JP3895519B2 - Glass container - Google Patents

Description

【００６３】
【発明の効果】
本発明によれば、容器外面に、セルロースと水溶性高分子からなる組成物を主体とする親水性膜から、固体滑剤粒子が頭を出している被覆を形成し、上記親水性膜の厚みを０．１乃至１．０μｍ、固体滑剤粒子の平均粒子径を０．２乃至２．０μｍとしたことにより、形成される親水性膜が耐擦り傷性と滑性とに優れていると共に親水性を有し、優れたラベル貼着性、水濡れ性、耐汚れ性、耐水性を有するガラス容器、特にガラスビンを提供することができる。
また、本発明によれば上記被覆をガラスビンの表面にコールドエンドコート（ＣＥＣ）によって容易に施すことができ、生産性に優れ、製造コストも低いという利点がある。
【図面の簡単な説明】
【図１】 本発明の被覆容器の断面構造を示す断面図である。
【図２】 被覆表面における固体滑剤粒子の粒子構造を示す電子顕微鏡写真である。
【符号の説明】
１ 基材
２ 親水性膜
３ 固体滑剤粒子
４ 膜表面[0001]
BACKGROUND OF THE INVENTION
  The present invention has a hydrophilic filmGlass such as glass bottlesIt relates to containers, and more specifically, the formed film has excellent scratch resistance and lubricity, as well as excellent label adhesion, water wettability, and dirt resistance.GlassConcerning the container.
[0002]
[Prior art]
  Glass bottles are excellent in transparency, rigidity and hygienic properties, have no environmental pollution problems, and can be recovered and reused for a long time, but they have the disadvantage of being easily scratched and easily broken. Also have. Nevertheless, there is a strong demand for lighter glass bottles from the standpoint of reducing distribution costs.
[0003]
  Glass bottles are known to significantly reduce the strength of glass bottles, although scratches or scratches generated on the surface are known to significantly reduce the strength of glass bottles, even though they are fairly strong in the early stages of molding with no scratches on the surface. The generation of scratches becomes a serious problem particularly in a glass bottle that has been reduced in weight.
[0004]
  Conventionally, in order to improve the scratch resistance of a glass bottle, it is known to perform a coating process called hot end coating or cold end coating on the surface of the glass bottle.
  For example, Japanese Patent Publication No. 42-1758 discloses a titanium-, zirconium-, tin-, or vanadium-containing compound capable of generating a metal oxide on a glass surface by pyrolysis, and the glass surface is the compound. An olefin polymer on the glass surface which is treated while being at a temperature equal to or higher than the pyrolysis temperature of the glass, cooling the treated surface to a temperature of 232 ° C. or less, and still being heated. A glass surface characterized by being sprayed with polyurethane, polystyrene or N-alkylamine acetate in an amount sufficient to produce a thin, tightly bonded, transparent, substantially colorless coating on the surface A method is described for increasing the wear resistance.
[0005]
[Problems to be solved by the invention]
  Formed coating of olefin polymer such as polyethylene mentioned aboveGlass bottleHowever, compared with the glass bottle itself, the label sticking property is inferior, and the water wettability is inferior.
  In addition, this polyethylene-coated glass bottle has a drawback that dirt substances are easily attached, and it is not yet satisfactory in terms of lubricity.
[0006]
  Therefore, the object of the present invention is that the formed film is excellent in scratch resistance and lubricity, and has excellent label stickability, water wettability, stain resistance, and water resistance.Glass such as glass bottlesIn providing a container.
  Another object of the present invention is glass.containerCoated glass which can be easily applied to the surface of the glass by a cold end coat (CEC), and the coating formed has the characteristics described abovecontainerTo provide.
[0007]
[Means for Solving the Problems]
  According to the present invention, on the outer surface of the container,Hydrophilic, mainly composed of cellulose and water-soluble polymerFrom the membrane, a coating is formed in which solid lubricant particles protrude, the membrane is 0.1 to 1.0 μm thick and the solid lubricant particles have an average particle size of 0.2 to 2.0 μm. Characterized byGlassA container is provided.
