WO2016076410A1 - 水性液状体に対する滑り性に優れた中空成形体 - Google Patents
水性液状体に対する滑り性に優れた中空成形体 Download PDFInfo
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- WO2016076410A1 WO2016076410A1 PCT/JP2015/081935 JP2015081935W WO2016076410A1 WO 2016076410 A1 WO2016076410 A1 WO 2016076410A1 JP 2015081935 W JP2015081935 W JP 2015081935W WO 2016076410 A1 WO2016076410 A1 WO 2016076410A1
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- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/08—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents adapted to discharge drops
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- 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
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
- B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
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- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0223—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by shape
- B65D1/023—Neck construction
- B65D1/0246—Closure retaining means, e.g. beads, screw-threads
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
Definitions
- the present invention relates to a hollow molded article excellent in slipperiness with respect to an aqueous liquid, particularly a highly viscous aqueous liquid.
- Plastic containers are widely used for various applications because they are easy to mold and can be manufactured at low cost.
- a bottle-shaped olefin resin container in which the inner surface of the container wall is formed of an olefin resin such as low density polyethylene and is formed by direct blow molding is a viscous material such as ketchup from the viewpoint that the contents can be easily squeezed out. It is suitably used as a container for storing a slurry-like or paste-like liquid material having poor fluidity.
- bottles containing highly viscous liquid materials that are difficult to flow the bottles are inverted so that the liquids (contents) can be discharged quickly or used cleanly without remaining in the bottle. It is often stored in. Therefore, when the bottle is turned upside down, a characteristic that the viscous liquid does not remain attached to the inner wall surface of the bottle and quickly drops is desired. Similar characteristics are also desired for hollow molded articles such as hollow pipes. In other words, a hollow pipe is often used to transport a viscous, difficult-to-flow liquid, and it does not remain attached to such a hollow pipe, and the difficult-to-flow liquid is flowed at a low pressure. It is necessary to make it.
- Patent Document 1 proposes a bottle having a multilayer structure in which an innermost layer is made of an olefin resin having an MFR (melt flow rate) of 10 g / 10 min or more.
- the innermost layer has excellent wettability to oily contents.
- the oily contents such as mayonnaise spread along the innermost surface.
- it can be discharged neatly without dropping and remaining attached to the inner wall surface of the bottle (the innermost layer surface).
- Patent Document 2 or Patent Document 3 contains a saturated or unsaturated aliphatic amide as a lubricant in the innermost layer.
- Polyolefin resin bottles have been proposed.
- Patent Documents 1 to 3 described above all improve the slipperiness with respect to the contents by the chemical composition of the thermoplastic resin composition forming the inner surface of the plastic container, and a certain degree of slipperiness improvement is achieved.
- the types and additives of the thermoplastic resin to be used are limited, there is a limit in improving the slipperiness, and the fact is that a dramatic improvement has not been achieved.
- Patent Document 4 proposes that the inner surface of the container be formed of a resin composition containing a molding resin and a liquid (a liquid that is immiscible with the contents).
- Patent Document 5 proposes that the inner surface of the container be formed of a resin composition containing a molding resin and a liquid (a liquid that is immiscible with the contents).
- a continuous liquid layer is formed on the inner surface of the container that comes into contact with the contents, and the slipperiness with respect to difficult-to-flow liquids such as ketchup, sauce, and mayonnaise jumps dramatically. Has been enhanced.
- an object of the present invention is to provide a hollow molded body in which slipperiness with respect to a hardly fluid liquid is dramatically improved and such slipperiness is exhibited over a long period of time.
- the inventors of the present invention are able to ensure a dramatic sliding property equivalent to the case where a continuous liquid layer is formed on this surface by distributing oily liquid droplets on the surface in contact with the aqueous liquid. At the same time, the inventors have found that such slipperiness is stably maintained over a long period of time, and have completed the present invention.
- a hollow molded body having a resin layer on the inner surface, wherein the oil-based liquid droplets are distributed on the surface of the resin layer forming the inner surface.
- the droplet has an equivalent circle diameter of 25 to 500 ⁇ m, (2) The droplets are distributed at a density of 100 to 1000 / cm 2 ; (3) The oily liquid is blended in the resin layer, (4) The resin layer surface forming the inner surface of the hollow molded body forms a hybrid surface containing a matrix resin and a substance having a critical surface tension smaller than that of the matrix resin, (5) The resin layer surface is formed of a matrix resin and a dispersion resin having a critical surface tension smaller than that of the matrix resin, (6) The matrix resin is an ethylene resin, and the dispersion resin is a propylene resin.
- the resin layer surface is formed from a matrix resin and a bleed organic additive having a critical surface tension smaller than that of the matrix resin.
- the matrix resin is an ethylene resin
- the bleed organic additive is a fatty acid metal salt.
- the hollow molded body is a direct blow bottle having a closed mouth portion, (10)
- the hollow molded body is a long pipe, Is preferred. Such a hollow molded body of the present invention is used by bringing an aqueous liquid into contact with the resin layer surface serving as the inner surface in a state where the droplets are distributed on the resin layer surface serving as the inner surface.
- the hollow molded body of the present invention has an inner surface in contact with the aqueous liquid material in use, but the stage before the aqueous liquid material contacts the inner surface (for example, in the container, the aqueous liquid that is the content) In the state before filling the body), the oily liquid is distributed as light droplets on the inner surface. For this reason, the fall by gravity is suppressed effectively and is stably hold
- an example in which oily liquid droplets are distributed on the inner surface of a direct blow bottle (hollow molded body) is shown. When the bottle is held upright, no oily liquid pool is formed at the bottom of the bottle. On the other hand, in the bottle of Comparative Example 1 in which the oily liquid is formed in a continuous layer shape, the oily liquid pool is observed at the bottom of the bottle after about 10 days have passed since the bottle is kept upright.
- the oily liquid is not a continuous layer but is distributed as droplets, but the oily liquid is a continuous layer with respect to a hardly flowable liquid (eg, ketchup). As with the case where it exists, it shows dramatically high slipperiness. The reason for this has not been clearly clarified, but it is probable that if a liquid material with poor fluidity is flowed on the surface where the droplets of the oily liquid are distributed, the droplets are spread and consequently hollow. It is assumed that an oily liquid layer is formed on the entire surface of the molded body.
- a hardly flowable liquid eg, ketchup
- the figure which shows the state of the inner surface of the hollow molded object of this invention The conceptual diagram which shows the cross-section of the inner surface resin layer which forms the inner surface in the hollow molded object of this invention.
- the hollow molded body has an inner surface 1 made of plastic (that is, the inner surface 1 is formed of a resin layer).
- the inner surface 1 is formed of a resin layer.
- the inner surface 1 exhibits a remarkably excellent slipperiness with respect to a viscous, hard-flowing aqueous liquid, and without being attached to the inner surface 1,
- the liquid can be passed quickly. That is, as explained above, when the hardly fluid aqueous liquid passes through the inner surface 1, the droplet 3 is probably spread, and the aqueous liquid is always formed by the spreading of the oily liquid droplet 3. Since it passes over the inner surface 1 while being in contact with the oily liquid layer, the slipperiness with respect to the aqueous liquid material is dramatically improved.
