WO2020149229A1 - Tube de dentifrice - Google Patents

Tube de dentifrice Download PDF

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Publication number
WO2020149229A1
WO2020149229A1 PCT/JP2020/000640 JP2020000640W WO2020149229A1 WO 2020149229 A1 WO2020149229 A1 WO 2020149229A1 JP 2020000640 W JP2020000640 W JP 2020000640W WO 2020149229 A1 WO2020149229 A1 WO 2020149229A1
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WO
WIPO (PCT)
Prior art keywords
layer
dentifrice
liquid
container
tubular body
Prior art date
Application number
PCT/JP2020/000640
Other languages
English (en)
Japanese (ja)
Inventor
洋介 阿久津
啓佑 丹生
智啓 田口
宏明 杉岡
英亮 中本
石原　隆幸
晋也 清藤
勇 大石
航 吉田
Original Assignee
東洋製罐株式会社
メビウスパッケージング株式会社
東洋製罐グループホールディングス株式会社
ライオン株式会社
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Application filed by 東洋製罐株式会社, メビウスパッケージング株式会社, 東洋製罐グループホールディングス株式会社, ライオン株式会社 filed Critical 東洋製罐株式会社
Publication of WO2020149229A1 publication Critical patent/WO2020149229A1/fr

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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K5/00—Holders or dispensers for soap, toothpaste, or the like
    • A47K5/06—Dispensers for soap
    • A47K5/12—Dispensers for soap for liquid or pasty soap
    • A47K5/122—Dispensers for soap for liquid or pasty soap using squeeze bottles or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02—Body construction
    • B65D35/10—Body construction made by uniting or interconnecting two or more components

Definitions

  • the present invention relates to a dentifrice container provided with a cylindrical body having a liquid layer formed on the inner surface thereof.
  • Patent Document 1 a liquid diffusion preventing layer that suppresses or blocks the diffusion of the lubricating liquid that forms the liquid layer is provided below the plastic base layer that is the base of the liquid layer (lubrication liquid layer). By forming such a liquid diffusion preventing layer, the lubricating liquid layer provided on the inner surface of the container is stably held.
  • a toothpaste is a viscous paste-like solid substance containing a large amount of solid parts such as an abrasive. It is also called toothpaste and is used by filling it into a tube-shaped container.
  • the container containing such a dentifrice is generally stored in an inverted state on a wash basin or the like when not in use, the dentifrice is always stored in the outlet part of the container. It is required that the dentifrice can be quickly discharged, and that the dentifrice can be used up as much as possible without remaining at the bottom of the container.
  • Patent Document 1 does not describe the dentifrice at all, the present inventors can effectively apply such an easily slipping technique to a dentifrice container, and further, a dentifrice container. It has been found that the dentifrice can be made to exhibit the discharging property of the contents by the easy slipping technique to the maximum extent by devising the form and the like.
  • an object of the present invention is to provide a dentifrice container capable of promptly discharging the dentifrice and effectively suppressing the remaining of the dentifrice in the container.
  • a container containing a dentifrice which has a tubular body portion whose lower end portion is closed, and has a smaller diameter than the tubular body portion at the upper end and
  • the tubular body has a base layer made of a thermoplastic resin on the inner surface, and the inner surface is provided with a liquid layer of a lubricating liquid for improving slipperiness for a dentifrice,
  • a liquid diffusion preventing layer that suppresses or blocks the diffusion of the lubricating liquid that forms the liquid layer is provided on the lower side of the base layer,
  • a dentifrice container characterized in that the distance between the liquid diffusion preventing layer and the surface of the underlayer in contact with the liquid layer is 200 ⁇ m or less.
  • ⁇ is a water contact angle on the surface of the thermoplastic resin underlayer
  • ⁇ A is a water contact angle on the lubricating liquid forming the liquid layer
  • ⁇ B is a water contact angle on a single thermoplastic resin forming the underlayer, That the liquid layer coverage F calculated by is maintained at 0.5 or more
  • the underlayer is an olefin resin layer, the underlayer contains a lubricating liquid for forming the liquid layer, and the lubricating liquid serves as a supply source of the liquid layer to form the liquid layer.
  • the lubricating liquid is edible oil, fatty acid triglyceride, fluorine-based surfactant or silicone oil
  • the dentifrice filled in the dentifrice container is a paste-like solid having a density at 23° C. of 1.1 to 1.6 g/cm 3 .
  • the outer surface layer forming the outer surface and two or more intermediate layers are provided, and the intermediate layer is ethylene- Including a vinyl alcohol copolymer layer, (5)
  • the oxygen concentration of the dentifrice container sealed without dentifrice was sealed so that the atmosphere in the container was replaced with nitrogen and the relative humidity was maintained at 100%, it was 22° C. 60
  • the increase in oxygen concentration when stored for 30 days under %RH is 0.5% or less
  • the increase in oxygen concentration when stored for 30 days under 40°C 75%RH is 2% or less, Is preferred
  • the dentifrice container of the present invention preferably has the following form. (6) At the upper end of the tubular body, a neck portion having the discharge port is formed integrally with the tubular body, or is connected to the tubular body by heat sealing. That (7) The lower end portion of the discharge port formed in the neck portion is provided with an inclined surface inclined by 30 to 70 degrees with respect to the axial direction in a side cross section. (8) The inner diameter D1 of the discharge port is in the range of 2 to 8 mm. (9) The tubular body has a ratio L/Dmax between the length L and the maximum inner diameter Dmax in the range of 1 to 4.
  • the tubular body has a ratio Dmax/Dmin of the maximum inner diameter Dmax and the minimum inner diameter Dmin in the range of 1 to 3.
  • the lid member used for closing the outlet has a horizontal surface having a size capable of holding the container upside down.