  Of the present inventionGlassIn the container
1. The solid lubricant particles are made of olefin resin or high melting point wax;
2. The solid lubricant particles are made of polyethylene wax or modified polyethylene wax;
3. Solid lubricant particle size /Hydrophilic film thicknessThe ratio of1.3 to 2.5Being
4).Cellulose and hydrophilicSolid lubricant particles hit the polymer5 to 40Present in an amount of% by weight,
Is preferred.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
[Action]
  Of the present inventionGlassIn the container
  A. On the outer surface of the container,Hydrophilic, mainly composed of cellulose and water-soluble polymerThat a film is formed,
  B. thisHydrophilicSolid lubricant particles protruding from the membrane, and
  C. The membrane is 0.1 to 1.0 μm thick and the solid lubricant particles have an average particle size of 0.2 to 2.0 μm;
Is a feature and is thereby formedHydrophilicIn addition to excellent scratch resistance and slipperiness, the film achieves the advantages in terms of action and effect that it is excellent in label sticking property, water wettability and stain resistance.
[0009]
  In the present invention,Hydrophilic, mainly composed of cellulose and water-soluble polymerMembraneGlassIt is basically important to provide it on the outer surface of the container. the aboveCellulose and water-soluble polymersBased onHydrophilicBy providing a membrane on the outer surface, imparting hydrophilicity to the outer surface of the membrane,GlassWater wettability is imparted to the outer surface of the container to prevent water droplets from being attached, which can cause malfunction of the inspection machine for liquid level detection in the filling process, improve label stickiness, and improve stain resistance. Can be improved.
[0010]
  NormalSuch as glass bottlesIn the glass container, the contents, the source, the expiration date, and the like are displayed by sticking a label. Traditionally, starch paste is widely used for sticking the label. This is essentially hydrophilic when the glass surface is not soiled, and when reusing the glass bottle, the label is peeled off by water immersion.InIt seems to be closely related.
  Coating in the present inventionGlassSince the outer surface of the container is essentially hydrophilic, the advantage of excellent label sticking is achieved.
[0011]
  In the filling process into the glass bottle, there are many opportunities for dirt to adhere to the glass bottle. First, in the glass bottle cleaning process, there is an opportunity for dirt substances derived from the coating material to adhere, in the filling process there is an opportunity for the contents blown out due to the generation of bubbles to adhere as dirt, and in the heat sterilization process,Glass bottleThe contents attached to the outer surface are dissolved or dispersed in hot water etc.Glass bottleMay adhere to the outer surface.
  This is because troublesome dirt among these adhered dirt is oily, and even if it comes into contact with water or hot water, it remains as it is without being removed from the glass surface.
  In the present invention, since the outer surface of the coated glass is made hydrophilic, the oily dirt is difficult to adhere, and even if temporarily attached, it is easily detached from the outer surface, so that it has excellent dirt resistance. Benefits are achieved.
[0012]
  In the present invention, the above-mentionedCellulose and water-soluble moleculesBased onHydrophilicThe second feature is that the coating structure is such that solid lubricant particles protrude from the surface of the membrane.
  In general, for the purpose of imparting lubricity to the coating, it is often done to add a lubricant to the coating. However, the improvement of the lubricity and the scratch resistance by such a general formulation of the lubricant are slight. In particular, when the coating film is hydrophilic, the improvement is slight as shown in the examples described later.
  On the other hand, according to the present invention, when the solid lubricant particles have a dispersed structure protruding from the film surface, as shown in the examples described later, the film surface can be provided with excellent lubricity and scratch resistant. It is possible to significantly improve the performance.
  The scratch resistance is naturally related to the slipperiness of the film, but at the same time, it is also related to the film strength. With the coating of the dispersed structure of the present invention, the film strength is also increased.
[0013]
  The covering structure isWater-dispersible cellulose and water-soluble polymer solutionDisperse the solid lubricant particles in a glass bottle or other dispersion.GlassIt is formed by applying to the container surface and drying, but it is important that the solid lubricant particles remain in the coating while maintaining the particle structure. By doing so, a coating structure in which a part of the solid lubricant particles protrudes from the smooth surface of the film is obtained.
