass container with respect to a resin member. Further, it is possible to provide a method for manufacturing a glass container having high slipperiness with respect to a resin member.

Explanatory drawing which shows the 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 the sliding angle test of the glass container with respect to the glass container (A: front view, B: side view), explanatory view of the sliding angle test of the glass container with respect to the resin member (C: front view) , D: Side view) (A), (B) Explanatory drawing of scratch test (A: front view, B: plan view) A table showing the results of the slip angle test of each sample manufactured by the first manufacturing method (recoating method). A table showing the results of scratch tests of each sample manufactured by the first manufacturing method (overcoating method). A table showing the results of appearance observation of each sample manufactured by the first manufacturing method (recoating method). A table showing the results of the slip angle test of each sample manufactured by the second manufacturing method (mixed coating method). A table showing the results of scratch tests of each sample manufactured by the second manufacturing method (mixed coating method). A table showing the results of appearance observation of each sample produced by the second production method (mixed coating method).

(Glass container)
Hereinafter, embodiments of the present invention will be described. The glass container according to the present embodiment is a soda lime-based glass, and contains silicon, sodium, and calcium as main components. 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 , sodium is 12 to 14% by weight in terms of Na 2} O, and calcium is 10 to 10% by weight in terms of CaO with respect to the total weight of the glass. It is 12% by weight, aluminum is 1.5 to 3.0% by weight in terms of _{Al 2} O ₃ , potassium is 0.0 to 1.5% by weight in terms of _{K 2 O, and magnesium is converted to Mg O.} 0.0 to 1.5 percent by weight, sulfur is 0.03 to 0.40 wt% converted to SO _3.

The glass container according to this embodiment is formed in the form of a 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 contains 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). The hot-end coating is formed immediately after the glass container molding process (hot end), and is formed by a hot-end coating process in which a film is formed on the surface of the high-temperature (400 ° C. to 700 ° C.) glass container before the slow cooling process. Will be done.

The thickness of the metal oxide layer is 2 nm or more and 50 nm or less, preferably 5 nm or more and 20 nm or less. 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 Co., Ltd., and has a correlation with the coating thickness. 1 CTU corresponds to 0.1-0.4 nm.

The silane coupling agent comprises 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. Silane coupling agents include, for example, 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, the silane coupling agent produces a silanol group by a hydrolysis reaction of an alkoxy group. The silanol group forms a covalent bond by dehydration condensation reaction with the hydroxyl group existing on the surface of the glass container. As a result, the silane coupling agent binds to the surface of the glass container. At the same time, the silane coupling agents form a siloxane bond by dehydration condensation of silanol groups. The silane coupling agent is layered on the surface of the glass container.

The nonionic surfactant is one or more 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 contain, for example, at least one of polyoxyethylene (20) sorbitan monooleate (see FIG. 2 (A)) and polyoxyethylene alkyl ether (see FIG. 2 (B)).

The nonionic surfactant binds 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 coordination bond and an ionic bond with the 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 treatment in which a film is formed on the surface of the glass container at a low temperature (70 ° C. to 150 ° C.) after the slow cooling step (cold end) of the glass container.

The cold end coating in the present 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, when the cold end coating contains other lubricants such as polyethylene wax, polyethylene, modified polyethylene wax, and carnauba wax, these weight concentrations are negligible with respect 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 the extent that it affects slipperiness.

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

(Manufacturing method of glass container: 1)
The first method for producing a glass container having a coating on the surface is 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. The second step is followed by a third step of applying an aqueous solution containing a nonionic surfactant to the surface. As described above, the first manufacturing method in which the coating of the silane coupling agent (second step) and the coating of the nonionic surfactant (third step) are independent of each other is called a recoating method.

The first step is performed by a hot end coating treatment immediately after the molding step. The hot-end coating treatment is performed on the surface of a glass container at a high temperature (400 ° C. to 700 ° C.) by a chemical vapor deposition method (CVD). 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 carried out by a cold end coating treatment after the slow cooling step. The cold end coating treatment is carried out by applying an aqueous solution containing at least one of a silane coupling agent or a nonionic surfactant to the surface of a glass container at a low temperature (70 ° C. to 150 ° C.). The coating may be performed by spray coating or immersion coating.

In the second step, the concentration of the silane coupling agent in the aqueous solution containing 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 and 0.30% by weight or less. It is good. If the concentration of the silane coupling agent is lower than 0.05% by weight, the adhesiveness of the nonionic surfactant is lowered. Therefore, the nonionic surfactant tends to flow 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 adhesiveness 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. If the concentration of the nonionic surfactant is lower than 0.05% by weight, it is not possible to impart appropriate slipperiness 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 hardly changes.

(Manufacturing method of glass container: 2)
The second method for producing a glass container having a coating on the surface is a first step of forming a metal oxide layer on the surface, and after the first step, an aqueous solution containing a silane coupling agent and a nonionic surfactant is added. It has a second step of applying to the surface. As described above, the second production method using an aqueous solution containing a silane coupling agent and a nonionic surfactant is referred to as a 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 carried out by a cold end coating treatment after the slow cooling step. The cold end coating treatment is carried out 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 coating may be performed by spray coating or immersion coating.