  • At least a part of the tubular body has an asymmetric shape with respect to the central axis of the container.
  • the thickness of the tubular body is in the range of 400 to 800 ⁇ m.
  • the ratio Dmax/D1 of the maximum inner diameter Dmax of the tubular body to the inner diameter D1 of the discharge port is in the range of 4 to 30.
  • the inner surface of the bottom that closes the lower end of the tubular body is a curved surface. According to the present invention, there is further provided a dentifrice product in which the dentifrice container is filled with the dentifrice and the outlet is closed by the lid member.
  • the inner surface of the tubular body is an underlayer made of a thermoplastic resin, and a liquid layer of a lubricating liquid (slipping property for the dentifrice is formed on the underlayer). Since a lubricating liquid layer) is formed, this lubricating liquid layer effectively prevents adhesion of the dentifrice to the inner surface of the tubular body, and furthermore, the dentifrice's discharge property from the container is significantly improved. Therefore, the dentifrice can be promptly discharged.
  • the liquid diffusion preventing layer for preventing the diffusion of the lubricating liquid is formed below the base layer holding the lubricating liquid layer, the liquid layer coverage F of this lubricating liquid layer is formed. Is effectively suppressed from decreasing with time, and the effect of improving lubricity by the lubricating liquid layer is stably exhibited for a long period of time.
  • the liquid diffusion preventing layer that suppresses or blocks the diffusion of the lubricating liquid is provided at a position where the distance from the surface of the underlayer is 200 ⁇ m or less.
  • this liquid diffusion prevention layer effectively prevents a decrease in the amount of the lubricating liquid forming the lubricating liquid layer, in other words, a decrease in the liquid layer coverage of the lubricating liquid layer, and an excellent sliding effect on the dentifrice.
  • the sexuality is exerted stably over a long period of time. For example, when the interval is larger than 200 ⁇ m, the amount of the lubricating liquid that can permeate and diffuse into the underlayer becomes large, so that the characteristics of this liquid diffusion preventing layer cannot be sufficiently exhibited, and the underlayer is prevented. Due to the permeation and diffusion into the inside, the liquid layer coverage of the lubricating liquid layer is greatly decreased with time, and the effect of improving the slipperiness of the lubricating liquid layer is decreased with time.
  • the slipperiness with respect to the dentifrice is high, the adhesion residual of the dentifrice in the container is effectively suppressed, and the viscous dentifrice can be quickly discharged.
  • slipperiness (discharging property) with respect to the dentifrice is stably exhibited for a long period of time.
  • the conceptual diagram which shows the schematic side cross section (a) of the container for dentifrice of this invention, and the schematic plane cross section (b) structure of a cylindrical body part.
  • the schematic diagram showing an example of the layer composition of the cylindrical trunk of the dentifrice container of the present invention.
  • the sectional side view which shows an example of the form of the dentifrice container of this invention obtained by direct blow molding.
  • the body part side sectional view (a) and body part sectional view (b) which show the example of the shape of the cylindrical body part in the dentifrice container of this invention obtained by direct blow molding.
  • the dentifrice container of the present invention is indicated by 1 as a whole and has a hollow tubular body portion 3, and the lower end of the tubular body portion 3 is , And is closed by the bottom portion 5 (see FIG. 1A).
  • the plane cross section of the tubular body 3 may be circular, but generally shows a flat elliptical shape, the maximum inner diameter of which is indicated by Dmax and the minimum inner diameter thereof is indicated by Dmin.
  • a neck portion 7 having a shape narrowed upward is provided on the upper part of the tubular body portion 3, and an upper end of the neck portion 7 has a discharge port 9a through which a dentifrice, which is the content, is discharged.
  • a mouth portion 9 having is formed.
  • the discharge port 9a is closed by the lid member 11.
  • the lid member 11 has a top plate 11a and a skirt wall 11b descending from the top plate 11a, and a seal ring 11c for sealing the discharge port 9a is provided on the inner surface of the top plate 11a. ..
  • the seal ring 11c is in close contact with the surface of the discharge port 9a (inner surface of the mouth portion 9) or the outer peripheral surface of the neck portion 7 to ensure a sealing structure.
  • the lid member 11 may be configured such that a thread is provided on the outer surface of the neck portion 7 and the like, and the lid member 11 is detachably attached to the container 1 by screw engagement, or is hinge-connected to the neck portion 7. May be included. When the lid member 11 is hinged to the neck portion 7, the lid member 11 is formed integrally with the neck portion 7.
  • the neck portion 7 is shown as being integrally connected to the upper end of the tubular body portion 3.
  • the neck portion 7 may be formed depending on the molding method of the container 1. It may be a separate body from the above, and may have a form joined to the tubular body portion 3 by heat sealing, fitting, or the like.
  • Such a container can be molded by utilizing direct blow molding, extrusion tube molding, or laminate molding, and the neck portion 7 and the lid member 11 have a form suitable for this molding method.
  • the neck 7 is formed separately from the tubular body 3, and after filling the tubular body 3 with a toothpaste, It is fitted and fixed to the upper end of the body 3.
  • the extruded parison is used to simultaneously form the neck portion 7 and the tubular body portion 3, and a cap formed separately from this is fitted and fixed, and then the bottom portion of the tubular body portion 3 is cut to open the bottom side opening.
  • the container 1 can be manufactured by filling the toothpaste from the portion and then closing the opening by heat sealing.
  • extrusion tube molding a hollow cylinder having openings at both ends is molded by extrusion molding, and then a separately molded neck portion 7 is joined to one opening portion by heat sealing or the like, and a discharge port 9a is formed by a lid member 11. In a closed state, the dentifrice is filled from the other opening, and then the opening is closed by heat sealing to manufacture the container 1.