[0014]
  In FIG. 1 for explaining the covering structure of the present invention,SuA hydrophilic film 2 is formed on the surface of the material 1, and solid lubricant particles 3 are blended in the hydrophilic film, and the solid lubricant particles 3 protrude from the film surface 4 and are exposed to the outside. In addition, due to the lubricity of the exposed solid lubricant particles 3, scratch resistance when the film is rubbed is eliminated.
  That is, the solid lubricant particles 3 act to prevent direct contact between the other object and the film surface 4, and reduce friction with the object by its own lubricity.
[0015]
  Actually, when the film surface according to the present invention is observed with an electron microscope, it is confirmed that solid lubricant particles are distributed in islands in the sea of the hydrophilic film as shown in the electron micrograph of FIG.
[0016]
[Hydrophilic membrane]
  In the present invention, the composition forming the hydrophilic film is composed of cellulose and a hydrophilic polymer. The cellulose is a water-dispersible organic polymer, while the water-soluble organic polymer is an anionic or nonionic water-soluble polymer. Organic polymers are used.
  Examples of the anionic polymer include sodium polyacrylate or a copolymer of sodium polyacrylate and polyacrylamide, polysodium methacrylate, sodium alginate, ammonium alginate, carboxymethyl starch, carboxymethylcellulose, acrylamide-acrylic acid Copolymer, chitosaEtc.Is used.
  Also,Nonionic polymers include polyvinyl alcohol (PVA), starch, cyanated starch, and methylcellulose.Su, hiDroxyethyl cellulose, bee gum, gelatin, etc.used.
  theseWater solubleThe polymers can be used alone or in combination of two or more.
[0017]
  BookThe hydrophilic membrane of the invention is particularly preferably formed from a composition of cellulose and a water-soluble polymer, particularly a water-soluble cellulose derivative. Cellulose is hydrophilic but water-insoluble, and when used in combination with a water-soluble polymer, the water dispersibility required for preparation of the coating solution and the coating properties required for film formation can be obtained. The advantage of having a certain degree of water resistance while achieving a hydrophilic coating is achieved.
  Generally speaking, cellulose (A) and water-soluble polymer (B) are:
          A: B = 98: 2 to 50:50,
          Especially 95: 5 to 75:25
Is preferably used in order to achieve the above advantages.
[0018]
[Solid lubricant particles]
  As the solid lubricant particles to be blended in the hydrophilic film, an organic solid lubricant is desirable, and a resin or wax-like material having lubricity is used alone or in combination of two or more.
  The organic solid lubricant to be used preferably has a heat resistance of 80 ° C. or higher, and is preferable in order to maintain the above-described film structure in the formed film. From this viewpoint, the resin-based solid lubricant and the olefin having lubricity A lubricant mainly composed of a resin, a fluorine resin or the like is advantageously used.
[0019]
  Particularly preferred resin-based lubricant particles are olefin-based resin particles such as low-, medium- or high-density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, polybutene-1, ethylene-butene- 1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ion-crosslinked olefin copolymer (ionomer), ethylene-acrylic acid ester copolymer Particles such as coalescence are used.
[0020]
  These olefin-based resins have a glass transition point lower than room temperature and are particularly excellent in scratch resistance. The molecular weight of the olefin resin is not particularly limited, but a relatively low molecular weight material generally called polyethylene wax gives an excellent effect. Modified olefin resins such as oxidized polyethylene wax and acid-modified polyethylene wax are also preferably used for the purpose of the present invention.
[0021]
  Another preferred example of the modified olefin resin-based lubricant particles is an acrylic resin having a glass transition point lower than room temperature.Acid changeAnd particles of a functional resin. Examples of the acrylic monomer constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. Examples include isobutyl acid, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate. it can. However, said (meth) acrylic acid shows acrylic acid or methacrylic acid, and these are 20 mol% or less copolymer products. These acrylic monomers may be copolymerized with other comonomers, such as styrene, acrylic acid, methacrylic acid, maleic anhydride, divinylbenzene, ethylene glycol dimethacrylate, and the like, if necessary.