- the size of the droplets 3 distributed on the inner surface 1 has a circle equivalent diameter (diameter) of 25 to 500 ⁇ m, particularly 50 to 400 ⁇ m. That is, if the droplet 3 is too large, the droplet is easily affected by gravity as its weight increases, so that the droplet 3 is likely to fall in a state where the inner surface 1 is upright, As a result, the slipperiness due to the oily liquid forming the droplets 3 is likely to deteriorate with time, and the advantages of the present invention may not be fully exhibited. On the other hand, if the droplet 3 is too small, it is advantageous for suppressing the dropping of the droplet 3 and the like. This is probably because the liquid droplet 3 is difficult to spread when the aqueous liquid passes over the inner surface 1. Therefore, in the present invention, it is preferable that the equivalent circle diameter (equivalent circle diameter) of the droplet 3 is adjusted within the above range.
- the liquid droplet 3 has the following characteristics in that the slipperiness due to the oily liquid when the aqueous liquid passes over the inner surface 1 is maximized, and at the same time, the liquid droplet 3 is effectively prevented from falling off due to the drop or the like. It is preferably distributed at a density of 100 to 1000 / cm 2 , particularly 200 to 600 / cm 2 . That is, if the density of the droplets 3 is too large, the droplets 3 are likely to be united with each other. As a result, the droplets 3 are likely to fall off due to dropping or the like. Further, if the density of the droplets 3 is too small, it is natural that it becomes difficult to sufficiently exhibit the slipperiness by the oily liquid.
- the present invention it is advantageous for achieving the object of the present invention to distribute the oily liquid droplets 3 having an appropriate size on the inner surface 1 with an appropriate density. Adjustment of the size and density of the droplet 3 is performed by blending an oily liquid that forms the droplet 3 with a resin that forms the inner surface 1, and bleeding the droplet 3 from the resin layer that forms the inner surface 1. Can be realized. That is, the above-described droplet 3 cannot be formed by external addition such as spraying. This is because when the density of the droplets 3 becomes too high, the droplets 3 coalesce and become too large. A means for forming the inner surface 1 in which the droplets 3 satisfying the above size and density are distributed will be described later.
- the aqueous liquid passing through the inner surface 1 is water or a hydrophilic substance containing water, but an appropriate one is used depending on the use of the hollow molded body, but generally its viscosity (25 C.) is preferably a viscous liquid having a viscosity of 100 mPa ⁇ s or more. That is, in the present invention, when a viscous liquid having a particularly high viscosity is passed over the inner surface 1, the maximum slipperiness can be exhibited. Possibly, when a highly viscous liquid is passed over the inner surface 1, the liquid droplets 3 are sufficiently spread to form a liquid layer on the inner surface 1. It is considered to be done. In a low-viscosity liquid material, the droplets 3 are not sufficiently spread out, and as a result, it may be difficult to exhibit high slipperiness.
- high-viscosity aqueous liquid as described above are not limited thereto, but examples thereof include cosmetic liquids such as ketchup, aqueous glue, honey, various sauces, mayonnaise, and emulsions. And liquid detergents, shampoos, rinses, conditioners and the like.
- the oily liquid used for forming the droplets 3 must be a non-volatile liquid having a low vapor pressure under atmospheric pressure, for example, a high boiling point liquid having a boiling point of 200 ° C. or higher. This is because when a volatile liquid is used, it easily evaporates and disappears with time, and it becomes difficult to form the droplet 3.
- an oily liquid may include various substances provided that the liquid is a high-boiling liquid as described above. The more greatly different, the higher the lubrication effect and the more immiscible with the aqueous liquid is suitable for the present invention. That is, considering that the aqueous liquid is water or a hydrophilic substance containing water, a liquid having a surface tension (23 ° C.) of 10 to 40 mN / m, particularly 16 to 35 mN / m is used. Typical examples include fluorinated liquids, fluorinated surfactants, silicone oils, fatty acid triglycerides, glycerin fatty acid esters, and various vegetable oils.
- Suitable vegetable oils include soybean oil, rapeseed oil, olive oil, rice oil, corn oil, ben flower oil, sesame oil, palm oil, castor oil, avocado oil, coconut oil, almond oil, walnut oil, sandwich oil, salad oil, etc. Can be used for In particular, medium chain fatty acid triglycerides can be preferably used. In the present invention, depending on the use of the hollow molded body and the type of the aqueous liquid passing through the inner surface 1, an appropriate one is selected from the above and used as an oily liquid for forming the droplet 3 do it.
- the inner surface resin layer that forms the inner surface 1 is molded by means according to the form of the hollow molded body using a moldable resin such as a thermoplastic resin.
- a moldable resin such as a thermoplastic resin.
- thermoplastic resins include, but are not limited to, low density polyethylene, high density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene, Polyolefin resins such as random or block copolymers of ⁇ -olefins such as 1-butene and 4-methyl-1-pentene; ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride Ethylene-vinyl compound copolymer resins such as copolymers; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, ABS, ⁇ -methylstyrene-s
- the amount of such an oily liquid is generally about 2 to 15 parts by weight, particularly about 3 to 10 parts by weight per 100 parts by weight of the above-mentioned thermoplastic resin forming the inner surface 1.
- an appropriate amount may be set within such a range that the moldability is not impaired.
- thermoplastic resins a thermoplastic resin that is suitable for bleeding of oily liquid and satisfies physical properties such as strength required for a hollow molded body is selected.
- two types of thermoplastic resins are selected, and a blend of a matrix resin and a dispersion resin having a critical surface tension smaller than that of the matrix resin is used as the resin for forming the inner surface 1. It is preferable to form the inner surface 1 with a resin composition containing the obtained oily liquid.
- these resins must be incompatible.
- the inner surface 1 when the inner surface 1 is formed using the resin composition as described above, as shown in FIG. 2 (droplet 3 is omitted in FIG. 2), the inner surface 1 has a critical surface tension. Although low dispersion resin 5 is distributed, such dispersion resin 5 is unevenly distributed. That is, the uneven distribution of the dispersion resin 5 results in a hybrid surface in which the local surface tension on the inner surface 1 is not uniform. The oily liquid 1 bleeds on the hybrid surface, but the surface tension is locally different on the hybrid surface due to the uneven distribution of the dispersion resin having a small critical surface tension. Since it is an energetically unstable state to form a layer, it is considered that an oily liquid is present in the form of droplets to form an energetically stabilized form.
- the oily liquid bleeds into droplets, and the droplets 3 are easily formed on the inner surface 1.
- the matrix resin is selected so that the critical surface tension of the matrix resin is larger than the surface tension of the oily liquid, and the dispersion resin 5 having a critical surface tension smaller than the critical surface tension of the matrix resin is selected and used, it is formed.
- the oily liquid 1 forms a very thin liquid film 4 while the oily liquid 1 is in droplets on the part where the dispersion resin 5 is relatively exposed. It is thought that it can be formed.
- the size and density of the droplet 3 can be adjusted, for example, considering that the bleeding property of the oily liquid is good, and further, the critical surface tension difference between the matrix resin and the dispersion resin It is desirable to select these resins so as to increase, and in particular, it is possible to select a resin whose critical surface tension is close to that of the oily liquid used or smaller than that of the oily liquid. This is suitable for adjusting the density. Further, it is preferable to select a matrix resin having a critical surface tension larger than that of the oily liquid. This is because when the matrix resin surface comes into contact with an aqueous liquid, it is considered that a thin liquid film 4 of oily liquid is formed on the surface of the matrix resin.
- the matrix resin and the dispersion resin are selected from olefin resins, and in particular, an ethylene resin typified by a copolymer mainly composed of polyethylene or ethylene is selected as the matrix resin.
- the dispersion resin it is desirable to select a propylene resin typified by a copolymer mainly composed of polypropylene or propylene.