  • laminate molding a laminated sheet having a predetermined layer structure is formed by extrusion molding or the like, and the ends of the sheet are heat-sealed to form a tube that forms a tubular body.
  • a neck part separately molded in the same manner as above is joined by heat sealing, compression molding, or the like, and then, a dentifrice is filled from the other opening, and finally the opening is heat-sealed to achieve the purpose.
  • the container 1 can be manufactured.
  • the dentifrice container 1 of the present invention has a predetermined layer structure regardless of which molding method is used.
  • the tubular body portion 3 has a liquid diffusion preventing layer 21 as an intermediate layer, and the inner surface of the liquid diffusion preventing layer 21.
  • a base layer 23 is formed on the side, and a liquid layer 25 showing slipperiness for a dentifrice is provided on the base layer 23.
  • An outer surface layer 27 is provided on the other surface of the liquid diffusion prevention layer 21.
  • the liquid diffusion preventing layer 21 blocks the permeation/diffusion of the liquid forming the liquid layer 25 (that is, the lubricating liquid exhibiting a slippery property with respect to the dentifrice), and by forming such a layer, The slipperiness of the dentifrice provided by the liquid layer 25 is stably maintained for a long period of time. That is, when the lubricating liquid forming the liquid layer 25 permeates and diffuses into the inside of the cylindrical body portion 3 through the base layer 23, the lubricating liquid forming the liquid layer 25 gradually increases from the surface to the inside.
  • the amount of the liquid decreases with time, and as a result, the slipperiness of the liquid layer 25 with respect to the dentifrice is lost with time.
  • the permeation and diffusion of the lubricating liquid from the liquid layer 25 is blocked, so that the reduction of the liquid amount of the liquid layer 25 is effectively suppressed, and the deterioration of the sliding characteristics can be avoided. it can.
  • the material of the liquid diffusion preventing layer 21 is not particularly limited as long as it can prevent the liquid from permeating and diffusing from the liquid layer 25 and can be formed into a tubular body portion, and is, for example, a metal. It may be formed from an inorganic material such as a foil, a metal vapor deposition film, or ceramics, or may be formed from a diamond-like carbon (DLC) vapor deposition film, a thermosetting resin, or the like, but liquid diffusion by these materials is possible.
  • a thermoplastic resin is used. It is preferably formed. That is, the thermoplastic resin has excellent moldability, and the form of the tubular body portion 3 is not limited.
  • thermoplastic resin for forming the liquid diffusion preventing layer 21 as described above one having a density of 1.00 g/cm 3 or more and a glass transition point (Tg) of 35° C. or more, or a crystallinity A value of 0.5 or more is used. That is, since such a thermoplastic resin is dense and the movement and diffusion of the lubricating liquid in the resin is considered to be very limited, the permeation and diffusion of the lubricating liquid can be effectively suppressed.
  • the liquid diffusion preventing layer 21 becomes a loose layer, weakening the limitation of the movement and diffusion of the lubricating liquid, and effectively permeating and diffusing the lubricating liquid. It will be difficult to prevent. Further, with a resin having a crystallinity of less than 0.5, there are few crystal components that limit the movement and diffusion of the lubricating liquid in the resin, and the limitation is weakened. Therefore, the permeation and diffusion of the lubricating liquid should be effectively prevented. Becomes difficult.
  • thermoplastic resin is inferior in liquid diffusion preventing performance as compared with inorganic materials such as metal foil and metal vapor deposition film, it is necessary to make the liquid diffusion preventing layer 21 relatively thick, for example, 2 ⁇ m or more, Particularly, it is preferable to form the liquid diffusion preventing layer 21 with a thickness of about 5 to 80 ⁇ m. That is, if this thickness is too thin, the liquid diffusion preventing ability may be unsatisfactory, and even if it is excessively thick, the tubular body portion 3 becomes unnecessarily thick, and also in terms of cost. This is because there is no merit.
  • the thermoplastic resin having the above-mentioned density and glass transition point (Tg) is not particularly limited, but generally, an ethylene/vinyl alcohol copolymer (saponified ethylene/vinyl acetate copolymer).
  • Gas barrier resins such as aromatic polyamide and cyclic polyolefin, polyester such as polyethylene terephthalate, polylactic acid and liquid crystal polymer, and polycarbonate are preferable.
  • the liquid diffusion preventing layer 21 when the liquid diffusion preventing layer 21 is formed of such a gas barrier resin, the liquid diffusion preventing layer 21 can be provided with a gas barrier property for preventing the permeation of gas such as oxygen, and the inside of the container 1 It is possible to prevent oxidative deterioration of the dentifrice housed in, which is extremely advantageous.
  • the ethylene/vinyl alcohol copolymer is most preferable because it shows a particularly excellent oxygen barrier property.
  • an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol %, particularly 25 to 50 mol %, and a saponification degree of 96 mol% or more are used.
  • a saponified copolymer obtained by saponification so as to have a content of 99 mol% or more are selectively used. Good to do.
  • gas barrier resins can be used alone, and as long as the density and the glass transition point (Tg) are within the above range, as shown in the examples below, a polyolefin such as polyethylene can be used. It is also possible to form the liquid diffusion preventing layer 21 by blending with a gas barrier resin.
  • the liquid diffusion preventing layer 21 is formed of the ethylene/vinyl alcohol copolymer as described above, a lab test is conducted in advance in order to fully exhibit its gas barrier property, and the liquid diffusion preventing layer 21 is measured as follows. It is preferable to set the thickness of the liquid diffusion preventing layer 21 so that the amount of increase in oxygen concentration within a certain range falls within a certain range. That is, when the oxygen concentration of the dentifrice container sealed without dentifrice was sealed so that the atmosphere in the container was replaced with nitrogen and the relative humidity was maintained at 100%, it was 22°C and 60%.