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 preferably 0.30% by weight or less. The concentration of the nonionic surfactant is preferably 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.

If the concentration of the silane coupling agent is lower than 0.05% by weight, the adhesiveness of the nonionic surfactant is lowered. Therefore, the nonionic surfactant tends to flow 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 adhesiveness of the nonionic surfactant increases as the concentration increases.

If the concentration of the nonionic surfactant is lower than 0.05% by weight, it is not possible to impart appropriate slipperiness 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 hardly changes. When the concentration of the nonionic surfactant is in the range of 0.30% by weight or more and 0.50% by weight, the lower the concentration, the better the appearance of the surface. It is considered that this is because the higher the concentration, the more excess nonionic surfactant is precipitated on the surface.

According to the above aspect, the slipperiness of the glass container with respect to the resin member can be improved. Coatings containing nonionic surfactants have higher slipperiness to resin members than coatings containing polyethylene wax. Since the nonionic surfactant binds to the silane coupling agent that is covalently bonded to the surface of the glass container, it is retained on the surface even after washing the glass container with water. Therefore, the glass container of this embodiment can also be used in a filling device including a water washing device and a pastorizer.

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.

In addition, nonionic surfactants are safer and have a lower environmental load than anionic surfactants and cationic surfactants. Therefore, a glass container having a coating containing a nonionic surfactant is suitable as a container for foods, beverages, and the like.

Examples of the above-described embodiment will be described below.

Each sample according to the example was produced based on the above-mentioned first production method (overcoating method) and second production method (mixed coating method).

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

Next, as a second step, an aqueous solution containing 3-aminopropyltriethoxysilane at a predetermined concentration (0.07% by weight, 0.20% by weight) was applied to the surface of the glass container by spraying. At this time, the glass container was preheated to 120 ° C. by an oven and rotated at 2 rps using a potter's wheel. The application by spray 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 rotated at about 120 ° C. and 2 rps using a potter's wheel. The application by spray was performed at a spray angle of 110 degrees and a flow rate of 35 to 40 mL / min for 1 second. In this way, the samples (Examples 1 to 4) according to the examples were prepared.

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 above-mentioned 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 a hot-end coating treatment. The hot-end coating treatment was carried out by CVD using tin tetrachloride in a glass container at 600 ° C., and the thickness of the tin oxide layer was set to 60 CTU.

Next, as a second step, any one of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, and vinyltriethoxysilane is added to a predetermined concentration (0.07% by weight, 0.20). The surface of the glass container is sprayed with an aqueous solution containing (% by weight) and containing polyoxyethylene (20) sorbitan monooleate or polyoxyethylene alkyl ether at a predetermined concentration (0.1% by weight, 0.4% by weight). Was applied to. At this time, the glass container was preheated to 120 ° C. by an oven. The coating was performed for 0.2 seconds at a flow rate of 30 mL / min using a spray gun running on a glass container. In this way, the samples according to the examples (Examples 11 to 22) were prepared.

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

The slip angle test was performed using the slip angle tester 1 shown in FIG. The slip angle tester 1 has a base 2 and a support plate 3 rotatably provided with respect to the base 2. The support plate 3 can rotate in the vertical direction from the initial position where the support surface becomes horizontal.

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

As shown in FIGS. 3 (A) and 3 (B), 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 each other 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 a plan view. The third sample 4C was placed in parallel with the first and second samples 4A and 4B, between and above each other. In this state, the third sample 4C comes into contact with and 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 at which the third sample 4C slid down with respect to the first and second samples 4A and 4B was read as the sliding angle [deg]. The smaller the value of the slip angle, the higher the slipperiness.

As shown in FIGS. 3C and 3D, a pedestal 5 formed of a resin material to be measured was used in the slipperiness 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 is formed on the upper surface of the pedestal in a plan view. The groove has a triangular cross section and has two sloping walls. The cylindrical sample 4D of the glass container was placed parallel in the groove. In this state, the sample 4D is in 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 slid down with respect to the pedestal 5 was read as the sliding angle [deg].

The material of the pedestal 5 is polyethylene (PE), ultra-high molecular weight polyethylene 1 (UHPE1, manufactured by Sakushin Kogyo Co., Ltd., product name Newlite, μs = 0.25), ultra-high molecular weight polyethylene 2 (UHPE 2, Sakushin Kogyo Co., Ltd.) Manufactured by, product name NL-supermu LF, μs = 0.11), polypropylene (PP), 6 nylon (PA6), polyacetal (POM).

The scratch test was performed using the scratch tester 10. The scratch tester 10 uses two cylindrical samples 11A and 11B of a glass container. The scratch tester 10 has 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. Has 12B and. The first and second holders 12A and 12B support the first and second samples 11B so that they intersect each other at 90 degrees in a plan view and are in contact with each other up and down. 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 any of the first sample 11A and the second sample 11B is scratched. did. In the test, the load applied to the second sample 11B was gradually increased, and the load when a scratch was generated was defined as the scratch generation load [kg]. The larger the value of the scratch generation load, the less likely it is that scratches will occur. The scratch test was performed in the dry state and the wet state in the same manner as the slip angle test.