- Matrix resin: dispersed resin 100: 3 to 100: 100 In particular, 100: 5 to 100: 50 Furthermore, 100: 10 to 100: 30 It is optimal to use at a mass ratio of
- a resin composition comprising a matrix resin and a bleed organic additive having a lower critical surface tension than that of the matrix resin as the resin for forming the inner surface 1, and the oily liquid described above blended therewith.
- the inner surface 1 can also be formed.
- the bleed organic additive needs to be insoluble or hardly soluble in the oily liquid. Examples of the bleed organic additive having this property include fatty acid metal salts that exhibit solid properties at room temperature.
- Typical examples of such fatty acid metal salts include fatty acid metal salts composed of C4 to C22 fatty acids and metals such as lithium, magnesium, calcium, potassium, and zinc, and are insoluble or hardly soluble in oily liquids. And what was suitably adjusted so that critical surface tension may become smaller than matrix resin can be used.
- a bleed additive having a small critical surface tension is distributed and unevenly distributed on the inner surface 1, and a hybrid surface having a non-uniform local surface tension is formed. . Since the oily liquid bleeds on such a hybrid surface, the oily liquid 1 can be obtained even when a bleed organic additive having a critical surface tension smaller than that of the matrix resin is used as in the case of the dispersion resin described above. It is considered that it can be formed on a droplet.
- the droplets 3 can be effectively distributed on the inner surface 1 with the size and density described above.
- the droplet 3 formed on the inner surface 1 comes into contact with the aqueous liquid material, the droplet 3 is spread and a layer of oily liquid is formed on a part or the whole surface of the hollow molded body.
- the contact angle of oil in water is set to 40 degrees or less as the surface characteristics of the inner surface 1 in order to stably hold the oily liquid layer after contact with the aqueous liquid. Is preferred.
- the contact angle of oil in water is large (for example, 90 degrees or more), the layer of oily liquid in the aqueous liquid is destabilized, so that the liquid layer may be peeled off and performance may be lost. High nature.
- a combination of a matrix resin and a dispersion resin so that the contact angle of oil in water is 40 degrees or less as the resin constituting the inner surface 1.
- the above-mentioned ethylene resin and propylene resin can be preferably used.
- fine particles can also be blended as a roughening additive in the resin composition for forming an inner surface containing the oily liquid described above. That is, by blending such fine particles in an appropriate amount, the inner surface 1 becomes an appropriate rough surface, which is effective for preventing the droplet 3 from falling.
- the fine particles used as the surface roughening additive include particles having an average particle diameter of 20 ⁇ m or less on a volume basis measured by a laser diffraction scattering method, and are metals such as titanium oxide, alumina, and silica.
- Typical are organic particles such as oxide particles, carbonates such as calcium carbonate, carbon-based fine particles such as carbon black, polymethyl (meth) acrylate, polyethylene particles, and silicone particles such as polyorganosilsesquioxane. These may be hydrophobized with a silane coupling agent or silicone oil.
- the fine particles used as such a surface roughening additive are usually in an amount of about 1 to 20 parts by mass per 100 parts by mass of the inner surface forming thermoplastic resin (total amount of matrix resin and dispersion resin). used.
- the hollow molded body of the present invention has a single-layer structure formed by a resin composition in which an oily liquid for forming the inner surface is blended as long as the inner surface 1 in which the droplets 3 are distributed is formed. It may have a multilayer structure in which other layers are laminated below the inner surface resin layer forming the inner surface 1.
- the amount of bleeding of the oily liquid onto the inner surface 1 is set to an appropriate value as described above.
- the liquid diffusion preventing layer for preventing the permeation and diffusion of the oily liquid has a multilayer structure provided below the inner surface layer. .
- the material of such a liquid diffusion preventing layer is not particularly limited as long as it can prevent the permeation and diffusion of the liquid and is suitable for forming a hollow molded body, for example, a metal foil, a metal vapor deposition film, or glass. Or an inorganic material such as ceramics, or a diamond-like carbon (DLC) vapor deposition film, or an organic material such as a thermosetting resin or a thermoplastic resin.
- the liquid diffusion prevention layer is formed of an organic material, particularly a thermoplastic resin.
- the density is 1.00 g / cm 3 or more and the glass transition point (Tg) is 35 ° C. or more, or the crystallinity is 0. .5 or more are used. That is, since such a thermoplastic resin is dense and the movement and diffusion of the liquid in the resin is considered to be very limited, it is possible to effectively suppress the permeation and diffusion of the oily liquid.
- the liquid diffusion prevention layer becomes a loose layer, and the limitation of liquid migration and diffusion is weakened, effectively preventing liquid penetration and diffusion. It becomes difficult.
- a resin having a crystallinity of less than 0.5 since there are few crystal components that restrict the movement and diffusion of liquid in the resin and the restriction is weakened, it is difficult to effectively prevent the permeation and diffusion of the liquid. It becomes.
- the thickness of the liquid diffusion preventing layer formed from such an organic material is preferably 2 ⁇ m or more, particularly about 5 to 80 ⁇ m. In other words, if this thickness is too thin, the liquid diffusion preventing ability may be unsatisfactory, and even if it is excessively thick, the hollow molded body becomes unnecessarily thick, which is advantageous in terms of cost. Because there is no.
- the thermoplastic resin having the above-described density and glass transition point (Tg) is not particularly limited, but in general, an ethylene / vinyl alcohol copolymer (saponified ethylene / vinyl acetate copolymer).
- Gas barrier resins such as aliphatic polyamides, aromatic polyamides and cyclic polyolefins, polyesters such as polyethylene terephthalate and liquid crystal polymers, and polycarbonates are preferred.
- the liquid diffusion preventing layer is formed of such a gas barrier resin, it is possible to provide the liquid diffusion preventing layer with a gas barrier property that prevents permeation of gas such as oxygen. In the case of a form like a container, the contents can be prevented from oxidative deterioration, which is extremely advantageous.
- an ethylene / vinyl alcohol copolymer is most preferable because it exhibits particularly excellent oxygen barrier properties.
- the ethylene-vinyl alcohol copolymer as described above is generally 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.
- a saponified copolymer obtained by saponification so as to be 99 mol% or more is suitable.
- those having a density and a glass transition point (Tg) in the above-mentioned range are selectively used. It is good to do.
- gas barrier resins described above can be used alone, respectively, and as long as the density and glass transition point (Tg) are within the above ranges, a polyolefin such as polyethylene and a gas barrier resin are blended. A liquid diffusion preventing layer can also be formed.
- the gas barrier resin as described above when used as the liquid diffusion preventing layer, it is adjacent to the liquid diffusion preventing layer in order to enhance adhesion with the inner surface resin layer having the inner surface 1 and prevent delamination. It is preferable to provide an adhesive resin layer. Thereby, the liquid diffusion preventing layer can be firmly bonded and fixed to the inner surface resin.
- Adhesive resins used for forming such an adhesive resin layer are known per se. For example, a carbonyl group (> C ⁇ O) is 1 to 100 meq / 100 g resin in the main chain or side chain, particularly 10 to 100 meq / 100 g.
- Resin contained in the amount of resin specifically, olefin resin graft-modified with carboxylic acid such as maleic acid, itaconic acid, fumaric acid or the like, anhydride, amide, ester, etc .; ethylene-acrylic acid copolymer; An ion-crosslinked olefin copolymer; an ethylene-vinyl acetate copolymer; and the like 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 is generally 0.5 to 20 ⁇ m, preferably about 1 to 8 ⁇ m.