  • Increase in oxygen concentration when stored for 30 days under RH is 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.1% or less, and stored for 30 days under 40°C 75% RH.
  • the increase in oxygen concentration is 2% or less.
  • the liquid diffusion preventing layer 21 is improved in order to enhance the adhesiveness with the underlayer 23 (or the outer surface layer 27) and prevent delamination. It is preferable to provide an adhesive resin layer (not shown) adjacent to. As a result, the liquid diffusion preventing layer 21 can be firmly adhered and fixed to the base layer 23 or the outer surface layer 27. That is, in the mode in which the gas barrier resin is used as the liquid diffusion preventing layer 21, it is basically preferable to provide one or two adhesive resin layers as the intermediate layer in addition to the liquid diffusion preventing layer 21.
  • Resins contained in 1, specifically, olefin resins graft-modified with carboxylic acids such as maleic acid, itaconic acid, fumaric acid or the like, anhydrides thereof, amides, esters, etc.; ethylene-acrylic acid copolymers; ion-crosslinked olefins A system copolymer; an ethylene-vinyl acetate copolymer, etc. are used as the adhesive resin.
  • the thickness of such an adhesive resin layer may be such that an appropriate adhesive force can be obtained, and it is generally 0.5 to 20 ⁇ m, preferably about 1 to 8 ⁇ m.
  • a metal foil or the like can be used as the liquid diffusion preventing layer 21, but in such a case, as an adhesive resin, for example, for dry lamination, anchor coat, or primer. What is generally used can also be used. For example, urethane resin, phenol resin, epoxy resin, alkyd resin, melamine resin, acrylic resin, polyester resin, amino resin, fluororesin, cellulose resin, isocyanate resin and the like can be used. These adhesive resins may be used alone or may be blended if necessary.
  • the above-mentioned liquid diffusion preventing layer 21 has a distance d from the surface of the underlayer 23 (interface between the underlayer 23 and the liquid layer 25) of 200 ⁇ m or less, preferably 150 ⁇ m or less. Should be formed in. That is, if the distance d is too large, even if the liquid diffusion preventing layer 21 prevents the liquid from permeating and diffusing, the lubricating liquid from the liquid layer 25 may be present between the liquid diffusion preventing layer 21 and the surface of the base layer 23. As a result, it becomes impossible to effectively suppress the disappearance of the liquid layer 25 over time.
  • the base layer 23 provided on the liquid diffusion preventing layer 21 is a layer for holding the liquid layer 25 formed on the surface so as not to drop off. That is, if the liquid layer 25 is formed directly on the liquid diffusion preventing layer 21, the lubricating liquid forming the liquid layer 25 does not permeate, so that the liquid layer 25 is liable to drop off and a certain liquid layer is formed. It becomes difficult to form the liquid layer 25 stably with the coverage. Therefore, it is necessary to provide the base layer 23 and form the liquid layer 25 on this.
  • the base layer 23 allows the liquid to permeate from the liquid layer 25 to some extent, and exhibits an anchor effect for the liquid layer 25. Therefore, as compared with the liquid diffusion preventing layer 21, it is formed of a resin that is relatively loose, for example, a thermoplastic resin whose density is lower than 1.0 g/cm 3 .
  • the thermoplastic resin for forming such an underlayer 23 is not particularly limited as long as it has a molecular weight such that a layer can be formed and the density is within the above range, but is generally an olefin resin.
  • Low density polyethylene linear low density polyethylene, medium or high density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene and the like.
  • it may be a random or block copolymer of ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene.
  • the olefin resin for forming the underlayer 23 that is particularly preferably used is polyethylene or polypropylene, and polyethylene is most suitable.
  • the squeeze property of the tubular body portion 3 is also high, and it is more suitable from the viewpoint of discharging viscous dentifrice. ..
  • polyester such as polyethylene terephthalate is not very suitable as a resin for forming the underlayer 23.
  • Such a polyester has a high wettability with respect to the lubricating liquid, and there is no problem in forming a thin and uniform thickness liquid layer 25. Because it will run away.
  • the underlayer 23 is formed such that the distance d between the surface (interface with the liquid layer 25) and the liquid diffusion preventing layer 21 is equal to or less than a certain value.
  • the liquid layer 25 has a thickness of at least 5 ⁇ m or more, and particularly 10 ⁇ m or more.
  • the above-described base layer 23 can be blended with a lubricating liquid, and the base layer 23 can be used as a supply source of the lubricating liquid forming the liquid layer 25. That is, by blending the lubricating liquid with the underlayer 23 formed of a low-density resin having a high permeation and diffusion property with respect to the lubricating liquid described above, the liquid layer 25 described later can be easily formed. Since the liquid diffusion preventing layer 21 is formed on the other side of the base layer 23, the lubricating liquid blended with the base layer 23 exudes to the surface of the base layer 23, thereby forming the liquid layer 25. be able to.
  • the amount of the lubricating liquid blended with the underlayer 23 is generally 0.1 to 50 g/m 2 , preferably 0.3 to 30 g/m 2 , such that the amount of the lubricating liquid that exudes on the surface to form the liquid layer 25 is More preferably, it may be set so as to be maintained in the range of 0.5 to 30 g/m 2 .
  • the liquid layer 25 formed on the inner surface of the tubular body portion 3 is formed of a lubricating liquid having a slip property with respect to a dentifrice, but as a matter of course, it is a non-volatile liquid having a small vapor pressure under atmospheric pressure.
  • the lubricating liquid layer 25 is formed of a liquid, for example, a high boiling point liquid having a boiling point of 200° C. or higher. Volatile liquids easily volatilize and disappear over time, and cannot function as a lubricating liquid.