[0022]
  Other examples of the resin fine particles include fluorine-based resins such as polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, polyvinyl fluoride, and polyvinylidene fluoride. These fluororesins have a glass transition point higher than room temperature, but their excellent slip properties are useful for scratch resistance.
[0023]
  Non-resin-based solid lubricants, such as waxes such as spalm acetyl wax, montan wax, carnauba wax, beeswax, wood wax, cotton wax, and high melting points such as stearic acid amide, erucic acid amide, stearic acid bisamide, and higher fatty acid ethylenediamine derivatives Waxes can also be used alone or in combination with a resin-based lubricant.
[0024]
  These solid lubricant particlesIs 0. Average particle diameter of 2 to 2.0 μm (volume-based median diameter)age,The particle shape of the solid lubricant particles is preferably spherical, but is not necessarily limited thereto, and may be irregular particles by a pulverization method or other regular particles.
[0025]
[Coating composition]
  Such as glass bottlesGlassThe coating composition used for coating the container is an essential component.Cellulose and water-soluble polymersIt comprises (I) and solid lubricant particles (II).
  Solid lubricant particles (II)Cellulose and water-solubleHit polymer (I)5Used in an amount of up to 40% by weight.
  If the amount of the solid lubricant particles is below the above range, the lubricity is insufficient, and the scratch resistance tends to be reduced. On the other hand, if the amount of the solid lubricant particles exceeds the above range, the film strength is reduced, and the scratch resistance is also reduced. However, when the amount of the solid lubricant particles is within the above range, the scratch resistance can be improved as compared with any of the above cases.
[0026]
  The coating composition is generally preferably used in the form of an aqueous dispersion. This aqueous dispersion isCellulose and water-solubleHigh molecularConsist ofIt can be prepared by dispersing solid lubricant particles in an aqueous dispersion.
  In aqueous dispersionsCellulose and water-solubleThe concentration of the polymer is not particularly limited, but is generally in the range of 0.1 to 50 g / L, particularly 0.5 to 10 g / L, expressed in g (gram) per liter of liquid. From the viewpoint of coating workability and controllability of thickness.
[0027]
  In the aqueous dispersion used in the present invention, the dispersibility of each component is improved, or the dispersion stability is improved.SuComponents for improving wettability to the vessel can be included.
  Such components include surfactants and water-miscible organic solvents.
[0028]
  Examples of the surfactant include primary higher alcohol sulfate, secondary higher alcohol sulfate, primary higher alkyl sulfonate, secondary higher alkyl sulfonate, higher alkyl disulfonate, sulfone. Higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid ester sulfonate salt, higher alcohol ether sulfate ester salt, higher alcohol ether sulfonate salt, higher fatty acid amide alkylol sulfate sulfate salt, alkylbenzene sulfonate salt, Anionic surfactants such as alkyl phenol sulfonates, alkyl naphthalene sulfonates, alkyl benzimidazole sulfonates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, Polyoxyethylene fatty acid esters, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester. Polyoxyethylene polyhydric alcohol fatty acid ester, fatty acid sucrose ester, alkylolamide, polyoxyalkylene block copolymer and the like are used.
  These surfactants are generally used in an amount of 1.0 g or less per liter of aqueous dispersion.
[0029]
  Water-miscible organic solvents include alcohol solvents such as methanol, ethanol, propanol and butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran and dioxane; ethyl acetate and butyl acetate Ester solvent such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, etc .; carbitol solvents such as methyl carbitol, ethyl carbitol, butyl carbitol, etc.
  These water-miscible organic solvents are generally used in an amount of 45 ml or less per liter of aqueous dispersion.
[0030]
  GlasscontainerHas the advantages of being chemically durable, non-breathable, hygienic, and high in shelf life, but has the disadvantage of being heavy, easily scratched and easily broken. . Efforts to reduce the weight of the former defect have been made conventionally, and it is important to improve the scratch resistance of the surface to improve the strength to improve the latter defect. A coating is required.