- Such an adhesive resin usually has the density, glass transition point, and crystallinity in the above-described range, and therefore has a function as a liquid diffusion preventing layer.
- another layer may be further formed on the liquid diffusion preventing layer.
- an outer surface layer formed using the thermoplastic resin used for forming the inner surface 1 described above can be appropriately laminated via the above-mentioned adhesive resin layer, and further, when forming this hollow molded body It is also possible to form a repro layer containing scrap resin such as burrs formed on the outer surface side.
- the hollow molded body of the present invention is formed by a molding means known per se, using the inner surface forming resin composition for forming the inner surface 1 described above.
- a hollow molded body may have various forms.
- the droplet 3 is stably held for a long period of time, and exhibits excellent slipperiness for a viscous aqueous liquid body over a long period of time. From this point of view, it is extremely useful as a container for containing such an aqueous liquid or a long pipe for passing the aqueous liquid, and is most suitably used as a container. It is not limited to these forms, and caps, spouts, and pipes may be cut to a predetermined size.
- Such a container is produced in the same manner as a conventionally known method except that the above inner surface forming resin composition is used.
- a preform for a container is molded by extrusion (extrusion molding) or injection (injection molding) of a molten resin (molded resin melt), and then blown into the preform maintained at a predetermined blow molding temperature. This is done by supplying a working fluid and shaping it into a container form.
- the form of the preform differs depending on the form of the target container.
- a biaxial stretch blow container has a test tube form, and an unstretched portion (to fasten the cap) that becomes the mouth of the container at the top.
- a part in which a screw and a support ring are formed is formed, and such a preform is usually formed by injection molding.
- the preform in the direct blow container has a pipe shape. For example, in the case of a bottle-shaped container, the portion that becomes the bottom of the container is pinched off and closed. Such a preform is formed by extrusion.
- FIG. 3 shows a state of an empty container immediately after molding of a food direct blow container that is preferably used for housing a viscous aqueous liquid.
- This empty container as a whole has a mouth portion 13 provided with a screw or the like at the top, and a blow portion (that is, a bottom portion formed so as to close the body portion and the body portion).
- the oily liquid droplet 3 is formed on the inner surface of the stretched portion).
- a closing portion 17 that closes the mouth portion 13 is formed at the upper portion of the mouth portion 13.
- the closed portion 17 is supplied with a small hole 17a into which a supply pipe for supplying a blowing fluid in blow molding is inserted.
- the small hole 17 a communicates with the inside of the empty container 10.
- the above-mentioned droplet 3 is distributed on the inner surface of the empty container 10 and is supplied to the user as it is.
- the closed portion 17 is cut out and filled with the contents in this state, and then the cap is opened.
- the container is fastened to the container and sealed for sale.
- it is difficult to sterilize the inside of the container 10 so that the empty container 10 before filling the contents is in such a form, so that the sterilized state is maintained and the entry of foreign matters is prevented. Because. Further, by using aseptic air for blow molding, various germs contained in the atmosphere can be prevented from entering the bottle, and further, heat sterilization can be performed by contacting the liquid with the heated preform.
- the direct blow empty container 10 may take a considerable time until it is filled with the contents (aqueous liquid material) after molding.
- a conventional liquid layer forming container if this time is long, the liquid film falls, and when filling the contents, the liquid phase falls to the bottom (or mouth), and the excellent slipperiness disappears. Or it may have fallen.
- the oily liquid exhibiting slipperiness with respect to the viscous liquid material is distributed as droplets, even when a long time elapses from molding to filling, the droplets are effectively dropped. Therefore, excellent slipperiness can be exhibited.
- the droplet 3 is formed on the inner surface of the empty container 10 whose upper portion is closed as described above. be able to.
- the droplet 3 cannot be formed in the empty container 10 as described above.
- the direct blow container as described above formed according to the present invention is extremely suitable as a container for containing the viscous aqueous liquid described above, and tilts or inverts the container even if it is a viscous aqueous liquid. By this, it can discharge
- a multilayer container which is a hollow molded article having a capacity of 500 g, produced by the method described later was stored in an upright state for a predetermined period in an environment of 22 ° C. and 60% RH. After storing for a predetermined period, the bottom of the container was carefully observed visually to evaluate whether there was a pool of oily liquid (liquid pool).
- the evaluation criteria are as follows. ⁇ : No liquid pool was confirmed. X: A liquid pool was confirmed.
- Content remaining amount test 500 g of a source (Otafuku Favorable Sauce, manufactured by Otafuku Sauce Co., Ltd.) was filled in a multilayer container which is a hollow molded body having a capacity of 500 g produced by the method described later. After filling, a cap was attached to the container mouth and 400 g of the contents were squeezed out at room temperature. Then, the bottle was inverted and left at room temperature for 30 minutes. After standing, the container was turned upside down, and the squeezing operation was repeated every 2 minutes, and the weight after 10 minutes (residual content weight + container weight) was measured.
- the contents remaining inside the container were washed with water, the weight of the container after washing was measured, and the difference between the obtained weights was obtained to obtain the remaining amount.
- the smaller the remaining amount the better the slipperiness on the inner surface of the container, and 5 g or less is better.
- ⁇ Oil liquid for droplet formation Medium chain fatty acid triglyceride (MCT) Surface tension: 29mN / m (23 ° C) Viscosity: 33.8 mPa ⁇ s (23 ° C) Boiling point: 210 ° C or higher Flash point: 242 ° C (reference value)
- the surface tension used the value measured at 23 degreeC using the solid-liquid interface analysis system DropMaster700 (made by Kyowa Interface Science Co., Ltd.).
- the density of the liquid necessary for the surface tension measurement was a value measured at 23 ° C. using a density specific gravity meter DA-130 (manufactured by Kyoto Electronics Industry Co., Ltd.).
- the viscosity is a value measured at 23 ° C. using a tuning fork type vibration viscometer SV-10 (manufactured by A & D Co., Ltd.).
- LDPE Low density polyethylene
- PP Polypropylene
- PP Density: 0.900 g / cm 3
- Cyclic olefin copolymer Critical surface tension: 31 mN / m or more Calcium stearate (Wako Pure Chemical Industries, Ltd.)
- a resin composition comprising low density polyethylene (LDPE), polypropylene (PP), and medium chain fatty acid triglyceride (MCT) was prepared.
- maleic anhydride-modified polyethylene was prepared as an adhesive layer forming resin, and an ethylene / vinyl alcohol copolymer was prepared as a liquid diffusion preventing layer forming resin.
- the structure of the resin layer at a position 60 mm from the bottom of the multilayer container is as follows. Inner layer (130) / Adhesive layer (30) / Liquid diffusion suppression layer (40) / Adhesive layer (20) / Base material layer (320) / Outer layer (60)
- the value in parentheses indicates the thickness of each layer (unit: ⁇ m or less).
- a multilayer container which is a hollow molded body, was produced in the same manner as in Example 1 except that the innermost layer forming resin was used. Using the produced multilayer container, the bottom accumulation property was evaluated. The results are shown in Table 1.
- a multilayer container which is a hollow molded body, was produced in the same manner as in Example 1 except that the innermost layer forming resin was used. Using the produced multilayer container, the bottom accumulation property was evaluated. The results are shown in Table 1.
- a multilayer container which is a hollow molded body, was produced in the same manner as in Example 1 except that the innermost layer forming resin was used. Using the produced multilayer container, the bottom accumulation property was evaluated. The results are shown in Table 1.