  • the dentifrice is hydrophilic and Typical examples are edible oils, fatty acid triglycerides, fluorosurfactants, and silicone oils because they improve the slipperiness of hydrophilic substances.
  • edible oils include soybean oil, rapeseed oil, olive oil, rice oil, corn oil, safflower oil, sesame oil, palm oil, castor oil, avocado oil, coconut oil, almond oil, walnut oil, mustard oil and salad oil. Can be mentioned.
  • the liquid layer 25 formed from such a lubricating liquid generally has a liquid amount of 0.1 to 50 g/m 2 , preferably 0.3 to 30 g/m 2 , and more preferably 0.5 to 30 g/m 2. It is formed so that it may become the range of. That is, when the liquid amount is small, it is difficult to impart sufficient slipperiness, while when the liquid amount is excessively large, the liquid is liable to drop off, the liquid amount fluctuates greatly, and stable slippage occurs. This is because there is a risk that it will not be possible to secure the sex.
  • the liquid amount so as to be in the range of 1.5 to 20 g/m 2 , and remarkably 1.9 to 10 g/m 2 .
  • Toothpaste is a viscous paste-like solid that contains a large amount of solids, and exhibits properties different from those of general fluid contents. Therefore, a suitable liquid amount range (lower limit) Value) is different from general liquid contents. Further, in the range of the liquid amount larger than 20 g/m 2 , the slipperiness does not change, so that it is not significant to make the liquid amount larger than this.
  • the liquid layer 25 as described above has the following formula (1) in order to impart the slipperiness by the lubricating liquid to the inner surface of the tubular body portion 3 stably and evenly.
  • F (cos ⁇ cos ⁇ B )/(cos ⁇ A ⁇ cos ⁇ B )(1)
  • ⁇ is a water contact angle on the surface of the underlayer 23
  • ⁇ A is a water contact angle on the lubricating liquid forming the liquid layer
  • ⁇ B is the water contact angle on the single thermoplastic resin forming the underlayer 23
  • the liquid layer coverage F of the liquid layer 25 calculated in step 1 is 0.5 or more, preferably 0.6 or more.
  • the liquid layer coverage F is 1.0 and the underlayer 23 has The whole is covered with the liquid layer 25.
  • the liquid layer 25 is formed in such a manner that the lubricating liquid is scattered on the inner surface even if the amount of the lubricating liquid is large, and exhibits sufficient slipperiness. It becomes difficult to do.
  • the above formula (1) is obtained by modifying the Cassie-Baxter formula expressing the apparent contact angle ⁇ on the composite surface in which the surface is formed of two kinds of components (A, B). This is expressed by the following formula.
  • F A represents the proportion of the A component
  • ⁇ A is the contact angle of water on the A component alone
  • ⁇ B is the contact angle of water on the B component alone.
  • the material of the outer surface layer 27 is generally formed of various thermoplastic resins, paper, and the like, and in particular, the outer surface layer 27 is formed using low density polyethylene or linear low density polyethylene.
  • an adhesive resin layer may be appropriately provided between the outer surface layer 27 and the liquid diffusion preventing layer 21, and the outer surface is formed of the above-mentioned low density polyethylene or linear low density polyethylene on condition that it is formed.
  • a gas barrier resin layer (which also functions as a liquid diffusion preventing layer) can be provided in the outer surface layer 27.
  • the layer structure of the tubular body is not limited to the layer structure shown in FIG. 2, and for example, a liquid diffusion adjusting layer may be provided between the base layer 23 and the liquid diffusion preventing layer 21. it can.
  • the liquid diffusion control layer contains the lubricating liquid that forms the liquid layer 25 described above. This mode is suitably applied to, for example, a mode in which the lubricating liquid for forming the liquid layer 25 is blended in the underlayer 23 and the liquid layer 25 of the lubricating liquid is formed by exudation of the lubricating liquid from the underlayer 23.
  • the lubricating liquid in the underlayer 23 permeates and diffuses also into the liquid diffusion adjusting layer, the amount of the lubricating liquid that exudes to the surface of the underlayer 23 is adjusted to an appropriate range, and the excessive amount of the liquid is adjusted. It is advantageous in preventing the exudation of the liquid and forming the liquid layer 25 with an appropriate amount of liquid. Further, the present invention can be suitably applied to a case where the lubricant layer forming the liquid layer 25 is not blended in the base layer 23, and the liquid layer 25 is formed by an operation such as coating the lubricant liquid on the surface of the base layer 23.
  • the liquid forming the liquid layer 25 permeates and diffuses into the base layer 23 over time.
  • the lubricating liquid contained in the liquid diffusion adjusting layer is removed from the liquid diffusion adjusting layer. It diffuses into the underlayer 23. As a result, the amount of lubricating liquid that permeates and diffuses from the liquid layer 25 into the base layer 23 is reduced, so that the amount of liquid in the liquid layer 25 can be adjusted.
  • the resin forming such a liquid diffusion adjusting layer may be basically any resin as long as it contains the lubricating liquid forming the liquid layer 25. For example, it has a liquid diffusion preventing ability.
  • the liquid diffusion adjusting layer can be formed using a resin that is not present, it is usually preferable to form the liquid diffusion adjusting layer using the same type of resin as the resin that forms the underlayer 23.
  • the distance d between the liquid diffusion prevention layer 21 and the surface of the underlayer 23 should be in the range described above, and the distance d should be set in such a range.
  • the thickness ratio t 1 / t 2 is liquid-diffusing be set in the range of 0.1 to 10 and the thickness t 2 of the thickness t 1 and the underlayer 23 of the liquid diffusion modulating layer It is preferable in that the function of the control layer is sufficiently exhibited.