[0031]
  GlasscontainerThe glass composition is not particularly limited, but so-called soda-lime glass is generally used.containerIn the manufacturing process, the glass is melted at a high temperature of 1500 ° C. or higher in the melting chamber, and gradually and gradually cooled through the throat, the working chamber and the hoar hearth, and cut into a candy-like glass lump (gob) of about 1100 ° C. with the feeder at the tip. Then, it is put into a mold of a bottle making machine, and molding is completed through a rough mold and a finish mold.
  In the present invention, immediately after the bottle is formed, the coating process is performed in the middle of the conveyor from the slow cooling kiln (lehr).
[0032]
  GlasscontainerExamples of the types include milk beverage bottles, cola, ramune, juice beverage bottles, soy sauce, vinegar and other seasoning bottles, beer, whiskey, sake beverages, etc. Especially suitable for one-way bottle applications.
  Glass as basecontainerMay be colorless and transparent, and may be made of brown or green UV-blocking glass for filling contents that impair the flavor by UV rays.
[0033]
  The present invention can also be applied to metal oxide coated glass bottles that can be used repeatedly as returnable bottles. The formation of a metal oxide coating on the surface of a glass bottle is generally called hot end coating, and is performed immediately after the bottle is formed and on the way to a slow cooling kiln (lehr).
[0034]
  Examples of the metal oxide include oxides of titanium and tin. The metal oxide layer is preferably provided as a continuous layer having a thickness of 150 to 480 angstroms.
  Hot end coating is a kind of chemical vapor deposition (CVD), and is brought into contact with a gas containing a glass bottle at a temperature of 500 to 650 ° C. in a reaction chamber provided before a slow cooling kiln. By doing.
  Examples of the metal component include organic titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, tetratitanate, tetraethyl titanate, tetraethylhexyl titanate, tetranonyl titanate, and chlorides such as titanium tetrachloride and tin tetrachloride. The
[0035]
[Coating and its manufacture]
  In the hydrophilic film of the present invention,Water-dispersible organic polymer cellulose and water-solubilityPolymer coatingIs 0. Provided with a thickness of 1 to 1.0 μmThe
  When the thickness of the film is less than the above range, hydrophilicity is insufficient and the film strength is low and impractical compared to the case where the thickness is within the above range. On the other hand, even if the thickness of the coating exceeds the above range, there is no particular advantage compared to the case where the thickness is within the above range, on the contrary, the original transparency of the glass bottle is lost, the processing cost increases, Since productivity falls, it is not preferable.
[0036]
  In the present invention, the particle size / hydrophilicity of the solid lubricantSex membraneThickness ratioIs 1. In the range of 3 to 2.5The
  Particle size / hydrophilicity of solid lubricantSex membraneIf the thickness ratio is less than the above range, the activity and scratch resistance tend to be lower than in the above range, which is not preferable. On the other hand, when this ratio exceeds the above range, the film strength is lowered or the hydrophilicity becomes insufficient, which is not preferable.
[0037]
  The treatment for forming the coating on the outer surface of the glass bottle is performed as a cold end coat, and the coating composition described above, ie, aqueous, is generally applied to a glass bottle having a temperature of 80 to 150 ° C. from the annealing furnace. This is done by spraying the dispersion.
[0038]
  In the present invention, the glass bottle surface is formed.HydrophilicSince the thickness of the film may be very small, it is an advantage that the coating treatment by spraying can be performed in a remarkably short time. For example, as shown in an example described later, it takes a short time of about 0.1 to 1.0 seconds. Can be done within.
  For this reason, the coating treatment of the present invention has the advantages of high productivity and low processing costs.
[0039]
【Example】
  The invention is further illustrated in the following examples, which areIsIt is not limited to the following examples.
  Various measurements in the examples were performed as follows.
[0040]
[Lubricity test]
  Two glass bottles were arranged in a side-by-side relationship on a support base capable of adjusting the angle, one glass bottle was placed on the two glass bottles, and the angle at which the upper glass bottle slides down was determined.
  It shows that it is excellent in slipperiness, so that an angle is small.