- LDPE low density polyethylene
- MCT medium chain fatty acid triglyceride
- LDPE low density polyethylene
- COC cyclic olefin copolymer
- MCT medium chain fatty acid triglyceride
- LDPE low density polyethylene
- COC cyclic olefin copolymer
- MCT medium chain fatty acid triglyceride
- FIG. 4B shows a microscope observation image of the surface of the molded body. Here, no droplets were observed on the surface. Moreover, the result of the shape observation of the oily liquid on the surface of the molded body by the white interferometer is shown in FIG.
- LDPE low density polyethylene
- PP polypropylene
- the structure of the resin layer of this container is as follows.
- MCT MCT
- Comparative Examples 2 and 3 using LDPE as the matrix resin, COC as the dispersion resin, and MCT as the oily liquid as the inner layer material It can be understood that the existence form of the oily liquid on the inner surface of the hollow molded body is lamellar (liquid layer form), and the existence form of the oily liquid is different.
- a cyclic olefin copolymer (COC) having a surface tension larger than that of the matrix resin (LDPE) was used as the dispersion resin, no droplets were formed.
- droplets were formed when polypropylene (PP) having a surface tension smaller than that of the matrix resin (LDPE) as the dispersion resin and calcium stearate (StCa) as the bleed organic additive were used. From this, it can be seen that it is necessary for the formation of droplets to disperse a component having a surface tension smaller than that of the matrix resin in the matrix resin.
- PP polypropylene
- LDPE matrix resin
- StCa calcium stearate
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Abstract
Description
また、同様の特性は、中空パイプのような中空成形体にも望まれている。即ち、粘稠な難流動性の液状体を移送するために中空パイプを使用する場合が多く、このような中空パイプ中に付着残存することなく、しかも低圧力で難流動性の液状体を流動させることが必要となるからである。
この多層構造ボトルは、最内層が油性内容物に対する濡れ性に優れており、この結果、ボトルを倒立させたり、或いは傾斜させたりすると、マヨネーズ等の油性内容物は、最内層表面に沿って広がりながら落下していき、ボトル内壁面(最内層表面)に付着残存することなく、綺麗に排出することができるというものである。
これら、特許文献4及び5では、何れも内容物が接触する容器内面に連続した液層が形成されるというものであり、ケチャップ、ソース、マヨネーズなどの難流動性の液状体に対する滑り性が飛躍的に高められている。
(1)前記液滴は、円相当径が25~500μmの大きさを有していること、
(2)前記液滴は、100~1000個/cm2の密度で分布していること、
(3)前記樹脂層中に、前記油性液体がブレンドされていること、
(4)前記中空成形体の内面を形成する前記樹脂層表面が、マトリックス樹脂と該マトリックス樹脂よりも臨界表面張力の小さい物質とを含む混成表面を形成していること、
(5)前記樹脂層表面が、マトリックス樹脂と、マトリックス樹脂よりも臨界表面張力の小さい分散樹脂とから形成されていること、
(6)前記マトリックス樹脂がエチレン系樹脂であり、前記分散樹脂がプロピレン系樹脂であること、
(7)前記樹脂層表面が、マトリックス樹脂と、マトリックス樹脂よりも臨界表面張力の小さいブリード性有機系添加剤とから形成されていること、
(8)前記マトリックス樹脂がエチレン系樹脂であり、前記ブリード性有機系添加剤が脂肪酸金属塩であること、
(9)前記中空成形体が、閉じられた形態の口部を有するダイレクトブローボトルであること、
(10)前記中空成形体が、長尺パイプであること、
が好ましい。
このような本発明の中空成形体は、内面となる前記樹脂層表面に前記液滴が分布している状態で、該内面となる樹脂層表面に水性液状体を接触させて使用される。
例えば、後述する実施例では、ダイレクトブローボトル(中空成形体)の内面に油性液体の液滴を分布させた例が示されているが、このようなボトルの成形後、約50日間、該ボトルを正立保持させたときにも、ボトルの底部に油性液体の液溜りは生じていない。一方、この油性液体を連続した層状に形成した比較例1のボトルでは、これを正立状態に保持して約10日経過後には、ボトル底部に油性液体の液溜りが観察されてしまう。
本発明の中空成形体の内面の状態を示す図1において、この中空成形体は、プラスチック製の内面1を有しており(即ち、内面1が樹脂層により形成されている)、この内面1には、油性液体の液滴3が分布している。即ち、このように分布している液滴3により、この内面1は、粘稠な難流動性の水性液状体に対して著しく優れた滑り性を示し、この内面1に付着させることなく、該液状体を速やかに通過させることができる。即ち、上記で説明したように、難流動性の水性液状体が内面1を通過するとき、この液滴3がおそらく押し広げられ、水性液状体は、常に油性液体の液滴3の拡がりにより形成された油性液体層と接触しながら、内面1上を通過するため、この水性液状体に対しての滑り性が飛躍的に向上するというものである。
従って、本発明においては、液滴3の円相当径(円相当直径)は、上記範囲に調整されていることが好適となる。
尚、上記のような大きさや密度を満足する液滴3が分布した内面1を形成するための手段については後述する。
本発明において、内面1を通過させる水性液状体は、水や水を含む親水性物質であるが、この中空成形体の用途に応じて適宜のものが使用されるが、一般に、その粘度(25℃)が100mPa・s以上の粘稠な液状体が好適に使用される。即ち、本発明では、特に粘度の高い粘稠な液状体を内面1上を通過させるときに、最大限の滑り性を発揮させることができる。おそらく、高粘性の液状体を内面1上を通過させるときに、液滴3が十分に押し広げられることにより、内面1上に液層が形成されるため、油性液体による滑り性が十分に発揮されるものと考えられる。低粘性の液状体では、液滴3の押し広げが十分に行われず、この結果、高い滑り性を発揮させることが困難となるおそれがある。
さらに、液滴3の形成に使用される油性液体は、当然、大気圧下での蒸気圧が小さい不揮発性の液体、例えば沸点が200℃以上の高沸点液体でなければならない。揮発性液体を用いた場合には、容易に揮散して経時と共に消失し、液滴3を形成することが困難となってしまうからである。
本発明においては、中空成形体の用途や内面1を通過させる水性液状体の種類等に応じて、上記の中から適当なものを選択して、液滴3を形成するための油性液体として使用すればよい。