  • an additive such as an antioxidant, a surfactant, and a coloring agent is appropriately blended in a range that does not impair the characteristics of each layer, depending on the type of material forming each layer. Good.
  • the dentifrice contained as contents in the container 1 described above is an abrasive such as calcium carbonate or aluminum hydroxide, a foaming agent or foaming agent such as sodium laurate, a moisturizing agent such as glycerin, sodium alginate or carboxymethyl cellulose. It contains a binder as a basic component, and further contains a medicinal component such as a fluoride, is a hydrophilic, extremely viscous paste-like solid substance, and its density (23°C) is generally 1.1. It is in the range of up to 1.6 g/cm 3 .
  • the container of the present invention contains a dentifrice that is extremely viscous and has a high density as compared with ketchup, mayonnaise, etc., as a content, but the inner surface of the cylindrical body 3 has a predetermined lubricating liquid. Since the liquid layer 25 is formed by the above, such a dentifrice can be promptly discharged, and the adhesion and remaining of the dentifrice in the container can be effectively prevented.
  • the liquid diffusion preventing layer 21 is provided below the underlayer 23 that holds the liquid layer 25, such disappearance of the liquid layer 25 with time is effectively prevented. ..
  • F 0 is the liquid layer coverage F of the liquid layer 25 one day after the start of the test
  • F 1 is the liquid layer coverage F of the liquid layer 25 14 days after the start of the test
  • the coating reduction rate ⁇ F represented by is suppressed to 40% or less, particularly 20% or less, and further 10% or less.
  • the liquid layer 25 can stably exhibit the slipperiness against the dentifrice over a long period of time.
  • the dentifrice container 1 of the present invention including the tubular body portion 3 having the above-mentioned layered structure has the basic form shown in FIG. 1, and the inner surface of the neck portion 7 has a slope connected to the discharge port 9a.
  • the surface 7a is formed.
  • the inclination angle ⁇ of the inclined surface 7a with respect to the axial direction is preferably in the range of 30 to 70 degrees, and the inclined surface having such an inclination angle is formed. For example, when the container 1 is held in an inverted state, the dentifrice which is the content flows toward the discharge port 9a more quickly, and excellent discharge performance can be secured.
  • the inclination angle ⁇ is smaller than 30 degrees, the height of the neck portion 7 becomes longer than necessary, which is not preferable. Further, when the inclination angle ⁇ is larger than 70 degrees, it becomes difficult for the contents to flow toward the discharge port 9a.
  • the inner diameter D1 of the discharge port 9a is preferably in the range of 2 to 8 mm. If the inner diameter D1 is smaller than 2 mm, a large pressing force is required when the outer surface of the tubular body portion 3 is pressed to push out the dentifrice, which may reduce usability. Further, when the inner diameter D1 exceeds 8 mm, when the amount of the dentifrice decreases, when the dentifrice is pushed out by pressing the outer surface of the tubular body portion 3, the dentifrice is pushed out together with the air, and Is likely to occur.
  • the cylindrical body 3 it is most preferable for the cylindrical body 3 to have a ratio L/Dmax of the length L and the maximum inner diameter Dmax in the range of 1 to 4 in order to push out the dentifrice.
  • the length L of the tubular body portion 3 is a portion that is not narrowed, that is, a length in a region showing the maximum inner diameter Dmax, and is a portion that does not include the region of the upper neck portion 7 and the bottom portion 5.
  • the ratio (Dmax/Dmin) of the maximum inner diameter Dmax and the minimum inner diameter Dmin of the cylindrical body portion 3 is preferably in the range of 1 to 3 from the viewpoint of the extrusion discharge property of the contents by pressing.
  • the upper surface of the top plate 11a of the lid member 11 is formed with a horizontal surface having a size that can stably hold the inverted state when the container 1 is inverted.
  • the container 1 (and the lid member 11) having the above-described configuration is manufactured by direct blow molding, extrusion tube molding, or laminate molding, and the liquid film 25 is filled with a dentifrice prior to filling. It can also be formed by applying a lubricating liquid to the inner surface of the tubular body 3 by spraying or the like, or by blending the lubricating liquid with the underlayer 23 or the resin forming the liquid diffusion adjusting layer described above. It can also be formed by performing various moldings.
  • the above-mentioned container for dentifrice can be formed by using direct blow molding, extrusion tube molding, or laminate molding.
  • the cylindrical body 3 is formed into a shape most suitable for discharging dentifrice.
  • Direct blow molding is the most suitable from the viewpoint of easy molding without subsequent processing.
  • the laminate molding has an advantage that an aluminum foil, a vapor deposition film, or the like can be used as the liquid diffusion preventing layer 21 described above.
  • FIG. 3 shows a side cross-sectional shape of the dentifrice container 1 formed by such direct blow molding.
  • This dentifrice container 1 has a basic structure as shown in FIG. 1, but the tubular body 3 closed by the bottom 5 is formed by direct blow molding, The upper end of the body portion 3 is formed with a fitting portion 3a that is slightly narrowed to have a small diameter. The separately molded neck portion 7 is fitted and fixed to the fitting portion 3a.
  • a mouth portion 9 having a discharge port 9a is formed on the neck portion 7, and a lid material 11 is formed integrally with the neck portion 7 by a hinge band 30 on the neck portion 7. That is, the lid member 11 is provided with a top plate 11a and a skirt portion 11b each having a flat horizontal surface suitable for holding upside down, and a seal ring 11c is formed on the inner surface of the top plate 11a. When is swirled and closed, the seal ring 11c comes into close contact with the surface of the discharge port 9a to ensure the hermeticity.