In the appearance observation, the glass container in the dry state and the wet state was visually confirmed, and white deposits (dirt) on the surface of the glass container were confirmed. The deposits are due to the precipitation of at least one of the silane coupling agent and the nonionic surfactant.

As shown in the slipperiness test result (recoating method) of FIG. 5, Examples 1 to 4 are a glass container (dry), a polyethylene-based resin (dry and wet), polypropylene (dry), and polyacetal (dry and wet). It was confirmed that it showed good slipperiness. Further, it was confirmed that in Examples 1 and 2 in which polyoxyethylene alkyl ether was used as the nonionic surfactant, good slipperiness was exhibited with respect to 6 nylon (dry).

Focusing on the slipperiness with the glass container (wet), it was confirmed that the slipperiness was improved by the presence of the silane coupling agent. Further, it was confirmed that the slipperiness was further improved by increasing the concentration of the silane coupling agent from 0.07% by weight to 0.20% by weight. It is considered that this is because the nonionic surfactant does not elute and is maintained on the surface of the glass container even in the environment where water is present due to the presence of the silane coupling agent.

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

As shown in the appearance test result (recoating method) of FIG. 7, Examples 1 to 4 having the silane coupling agent and the nonionic surfactant all show good appearance in the dry state and the wet state. Was confirmed. It is considered that the reason why the wet state shows a better appearance than the dry state is that the excess nonionic surfactant is eluted by water. It was also confirmed that the appearance was better when polyoxyethylene (20) sorbitan monooleate was used than when polyoxyethylene alkyl ether was used.

As shown in the slipperiness test result (mixed coating method) of FIG. 8, Examples 11 to 22 have good slipperiness with respect to a glass container (dry), a polyethylene resin (dry and wet), and a polyacetal (dry). Was confirmed to indicate. Further, it was confirmed that Examples 11 to 14 in which 3-aminopropyltriethoxysilane was used as the silane coupling agent further exhibited good slipperiness with respect to polypropylene (dry). Further, it was confirmed that Examples 15 to 18 in which 3-glycidoxypropyltriethoxysilane was used as the silane coupling agent further showed good slipperiness with respect to polypropylene (dry) and 6 nylon (dry).

Focusing on the slipperiness with the glass container (wet), Examples 11 to 14 in which 3-aminopropyltriethoxysilane was used as the silane coupling agent were compared with Example 15 in which 3-glycidoxypropyltriethoxysilane was used. It was confirmed that the slipperiness was higher than that of Examples 19 to 22 using -18 and vinyltriethoxysilane. Focusing on the slipperiness with PE, Examples 15 to 18 in which 3-glycidoxypropyltriethoxysilane was used as the silane coupling agent, and Examples 11 to 14 in which 3-aminopropyltriethoxysilane was used. And it was confirmed that the slipperiness was higher than that of Examples 19 to 22 using vinyltriethoxysilane.

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

As shown in the scratch test result (mixed coating method) of FIG. 9, it was confirmed that Examples 11 to 22 having the tin oxide layer exhibited 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 when the concentration was 0.07% by weight.

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

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

Although the description of the specific embodiment is completed above, the present invention can be widely modified without being limited to the above embodiment.

1: Sliding angle tester 2: Base 3: Support plate 4A to 4D: Sample 5: Pedestal 10: Scratch tester 11A, 11B Sample 12A: 1st holder 12B: 2nd holder

Claims (9)

A method for manufacturing a glass container having a coating on its surface.
The first step of forming a metal oxide layer on the surface and
After the first step, a second step of applying an aqueous solution containing a silane coupling agent to the metal oxide layer, and
A method for producing a glass container, which comprises, after the second step, a third step of applying an aqueous solution containing a nonionic surfactant to the metal oxide layer coated with the silane coupling agent. 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 method for manufacturing a glass container according to claim 1 , wherein the method is characterized by the above. The method for producing a glass container according to claim 1 or 2 , wherein the nonionic surfactant contains at least one of polyoxyethylene (20) sorbitan monooleate and polyoxyethylene alkyl ether. .. The glass container according to claim 3 , wherein the concentration of the nonionic surfactant in the aqueous solution containing the nonionic surfactant is 0.05% by weight or more and 0.50% by weight or less. Production method. The glass container according to claim 3 , wherein the concentration of the nonionic surfactant in the aqueous solution containing the nonionic surfactant is 0.05% by weight or more and 0.20% by weight or less. Production method. The glass according to any one of claims 1 to 5 , wherein the silane coupling agent contains at least one of an amino group, a vinyl group, an epoxy group, a ureido group, and an isocyanate group. How to make a container. The method for producing a glass container according to claim 6 , wherein the concentration of the silane coupling agent in the aqueous solution containing the silane coupling agent is 0.05% by weight or more and 0.30% by weight or less. The method for producing a glass container according to claim 7 , wherein the concentration of the silane coupling agent in the aqueous solution containing the silane coupling agent is 0.15% by weight or more and 0.30% by weight or less. The method for producing a glass container according to any one of claims 1 to 8 , wherein the metal oxide layer is a tin oxide layer.

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