本発明においては、上記内面1を形成する内面樹脂層は、成形可能な樹脂、例えば熱可塑性樹脂を用い、中空成形体の形態に応じた手段で成形される。このような熱可塑性樹脂としては、これに限定されるものではないが、例えば、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリ1-ブテン、ポリ4-メチル-1-ペンテン、或いはエチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン等のα-オレフィン同士のランダム乃至ブロック共重合体等のポリオレフィン系樹脂;エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体、エチレン-塩化ビニル共重合体等のエチレン-ビニル化合物共重合体樹脂;ポリスチレン、アクリロニトリル-スチレン共重合体、ABS、α-メチルスチレン-スチレン共重合体等のスチレン系樹脂;ポリビニルアルコール、ポリビニルピロリドン、ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル-塩化ビニリデン共重合体、ポリアクリル酸、ポリメタクリル酸、ポリアクリル酸メチル、ポリメタクリル酸メチル等のビニル系樹脂;ナイロン6、ナイロン6-6、ナイロン6-10、ナイロン11、ナイロン12等のポリアミド樹脂;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル樹脂;ポリカーボネート;ポリフェニレンオキサイド;カルボキシメチルセルロース、ヒドロキシエチルセルロースなどのセルロース誘導体;酸化澱粉、エーテル化澱粉、デキストリンなどの澱粉;及びこれらの混合物からなる樹脂;などを挙げることができる。
このような油性液体の配合量は、一般に、内面1を形成する上記の熱可塑性樹脂100質量部当り、2~15質量部、特に3~10質量部程度であり、用いる油性液体の種類や熱可塑性樹脂の種類に応じて、かかる範囲から成形性が損なわれない程度に、適宜の量を設定すればよい。
さらに、マトリックス樹脂の臨界表面張力が油性液体の表面張力よりも大きいものを選択し、かつ、マトリックス樹脂の臨界表面張力よりも臨界表面張力が小さい分散樹脂5を選択して使用すれば、形成された混成表面上のマトリックス樹脂が露出している部分においては、油性液体1は極めて薄い液膜4を形成しながら、分散樹脂5が比較的多く露出している部分に油性液体1を液滴状に形成することが可能となると考えられる。
このような観点から、本発明では、マトリックス樹脂及び分散樹脂をオレフィン系樹脂の中から選択し、特にマトリックス樹脂として、ポリエチレンやエチレンを主体とする共重合体に代表されるエチレン系樹脂を選択し、分散樹脂として、ポリプロピレンやプロピレンを主体とする共重合体に代表されるプロピレン系樹脂を選択することが望ましい。
マトリックス樹脂:分散樹脂=100:3~100:100
特に、100:5~100:50
さらには、100:10~100:30
の質量比で使用することが最適である。
マトリックス樹脂:ブリード性添加剤
=100:0.03~100:2
特に、 =100:0.05~100:1
さらには、=100:0.01~100:0.5
の質量比で使用することが最適である。
このような粗面化用添加剤として使用される微細粒子としては、例えばレーザー回折散乱法で測定した体積基準での平均粒径が20μm以下の粒子であり、酸化チタン、アルミナ、シリカ等の金属酸化物粒子、炭酸カルシウムなどの炭酸塩、カーボンブラックなどの炭素系微粒子、ポリメチル(メタ)アクリレートや、ポリエチレン、ポリオルガノシルセスキオキサンに代表されるシリコーン粒子などから成る有機微粒子が代表的であり、これらは、シランカップリング剤やシリコーンオイル等により疎水化処理されていてもよい。このような粗面化用添加剤として使用される微細粒子は、通常、内面形成用の熱可塑性樹脂(マトリックス樹脂と分散樹脂との合計量)100質量部当り1~20質量部程度の量で使用される。
本発明の中空成形体は、前述した液滴3が分布した内面1が形成されている限り、該内面を形成するための油性液体がブレンドされている樹脂組成物により形成された単層構造を有するものであってもよいし、該内面1を形成する内面樹脂層の下側に他の層が積層された多層構造を有していてもよい。
本発明の中空成形体は、前述した内面1を形成するための内面形成用樹脂組成物を用い、それ自体公知の成形手段によって形成される。このような中空成形体は、種々の形態を有していてよいが、特に、液滴3が長期にわたって安定に保持され、粘稠な水性液状体に対して優れた滑り性を長期にわたって示すはという観点から、このような水性液状体を収容する容器や該水性液状体を通すための長尺パイプとして極めて有用であり、容器として最も好適に使用される。これらの形態に限られなく、キャップ、スパウト、パイプを所定の大きさにカットしたものであってもよい。
例えば、溶融樹脂(成形用樹脂の溶融物)の押出(押出成形)或いは射出(射出成形)により容器用のプリフォームを成形し、次いで所定のブロー成形温度に維持された該プリフォーム内にブロー用流体を供給して容器の形態に賦形することにより行われる。
一方、ダイレクトブロー容器でのプリフォームは、パイプ形状を有しており、例えばボトル形状の容器の場合、容器の底部となる部分はピンチオフされて閉じられている。このようなプリフォームは、押出成形により成形される。
全体として10で示すこの空容器は、上部に螺子等を備えた口部13を有しており、口部13に連なるブロー部分(即ち、胴部及び胴部を閉じるように形成されている底部を備えた延伸部分)の内面には、上記の油性液体の液滴3が形成されている。
また、口部13の上部には、これを閉じている閉塞部17が形成されている。この閉塞部17には、ブロー成形に当ってブロー用流体を供給するための供給管が挿入される小孔17aが供給されている。この小孔17aは、空容器10の内部に通じている。
内容物充填前の空容器10をこのような形態とするのは、先にも述べたように、容器10の内部を殺菌することが難しいため、滅菌状態を維持し且つ異物の侵入を防止するためである。また、ブロー成形に無菌エアーを用いることで、大気中に含まれる雑菌をボトル内に侵入させず、さらに、加熱されたプリフォームに液体が接触することで加熱殺菌することもできる。
しかるに、本発明では、粘稠な液状体に対して滑り性を示す油性液体が液滴として分布しているため、成形から充填までに長時間が経過した場合にも、液滴の落下は有効に抑制され、優れた滑り性を発揮することができるのである。
尚、以下の実施例等で行った各種の特性、物性等の測定方法及び中空成形体(容器)の成形に用いた樹脂等は次の通りである。
後述の方法で作製した容量500gの中空成形体である多層容器の胴部から20mm×40mmの試験片を切り出し、試験片の内面側の表面状態をデジタルマイクロスコープ(VHX-1000、(株)キーエンス製)にて観察し、画像を撮影した。
画像解析ソフトとして、Image-Pro Plus(Ver.5.0.2.9、Media Cybernetics,Inc.製)を用いて、得られた画像から液滴の分布状態を解析した。解析項目としては、表面に形成された各々の液滴に対し、円相当径(円相当直径)をもとめ、1cm2あたりの分布状態(サイズ、密度)を評価した。
後述の方法で作製した容量500gの中空成形体である多層容器の胴部から20mm×20mmの試験片を切り出し、非接触表面形状測定機(NewView7300,zygo社製)を用いて、成形体表面の形状測定を行った。測定ならびに画像解析には、アプリケーションとして、MetroPro(Ver.9.1.4 64-bit)を用いた。
1.40mmx1.05mmの範囲を測定し、液体の3次元像を観察した。
後述の方法で作製した容量500gの中空成形体である多層容器を22℃60%RHの環境下において、正立状態で所定の期間保管した。所定期間保管した後、容器底部を注意深く目視にて観察し、油性液体の溜まり(液溜まり)があるかを評価した。評価基準は、次のとおりである。
〇:液溜まりが確認されなかった。
×:液溜まりが確認された。
後述の方法で作製した容量500gの中空成形体である多層容器にソース(オタフクお好みソース、オタフクソース(株)製)を室温で500g充填した。充填後、容器口部にキャップを装着して室温下にて400gの内容物を絞り出した後、該ボトルを倒立させて室温下で30分放置した。
放置後、容器を倒立した状態にして、絞り出す操作を2分毎に繰り返し、10分後の重量(残存内容物重量+容器重量)を測定した。測定後、容器内部に残存した内容物を水洗浄し、洗浄後の容器重量を測定し、得られた重量の差分を求め、残存量とした。残存量が少ない程、容器内面での滑り性に優れており、5g以下が良好である。
中鎖脂肪酸トリグリセライド(MCT)
表面張力:29mN/m(23℃)
粘度:33.8mPa・s(23℃)
沸点:210℃以上
引火点:242℃(参考値)
尚、表面張力は、固液界面解析システムDropMaster700(協和界面科学(株)製)を用いて23℃にて測定した値を用いた。また、表面張力測定に必要な液体の密度は、密度比重計DA-130(京都電子工業(株)製)を用いて23℃で測定した値を用いた。
さらに、粘度は音叉型振動式粘度計SV-10((株)エー・アンド・デイ製)を用いて23℃にて測定した値を示した。
低密度ポリエチレン(LDPE)
密度:0.922g/cm3
臨界表面張力:31mN/m
ポリプロピレン(PP)
密度:0.900g/cm3
臨界表面張力:29mN/m
環状オレフィン系共重合体
臨界表面張力:31mN/m以上
ステアリン酸カルシウム(和光純薬工業(株)製)
臨界表面張力:28mN/m
エチレン・ビニルアルコール共重合体(EVOH)
密度:1.20g/cm3
Tg:60℃
無水マレイン酸変性ポリエチレン
ポリプロピレン(PP)
密度:0.900g/cm3
ポリプロピレン(PP)
密度:0.900g/cm3
直鎖状低密度ポリエチレン(LLDPE)
密度:0.905g/cm3
最内層形成樹脂として、低密度ポリエチレン(LDPE)とポリプロピレン(PP)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/PP/MCT=100/10.3/4.6
である。