  • the thickness of the tubular body portion 3 is in the range of 400 to 800 ⁇ m. Is preferred. That is, when the thickness is in such a range, pressing the tubular body 3 promptly dents the body 3, and the toothpaste, which is the content, is pushed out from the discharge port 9a and the pressing is stopped. Then, the body portion 3 quickly returns from the depressed state to the initial shape, a negative pressure is generated in the body portion 3, and the dentifrice present in the vicinity of the discharge port 9a falls into the tubular body portion 3. Becomes
  • the ratio Dmax/D1 of the maximum inner diameter Dmax of the tubular body portion 3 to the inner diameter D1 of the discharge port 9a is in the range of 4 to 30. That is, if this ratio is less than 4, a large amount of dentifrice may be expelled at once when the body part 3 is pressed and scattered. Further, if the above ratio is larger than 30, it becomes difficult to grip the body portion 3, and the usability is reduced. Therefore, in such a container, in consideration of the above points, the inner diameter D1 of the discharge port 9a is generally set to 2 to 8 mm, and the maximum diameter Dmax of the tubular body portion 3 is set to about 20 to 60 mm.
  • the inner surface of the bottom portion 5 that closes the lower end of the tubular body portion 3 is a curved surface. That is, by making the bottom portion 5 a curved surface, the dentifrice in contact with the inner surface of the bottom portion 5 can easily drop to the discharge port 9a side, and can be used more reliably without leaving the dentifrice. .. Further, with such a curved surface, a general user can visually recognize that the dentifrice container 1 is suitable for holding upside down.
  • secondary processing is required in extrusion tube molding and laminate molding, but in the direct blow method of shaping by blowing air or the like, Such a form can be formed without performing subsequent processing.
  • the tubular body portion 3 is connected to the central axis O of the container.
  • the shape can be asymmetric with respect to.
  • the container 1 for dentifrice of the present invention in which the liquid layer 25 of the lubricating liquid is formed on the inner surface of the tubular body portion 3 has a viscous paste-like solid substance by having the above-described shape. It is possible to more smoothly discharge the dentifrice, and it is possible to effectively prevent the dentifrice from remaining in the container 1.
  • Oxygen permeability evaluation Six bottles were prepared to evaluate the oxygen permeability of the dentifrice container (bottle) molded by the method described below. Distilled water (2 mL) was placed in each of the six bottles so that the relative humidity in the bottles was maintained at 100%, and the atmosphere in the bottles was replaced with nitrogen so that the initial oxygen concentration was 0.06% or less. , A polyethylene (inner layer)/aluminum foil/polyester (outer layer) was heat-sealed and sealed, and stored at 22° C. 60% RH and 40° C. 75% RH under three conditions.
  • the oxygen concentration in the multi-layer bottle after 30 days of storage under the above two storage conditions was measured using gas chromatography (GC-14A, manufactured by Shimadzu Corporation), and the value obtained by subtracting the initial oxygen concentration from the measured value was used. The average value was taken as the increase in oxygen concentration. The smaller the increase in oxygen concentration, the smaller the oxygen permeability and the better the oxygen barrier property.
  • ⁇ is a water contact angle on the surface of the underlayer made of a thermoplastic resin
  • ⁇ A is the water contact angle on the liquid forming the liquid layer
  • ⁇ B is the water contact angle on the thermoplastic resin simple substance forming the underlayer.
  • ⁇ A 80.3° (Value on medium-chain fatty acid triglyceride (liquid))
  • a liquid layer coverage of 0 indicates that no liquid layer has been formed, and a liquid layer coverage of 1 indicates that the resin is completely exposed to the liquid without being exposed to the surface. ..
  • the liquid layer (lubrication liquid layer) formed on the inner surface of the container was treated with 30 mL of a solvent (heptane) miscible with the lubricating liquid. After recovering and concentrating using an evaporator, the residue was transferred to an evaporation dish, and the weight of the liquid layer component was determined. The obtained weight was divided by the area of the inner surface of the container to obtain the liquid layer coating amount (g/m 2 ) on the inner surface of the bottle. The smaller this value, the thinner the liquid layer is formed on the inner surface of the container.
  • Container Toothpaste container (bottle, cap) prepared by the method described below was prepared. First, the total weight of the bottle and cap (empty container weight) was measured. Next, 90 g of any of the dentifrices A, B, and C described below was filled from the mouth of the bottle. After filling, after mounting the cap, the top side of the cap was faced down and stored in an environment of 23° C. for 1 day. After storage, the cap was opened, the cylindrical body of the container was pressed, and 30 g of the dentifrice was taken out.
  • the cap was opened, the tubular body was pushed, the dentifrice was taken out 4 g at a time, the cap was closed, and the top side of the cap was faced down.
  • the weight (A) of the dentifrice container when 4 g of the cylindrical body was pushed out and could not be taken out was measured and recorded. After this, put the cap on the bottom, tap the cap top of the dentifrice container on the laboratory table ten times in a row (tapping), press the tubular body again to take out 4g of dentifrice each time, and close the cap.
  • the surface tension of the liquid was a value measured at 23° C. using a solid-liquid interface analysis system DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.).
  • the density of the liquid required for measuring the surface tension of the liquid was a value measured at 23° C. using a density-specific gravity meter DA-130 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • the viscosity of the liquid is a value measured at 23° C. using a tuning fork type vibration viscometer SV-10 (manufactured by A&D Co., Ltd.).
  • Resin A Polyethylene (LDPE) MFR: 0.3g/10min (190°C, 2.16Kg) Density: 0.922 g/cm 3
  • Resin B Random polypropylene (rPP) Density: 0.9 g/cm 3
  • Lubricant Medium chain fatty acid triglyceride (MCT) (Surface tension 28.8 mN/m, viscosity 33.8 mPa ⁇ s, all values at 23° C. Boiling point: 210° C.