[0041]
[Abrasion resistance]
  Two glass bottles are supported by upper and lower support bases in a vertical and vertical positional relationship, a load of 0.4 to 5 MPa is applied to the upper support base, and the lower support base is moved horizontally under the above load. The glass bottles were rubbed together, and it was examined whether or not scratches were generated.
  Eighteen samples were used in one test, and are shown as a percentage of the number of items that do not cause scratches.
[0042]
[Labelability]
  The starch paste was applied to the back surface, and a label with a pre-marked outer surface was attached to a glass bottle. After the glue was dried at room temperature for a whole day and night, the label was peeled off, and the area that did not peel off was shown as a percentage. .
  It shows that label stickability is excellent, so that a numerical value is large.
[0043]
[Water wettability]
  The glass bottle was immersed in water at 17 to 22 ° C. for 5 seconds, the glass bottle taken out from the water was held in an upright state for 5 seconds, and then evaluated from the attached state of water droplets according to the following evaluation criteria.
      ○ The entire surface of the glass bottle is wet smoothly with water, and no water droplets are observed.
      Δ: Adherence of water droplets is observed in various portions of the glass bottle.
      X: Water droplets are observed throughout the glass bottle.
[0044]
[Stain adhesion]
  An aqueous solution of 1% by weight of lanolin is homogenized and completely emulsified. The solution at a temperature of 60 ° C. is brought into contact with the glass bottle by the dipping method, and the adhesion state of the soil is evaluated from the adhesion state of the lanolin to the glass bottle according to the following evaluation criteria. did.
      ○ ... No or almost no dirt adheres to the glass bottle.
      Δ: Stain adherence to the glass bottle is observed in some places.
      × ··· Adhering of dirt to the glass bottle is considerably observed.
[0045]
[water resistant]
  The cold-end coated glass bottle was immersed in water at 80 ° C. for 30 minutes and pulled up from the water, and then the coating state was evaluated according to the following evaluation criteria.
      ○ …… No or little change in coating.
      Δ: Partial dissolution or whitening is observed in the coating.
      × ··· The coating is remarkably dissolved.
[0046]
[Surface condition]
  The cold-end coated glass bottle was observed with the naked eye using the untreated glass bottle as a reference, and evaluated according to the following evaluation criteria.
      ○ ... Almost no cloudiness or unevenness is observed on the coating.
      Δ: Slight cloudiness or unevenness is observed on the coating.
      × .. The cloudiness or unevenness of the coating is remarkable.
[0047]
  The materials used are as follows.
I Film forming material
(1) Water dispersible celluloseAnd hydrophilic polymers
  Water dispersible cellulosePowder89% by weight of crushed cellulose,as well asAs a hydrophilic polymerA composition of 11% by weight carboxymethylcellulose (CMC) was used.
(2) Polyvinyl alcohol (PVA)
  Polyvinyl alcohol having an average polymerization degree of 500 and a saponification degree of 98 mol% was used.
(3) Cellulose acetate
  Cellulose acetate having a degree of esterification of 99% was used.
(4) Cellulose xanthate
  Viscose obtained by reacting alkali disulfide with carbon disulfide was used.
(5) Polyethylene wax
  A polyethylene wax emulsion was used.
[0048]
[Reference Example 1]
  Water dispersible celluloseAnd hydrophilic polymersA 0.2 wt% aqueous dispersion was used, a glass plate was immersed in the aqueous dispersion, a film was formed on the glass plate, and the above-described various tests were performed on this coated glass plate.
  The film strength was evaluated by a method according to JIS K 5400 (Paint General Test Method). That is, the film scratching by the pencil scratch test method using a 4H pencil and the film adhesion by the cross-cut tape test method were comprehensively evaluated.
  ○ No change was observed in the pencil scratch test and the cross cut tape test.
  Δ: The film is partially removed by the pencil scratch test. Or part of the film is peeled off by the cross-cut tape test.
  ×: Most of the film is scraped off by the pencil scratch test. Or, most of the film is peeled off by the cross-cut tape test.
  The obtained results are shown in Table 1.