また、接着層形成用樹脂として無水マレイン酸変性ポリエチレンを用意し、液拡散防止層形成用樹脂としてはエチレン・ビニルアルコール共重合体を用意した。
さらに基材層形成用樹脂としてポリプロピレン(PP)を用意し、外層形成用樹脂としてポリプロピレン(PP)と直鎖状低密度ポリエチレン(LLDPE)とからなる樹脂組成物(PP/LLDPE=100/17.6(質量比))を用意した。
40mm押出機に上記の最内層形成樹脂、30mm押出機Aに上記の接着層形成用樹脂、30mm押出機Bに上記の液拡散防止層形成用樹脂としてエチレン・ビニルアルコール共重合体を、30mm押出機Cに外層形成用樹
脂、50mm押出機に上記の基材層形成用樹脂、及び30mm押出機Cに上記の外層用形成樹脂を、それぞれ供給し、温度210℃の多層ダイヘッドより溶融パリソンを押し出し、金型温度24℃にてダイレクトブロー成形を行い、内容量500g、重量24gの中空成形体である多層容器を作製した。
なお、多層容器の底部から60mmの位置で樹脂層の構成は下記の通りである。
内層(130)/接着層(30)/液拡散抑制層(40)/接着層(20)/
基材層(320)/外層(60)
ここで、括弧内の値は各層の厚みを示す(単位:μm 以下同様)。
作製した容器を用い、成形体表面の顕微鏡観察および液滴の分布状態評価、底溜まり性の評価、および内容物残存量試験を行った。結果をまとめて表1に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)とポリプロピレン(PP)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/PP/MCT=100/14.5/6.0
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
この容器の樹脂層の構成は下記の通りである。
内層(130)/接着層(30)/液拡散抑制層(40)/接着層(20)/
基材層(320)/外層(60)
作製した容器を用い、成形体表面の顕微鏡観察および液滴の分布状態評価、底溜まり性の評価、および内容物残存量試験を行った。結果をまとめて表1に示す。また、成形体表面の顕微鏡観察像を図4(a)に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)とポリプロピレン(PP)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/PP/MCT=100/17.5/7.5
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
この容器の樹脂層の構成は下記の通りである。
内層(130)/接着層(30)/液拡散抑制層(40)/接着層(20)/
基材層(320)/外層(60)
作製した容器を用い、成形体表面の顕微鏡観察および液滴の分布状態評価、白色干渉計による成形体表面における油性液体の形状観察、底溜まり性の評価、および内容物残存量試験を行った。結果をまとめて表1に示す。また、白色干渉計による成形体表面における油性液体の形状観察の結果を図5(a)に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)とステアリン酸カルシウム(StCa)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/StCa/MCT=100/0.03/4.1
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
作製した多層容器を用いて、底溜まり性の評価を行った。結果を表1に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)とステアリン酸カルシウム(StCa)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/StCa/MCT=100/0.18/4.1
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
作製した多層容器を用いて、底溜まり性の評価を行った。結果を表1に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)とステアリン酸カルシウム(StCa)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/StCa/MCT=100/0.20/4.1
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
作製した多層容器を用いて、底溜まり性の評価を行った。結果を表1に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/MCT=100/5.3
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
この容器の樹脂層の構成は下記の通りである。
内層(130)/接着層(30)/液拡散抑制層(40)/接着層(20)/
基材層(320)/外層(60)
作製した容器を用い、成形体表面の顕微鏡観察および液滴の分布状態評価、底溜まり性の評価、および内容物残存量試験を行った。結果をまとめて表1に示す。成形体表面の顕微鏡観察では、表面に液滴は観察されなかった。
最内層形成樹脂として、低密度ポリエチレン(LDPE)と環状オレフィン共重合体(COC)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/COC/MCT=100/10.3/4.6
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
この容器の樹脂層の構成は下記の通りである。
内層(100)/接着層(20)/液拡散抑制層(30)/接着層(20)/
基材層(410)/外層(60)
作製した容器を用い、成形体表面の顕微鏡観察および液滴の分布状態評価、底溜まり性の評価、および内容物残存量試験を行った。結果をまとめて表1に示す。成形体表面の顕微鏡観察では、表面に液滴は観察されなかった。
最内層形成樹脂として、低密度ポリエチレン(LDPE)と環状オレフィン共重合体(COC)と中鎖脂肪酸トリグリセライド(MCT)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/COC/MCT=100/14.5/6.0
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
この容器の樹脂層の構成は下記の通りである。
内層(100)/接着層(20)/液拡散抑制層(30)/接着層(20)/
基材層(410)/外層(60)
作製した容器を用い、成形体表面の顕微鏡観察および液滴の分布状態評価、白色干渉計による成形体表面における油性液体の形状観察、底溜まり性の評価、および内容物残存量試験を行った。結果をまとめて表1に示す。成形体表面の顕微鏡観察像を図4(b)に示す。ここで、表面に液滴は観察されなかった。また、白色干渉計による成形体表面における油性液体の形状観察の結果を図5(b)に示す。
最内層形成樹脂として、低密度ポリエチレン(LDPE)とポリプロピレン(PP)とからなる樹脂組成物を用意した。この樹脂組成物での各成分の質量比は、
LDPE/PP=100/11.1
である。
上記の最内層形成用樹脂を用いた以外は、実施例1と同様に中空成形体である多層容器を作製した。
この多層容器では、内層材として、油性液体は使用していないので、内面に液体は存在していない。
この容器の樹脂層の構成は下記の通りである。
内層(100)/接着層(20)/液拡散抑制層(20)/接着層(20)/
基材層(370)/外層(80)
作製した容器を用い、内容物残存量試験を行った。結果をまとめて表1に示す。
一方、内層材として、LDPEと油性液体としてMCTを用いた比較例1、および、内層材として、マトリックス樹脂にLDPE、分散樹脂にCOC、油性液体としてMCTを用いた比較例2と3、においては、中空成形体内面での油性液体の存在形態は層状(液層状)であることが分かり、油性液体の存在形態が異なっていることが理解できる。
表面張力がマトリックス樹脂(LDPE)よりも大きい環状オレフィン系共重合体(COC)を分散樹脂として使用した場合、液滴は形成されなかった。
一方、分散樹脂としてマトリックス樹脂(LDPE)よりも表面張力が小さいポリプロピレン(PP)およびブリード性有機系添加剤としてステアリン酸カルシウム(StCa)を用いた場合に液滴が形成された。このことから、マトリックス樹脂中にマトリクス樹脂よりも小さい表面張力を有する成分を分散させることが液滴形成に必要であることが分かる。
実施例1~3および比較例1~4での内容物残存量試験の結果から次のことが判る。
内面に油性液体が存在していない比較例4では残存量が12.8gであるのに対し、内面に油性液体が存在している実施例1~3および比較例1~3では残存量が5g以下となっており、水性液状体であるソースの滑り性が飛躍的に向上されており、油性液体が滴状に存在している実施例1~3においても、残存量を低減できることが分かる。
また、実施例1~3の液滴の分布状態評価の結果から、液滴の密度が高いほど、残存量が低減される傾向があることが分かり、液滴の密度を調整することが残存量低減に有効であることが示唆される。
3:液滴
5:分散樹脂
10:空容器
13:口部
15:ブロー成形部
17:閉塞部
Claims (12)