  • ⁇ Outermost layer forming resin> Polypropylene (PP) MFR: 1.6g/10min (230°C, 2.16Kg) ⁇ Adhesive layer forming resin> Acid-modified polyethylene ⁇ Resin for intermediate layer formation> Ethylene-vinyl alcohol copolymer (density: 1.19 g/cm 3 , Tg: 61°C) ⁇ Resin for forming main layer> Polypropylene (PP) MFR: 1.6g/10min (230°C, 2.16Kg) ⁇ Cap resin> Random polypropylene (rPP) MFR 25 (230°C, 2.16kg)
  • Polypropylene (PP) was used as the outermost layer forming material in the 40 mm extruder A, polypropylene (PP) was used as the main layer forming resin in the 50 mm extruder, and acid anhydride-modified polyethylene was used as the adhesive layer forming resin in the 30 mm extruder A.
  • an ethylene-vinyl alcohol copolymer is used as a resin for forming an intermediate layer
  • low density polyethylene (LDPE), random polypropylene (rPP), and a medium chain fatty acid triglyceride ( MCT) blends are each supplied, the molten parison is extruded from a multilayer die head at a temperature of 210° C., and the internal temperature is 100 mL and the weight is 9.5 g of 5 types of 9 layers by a known direct blow molding method at a mold temperature of 22° C.
  • a multilayer bottle having an asymmetric body shape and a curved inner surface at the bottom was manufactured.
  • the layer structure of the tubular body of the bottle and the total thickness of the container body are as follows.
  • Layer composition (thickness ratio (%)): Outermost layer/adhesive layer/intermediate layer/adhesive layer/main layer/adhesive layer/intermediate layer/adhesive layer/base layer 17.4/2.7/2.7/2.1/53.1/1.8 /3.9/2.1/14.2
  • Total thickness 564 ⁇ m
  • Distance between base layer and liquid diffusion prevention layer 92 ⁇ m
  • a hinge cap having an inner diameter D1 of the discharge port of 8 mm and a sloped surface of 50° with respect to the axial direction when viewed in a side cross section was produced.
  • the measurement of the liquid layer coverage, the measurement of the liquid layer coverage, the measurement of the residual amount of dentifrice in the container, and the measurement of oxygen permeability were performed.
  • the cylindrical body is asymmetric with respect to the center axis of the container, and the shape of the discharge neck has an inclined surface of 50 degrees with respect to the axial direction is extremely effective for reducing the residual amount of the dentifrice.
  • the increase in oxygen concentration when stored at 22° C. and 60% RH for 30 days is 0.5% or less, and a dentifrice container having an excellent oxygen barrier property is obtained. You can see that it is now possible to provide.
  • Toothpaste container 3 Cylindrical body part 5: Bottom part 7: Neck part 7a: Inclined surface 9: Mouth part 9a: Discharge port 11: Lid material 11a: Top plate 11b: Skirt part 11c: Seal ring 21: Liquid diffusion Prevention layer 23: Underlayer 25: Liquid layer 27: Outer surface layer

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Tubes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'objet de la présente invention est de fournir un tube de dentifrice qui permet de faire sortir rapidement le dentifrice, et en outre de réduire efficacement la quantité de dentifrice restant dans le tube. La présente invention concerne un tube de dentifrice (1), qui est un tube (1) dans lequel est logé un dentifrice, le tube de dentifrice (1) ayant une partie cylindrique (3) dont la partie d'extrémité inférieure est fermée, et ayant également, dans son extrémité supérieure, une ouverture d'évacuation de contenu qui a un diamètre inférieur à celui de la partie cylindrique et qui est fermée par un couvercle, le tube de dentifrice (1) étant caractérisé en ce que : la partie cylindrique (3) a une couche de base en résine thermoplastique (23) sur sa surface interne, et est conçue de sorte qu'une couche de liquide (25) formée à partir d'un liquide lubrifiant pour améliorer la performance de glissement d'un dentifrice est fournie à la surface interne ; une couche anti-diffusion de liquide (21) pour supprimer ou bloquer la diffusion du liquide lubrifiant formant la couche de liquide (25) est disposée sur le côté inférieur de la couche de base (23) ; et l'espace entre la couche anti-diffusion de liquide (21) et la surface de la couche de base (23) qui est en contact avec la couche de liquide (25) est inférieure ou égale à 200 μm.
PCT/JP2020/000640 2019-01-16 2020-01-10 Tube de dentifrice WO2020149229A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53154136U (fr) * 1977-05-10 1978-12-04
JPS5428645U (fr) * 1977-07-26 1979-02-24
JP5673905B1 (ja) * 2013-05-23 2015-02-18 東洋製罐グループホールディングス株式会社 液層を表面に有する多層構造体
JP2017013369A (ja) * 2015-07-01 2017-01-19 東洋製罐グループホールディングス株式会社 潤滑層を有する構造体
JP2018087034A (ja) * 2016-11-29 2018-06-07 東罐興業株式会社 キャップ及び容器
JP2018167860A (ja) * 2017-03-29 2018-11-01 大日本印刷株式会社 チューブ容器

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53154136U (fr) * 1977-05-10 1978-12-04
JPS5428645U (fr) * 1977-07-26 1979-02-24
JP5673905B1 (ja) * 2013-05-23 2015-02-18 東洋製罐グループホールディングス株式会社 液層を表面に有する多層構造体
JP2017013369A (ja) * 2015-07-01 2017-01-19 東洋製罐グループホールディングス株式会社 潤滑層を有する構造体
JP2018087034A (ja) * 2016-11-29 2018-06-07 東罐興業株式会社 キャップ及び容器
JP2018167860A (ja) * 2017-03-29 2018-11-01 大日本印刷株式会社 チューブ容器

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