[0049]
[Reference Example 2]
  Water dispersible celluloseAnd hydrophilic polymersA coated glass plate was produced in the same manner as in Reference Example 1 except that a 0.2% by weight aqueous solution of PVA was used instead of PVA, and the test was performed in the same manner as in Reference Example 1.
  The obtained results are shown in Table 1.
[0050]
[Reference Example 3]
  Water dispersible celluloseAnd hydrophilic polymersA coated glass plate was produced in the same manner as in Reference Example 1 except that a 2-butane solution having a cellulose acetate concentration of 0.2% by weight was used instead of the above, and the test was performed in the same manner as in Reference Example 1.
  The obtained results are shown in Table 1.
[0051]
[Reference Example 4]
  Water dispersible celluloseAnd hydrophilic polymersA coated glass plate was produced in the same manner as in Reference Example 1 except that a 0.2 wt% (cellulose equivalent) aqueous solution of cellulose xanthate was used and the formed film was treated with a sulfuric acid aqueous solution. The test was conducted in the same manner as in Example 1.
  The obtained results are shown in Table 1.
[0052]
[Reference Example 5]
  Water dispersible celluloseAnd hydrophilic polymersA coated glass plate was produced in the same manner as in Reference Example 1 except that a 0.2% by weight aqueous emulsion of polyethylene wax was used instead of and a test was conducted in the same manner as in Reference Example 1.
  The obtained results are shown in Table 1.
[0053]
[Table 1]
    Reference example 1 2 3 4 5
    Lubricity △ △ △ △ ○
    Film strength ○ △ − ○ △
    Label adhesion ○ ○ × ○ ×
    Water leakage ○ ○ △ ○ ×
    Anti-stain adhesion ○ ○ × ○ ×
    Surface condition ○ ○ ○ △ ○
    Water resistance ○ △ ○ ○ △
[0054]
  Polyethylene wax, which has been widely used for cold end coating of glass bottles in the past, is excellent in lubricity, but has poor film strength, and is unacceptable in terms of label stickability, water wettability, and dirt adhesion. there were.
  Meanwhile, water dispersible celluloseAnd hydrophilic polymersAlthough the film was slightly inferior in terms of lubricity, it was acceptable in all respects of film strength, label stickability, water wettability, and adhesion to dirt.
[0055]
[Example 1]
  As the solid lubricant particles, polyethylene wax having an average particle diameter of 0.6 μm and a melting point of 115 ° C. was used.
  The water dispersible cellulose mentioned aboveAnd hydrophilic polymersIs dispersed in water and homogenized, and then the polyethylene wax is further dispersed to obtain water-dispersed cellulose.And hydrophilic polymersContaining 2 g / L of polyethylene and 0.4 g / L of polyethylene waxdispersionA liquid was prepared.
[0056]
  A beverage glass bottle having an internal volume of 100 ml and a height of 130 mm maintained at a temperature of 110 ° C. is maintained in an upright state, and the glass bottle is rotated (spun) at a speed of 240 rpm, and the aqueous dispersion is passed through the spray nozzle to the glass bottle. Sprayed for 0.5 seconds.
[0057]
  The thickness of the formed hydrophilic film was 0.3 μm, and the area ratio of polyethylene wax on the surface of the hydrophilic film was 11%.
  A scanning electron micrograph of the surface of the formed coating is shown in FIG. From this Fig. 2, water dispersionsexcelluloseAnd hydrophilic polymersA state in which the polyethylene wax particles protrude from the hydrophilic coating consisting of is observed.
  The obtained coated glass bottle was tested for each item described above, and the results obtained are shown in Table 2.
  The test for scratch resistance was performed under a load of 5 MPa.
[0058]
[Example 2]
  Instead of the aqueous dispersion of Example 1, the following composition
      Water dispersible celluloseAnd hydrophilic polymers    2g / L
      Polyethylene wax 0.2g / L
      Potassium oleate 0.05g / L
      Isobutyl alcohol 20ml / L
A coated glass bottle was produced in the same manner as in Example 1 except that the aqueous dispersion was used and the spraying time was 0.75 seconds.