- 内面に樹脂層を備えた中空成形体において、内面を形成している樹脂層の表面には、油性液体の液滴が分布していることを特徴とする中空成形体。
- 前記液滴は、円相当径が25~500μmの大きさを有している請求項1に記載の中空成形体。
- 前記液滴は、100~1000個/cm2の密度で分布している請求項1に記載の中空成形体。
- 前記樹脂層中に、前記油性液体がブレンドされている請求項1に記載の中空成形体。
- 前記中空成形体の内面を形成する前記樹脂層表面が、マトリックス樹脂と該マトリックス樹脂よりも臨界表面張力の小さい物質とを含む混成表面を形成している請求項1に記載の中空成形体。
- 前記樹脂層表面が、マトリックス樹脂と、マトリックス樹脂よりも臨界表面張力の小さい分散樹脂とから形成されている請求項5に記載の中空成形体。
- 前記マトリックス樹脂がエチレン系樹脂であり、前記分散樹脂がプロピレン系樹脂である請求項6に記載の中空成形体。
- 前記樹脂層表面が、マトリックス樹脂と、マトリックス樹脂よりも臨界表面張力の小さいブリード性有機系添加剤とから形成されている請求項5に記載の中空成形体。
- 前記マトリックス樹脂がエチレン系樹脂であり、前記ブリード性有機系添加剤が脂肪酸金属塩である請求項8に記載の中空成形体。
- 前記中空成形体が、閉じられた形態の口部を有するダイレクトブローボトルである請求項1に記載の中空成形体。
- 前記中空成形体が、長尺パイプである請求項1に記載の中空成形体。
- 請求項1に記載の中空成形体の使用方法であって、内面となる前記樹脂層表面に前記液滴が分布している状態で、該内面となる樹脂層表面に水性液状体を接触させる中空成形体の使用方法。
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WO2017033558A1 (ja) * | 2015-08-21 | 2017-03-02 | 東洋製罐株式会社 | 液膜を有する構造体及びその製造方法 |
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JP7497996B2 (ja) | 2020-02-19 | 2024-06-11 | 国立研究開発法人産業技術総合研究所 | 包装材、及び包装容器 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011255901A (ja) * | 2010-06-04 | 2011-12-22 | Toyo Seikan Kaisha Ltd | 多層プラスチック容器 |
WO2013022467A2 (en) * | 2011-08-05 | 2013-02-14 | Massachusetts Institute Of Technology | Liquid-impregnated surfaces, methods of making, and devices incorporating the same |
WO2013065735A1 (ja) * | 2011-10-31 | 2013-05-10 | 東洋製罐株式会社 | ポリエチレン樹脂組成物及びそれを用いた容器 |
US20130251769A1 (en) * | 2012-03-23 | 2013-09-26 | Massachusetts Institute Of Technology | Self-lubricating surfaces for food packaging and food processing equipment |
WO2014010534A1 (ja) * | 2012-07-13 | 2014-01-16 | 東洋製罐株式会社 | 内容物に対する滑り性に優れた包装容器 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0699481A (ja) * | 1992-09-18 | 1994-04-12 | Toppan Printing Co Ltd | 多層ポリエチレン容器 |
US6632493B1 (en) * | 1997-03-31 | 2003-10-14 | The Procter & Gamble Company | Multi-layered plastic container providing good product drainage |
US6247603B1 (en) * | 1999-08-20 | 2001-06-19 | Continental Plastic Containers, Inc. | Container coating for increasing product outage |
JP5225552B2 (ja) | 2006-04-12 | 2013-07-03 | 東洋製罐株式会社 | 水中油型又は油中水型乳化物を収容した製品及び多層構造容器 |
JP4218729B2 (ja) | 2007-03-15 | 2009-02-04 | 東洋製罐株式会社 | 非油性内容物用ポリエチレン製容器 |
JP5125635B2 (ja) | 2008-03-11 | 2013-01-23 | 東洋製罐株式会社 | 非油性内容物用多層プラスチック容器 |
JP6007901B2 (ja) * | 2011-04-18 | 2016-10-19 | キョーラク株式会社 | 製袋用フィルム及び包装袋 |
WO2013022476A1 (en) * | 2011-08-02 | 2013-02-14 | Pegalozi, LLC | Personal watercraft water removal systems and methods |
CN110077686B (zh) | 2013-02-08 | 2020-10-09 | 东洋制罐集团控股株式会社 | 对流动性内容物具有优良的滑动性的容器 |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011255901A (ja) * | 2010-06-04 | 2011-12-22 | Toyo Seikan Kaisha Ltd | 多層プラスチック容器 |
WO2013022467A2 (en) * | 2011-08-05 | 2013-02-14 | Massachusetts Institute Of Technology | Liquid-impregnated surfaces, methods of making, and devices incorporating the same |
WO2013065735A1 (ja) * | 2011-10-31 | 2013-05-10 | 東洋製罐株式会社 | ポリエチレン樹脂組成物及びそれを用いた容器 |
US20130251769A1 (en) * | 2012-03-23 | 2013-09-26 | Massachusetts Institute Of Technology | Self-lubricating surfaces for food packaging and food processing equipment |
WO2014010534A1 (ja) * | 2012-07-13 | 2014-01-16 | 東洋製罐株式会社 | 内容物に対する滑り性に優れた包装容器 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3219643A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017033558A1 (ja) * | 2015-08-21 | 2017-03-02 | 東洋製罐株式会社 | 液膜を有する構造体及びその製造方法 |
JP2019177941A (ja) * | 2018-03-30 | 2019-10-17 | 東洋製罐株式会社 | プラスチック製中栓 |
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US10507948B2 (en) | 2019-12-17 |
JP5962879B1 (ja) | 2016-08-03 |
CN107108112A (zh) | 2017-08-29 |
EA032163B1 (ru) | 2019-04-30 |
JPWO2016076410A1 (ja) | 2017-04-27 |
EP3219643B1 (en) | 2019-10-16 |
AU2015347655A1 (en) | 2017-05-25 |
CN107108112B (zh) | 2018-12-04 |
CA2967280A1 (en) | 2016-05-19 |
EP3219643A1 (en) | 2017-09-20 |
CA2967280C (en) | 2019-01-29 |
EP3219643A4 (en) | 2018-08-22 |
AU2015347655B2 (en) | 2018-06-21 |
KR20170078766A (ko) | 2017-07-07 |
US20180305065A1 (en) | 2018-10-25 |
PL3219643T3 (pl) | 2020-04-30 |
KR101950006B1 (ko) | 2019-02-19 |
EA201791034A1 (ru) | 2017-09-29 |
ES2760540T3 (es) | 2020-05-14 |
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