  The thickness of the formed hydrophilic film was 0.4 μm, and the area ratio of the polyethylene wax on the surface of the hydrophilic film was 8%.
  The obtained coated glass bottle was tested in the same manner as in Example 1, and the obtained results are shown in Table 2.
[0059]
[Example 3]
  As the solid lubricant particles, polyethylene wax having an average particle diameter of 1.0 μm and a melting point of 102 ° C. was used, and instead of the aqueous dispersion of Example 1, the following composition was used.
      Water dispersible celluloseAnd hydrophilic polymers        5g / L
      Polyethylene wax 0.5g / L
A coated glass bottle was produced in the same manner as in Example 1 except that the aqueous dispersion was used.
  The thickness of the formed hydrophilic film was 0.6 μm, and the area ratio of polyethylene wax on the surface of the hydrophilic film was 6%.
  The obtained coated glass bottle was tested in the same manner as in Example 1, and the obtained results are shown in Table 2.
[0060]
[Example 4]
  As the solid lubricant particles, carnauba wax having an average particle diameter of 2.0 μm and a melting point of 84 ° C. was used instead of the aqueous dispersion of Example 1, and the following composition:
      Water dispersible celluloseAnd hydrophilic polymers      5 g / L,
      Carnauba wax 1.0g / L
A coated glass bottle was produced in the same manner as in Example 1 except that the aqueous dispersion was used.
  The thickness of the formed hydrophilic film was 0.6 μm, and the area ratio of carnauba wax on the hydrophilic film surface was 7%.
  The obtained coated glass bottle was tested in the same manner as in Example 1, and the obtained results are shown in Table 2.
[0061]
  [Comparative example]
  Instead of the aqueous dispersion of Example 1, an emulsion solution consisting of 2 g / L of polyethylene wax having a melting point of 104 ° C. and an average dispersion particle size of 0.2 μm, and 0.6 g / L of potassium oleate was used, and the spray time was set to 0.00. A coated glass bottle was produced in the same manner as in Example 1 except for 5 seconds.
  The thickness of the formed film was 0.3 μm.
  The obtained coated glass bottle was tested in the same manner as in Example 1, and the obtained results are shown in Table 2.
[0062]
[Table 2]

[0063]
【The invention's effect】
  According to the present invention, on the outer surface of the container,Cellulose and water-solubleHigh molecularA composition comprisingBased onHydrophilicFrom the membrane,A solid lubricant particle forms a protruding coatingThe thickness of the hydrophilic film is 0.1 to 1.0 μm, and the average particle size of the solid lubricant particles is 0.2 to 2.0 μm.Formed byHydrophilicThe film is excellent in scratch resistance and lubricity and hydrophilic, and has excellent label adhesion, water wettability, dirt resistance, and water resistance.GlassContainers, particularly glass bottles, can be provided.
  Also according to the present inventionAboveCoatingTheIt can be easily applied to the surface of Rasbin by cold end coating (CEC), and has the advantages of excellent productivity and low production cost.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a cross-sectional structure of a coated container of the present invention.
FIG. 2 is an electron micrograph showing the particle structure of solid lubricant particles on a coated surface.
[Explanation of symbols]
    1 Base material
    2 Hydrophilic membrane
    3 Solid lubricant particles
    4 Membrane surface

Claims (5)

The outer surface of the container, the hydrophilic film mainly made of a composition consisting of cellulose and a water-soluble polymer, coating the solid lubricant particles are put his head is formed, the hydrophilic film is 0.1 to 1.0μm in A glass container having a thickness and an average particle size of solid lubricant particles of 0.2 to 2.0 μm. 2. The glass container according to claim 1, wherein the solid lubricant particles are made of an olefin resin or a high melting point wax. 3. The glass container according to claim 1, wherein the solid lubricant particles are made of polyethylene wax or modified polyethylene wax. The glass container according to any one of claims 1 to 3, wherein the ratio of solid lubricant particle diameter / hydrophilic film thickness is 1.3 to 2.5 . 5. A glass container according to claim 1, wherein the solid lubricant particles are present in an amount of 5 to 40 % by weight per cellulose and hydrophilic polymer .

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