WO2014175378A1 - 流動性内容物に対する滑り性に優れたブロー成形容器及びその製造方法 - Google Patents
流動性内容物に対する滑り性に優れたブロー成形容器及びその製造方法 Download PDFInfo
- Publication number
- WO2014175378A1 WO2014175378A1 PCT/JP2014/061565 JP2014061565W WO2014175378A1 WO 2014175378 A1 WO2014175378 A1 WO 2014175378A1 JP 2014061565 W JP2014061565 W JP 2014061565W WO 2014175378 A1 WO2014175378 A1 WO 2014175378A1
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- Prior art keywords
- liquid
- container
- layer
- blow
- liquid layer
- Prior art date
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0633—LDPE, i.e. low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0058—Liquid or visquous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7128—Bags, sacks, sachets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7132—Bowls, Cups, Glasses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
Definitions
- the present invention relates to a blow molded container excellent in slipperiness with respect to a fluid content, particularly a highly viscous fluid content, and a method for producing the same.
- 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 containing a slurry-like or paste-like fluid content.
- bottles containing highly viscous fluid contents store the bottles in an inverted state so that the contents can be discharged quickly or used up to the end without remaining in the bottle. In many cases. Therefore, when the bottle is turned upside down, there is a demand for the characteristic that the viscous contents do not remain attached to the inner wall surface of the bottle and fall quickly.
- 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 describes a saturated or unsaturated aliphatic amide as a lubricant in the innermost layer.
- a polyolefin resin bottle in which is blended.
- 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 a packaging material comprising a composition in which an additive having an HLB of 5.0 or less is blended within a range of 0.3 to 3 parts by weight with respect to 100 parts by weight of a polyolefin resin. Yes.
- the packaging material of patent document 4 is excellent in the peelability with respect to emulsified type contents, such as chocolate cream and custard cream. That is, such emulsified contents are unlikely to adhere to the packaging material, and it is possible to avoid inconveniences such as a large amount of contents adhering to the inner surface of the lid material.
- a container formed from such a composition has not improved the slipperiness with respect to fluid contents such as a sauce.
- the inventors of the present invention have previously described a container in which the inner surface of the container, that is, the surface in contact with the contents is a liquid-permeable surface, and the liquid is held on the liquid-permeable surface (Japanese Patent Application No. 2012 1992236) and a container (Japanese Patent Application No. 2013-23468) in which the inner surface of the container is formed of a resin composition containing a molding resin and a liquid (a liquid that is immiscible with the contents).
- a liquid layer is formed at the portion where the contents come into contact, and the slipperiness for fluid contents such as ketchup, sauce, mayonnaise is remarkably enhanced.
- molding is performed by mixing a liquid with a molding resin, but the liquid layer formed on the inner surface of the container is formed by bleed-out from the blend resin that forms the inner layer. For this reason, there is a problem that the liquid that does not bleed remains in the resin layer forming the inner layer and is wasted.
- an object of the present invention is to provide a container in which a liquid layer exhibiting slipperiness with respect to fluid contents is formed thinly and uniformly on the inner surface.
- the present inventors have found that when the blow fluid is supplied and blow molding is performed in the presence of the liquid, As a result, the inventors have found that the layer can be formed thinly and uniformly over the entire inner surface, thereby completing the present invention.
- a blow molded container characterized in that a liquid layer having an amount of 10 g / m 2 or less is formed over the entire inner surface of the stretched portion.
- the liquid layer is formed of a liquid having a boiling point higher than the blow temperature
- the contact angle ⁇ * of the liquid on the resin forming the innermost layer is 40 degrees or less
- ⁇ is the water contact angle on the inner surface of the container
- ⁇ A is a water contact angle on the liquid layer
- ⁇ B is the water contact angle at the surface of the container where the liquid layer is not formed. It is formed so that the coverage F represented by (4)
- the mouth portion is integrally formed in a closed state and the liquid layer is formed on the inner surface. Is preferred.
- a method for producing a blow molded container by blowing a blow fluid into a container preform formed by extrusion or injection of a molten resin and shaping the container into a container shape A method is provided in which a blowing fluid is blown under a condition in which a liquid exists in the inner space of the preform.
- 1) The liquid is supplied to the preform inner space together with the blowing fluid.
- a thin liquid layer having an amount of 10 g / m 2 or less (particularly 0.1 to 10 g / m 2 ) is formed on the inner surface of the container.
- a lubricating liquid for example, even if the contents are highly viscous such as sauce or mayonnaise.
- the contents can be discharged quickly and without remaining on the inner surface of the container. That is, when discharging the contents by inverting or tilting the container, the contents fall in contact with the immiscible liquid layer and the contents fall in a short time. Moreover, it is possible to effectively avoid the contents remaining on the inner surface of the container, and the contents can be effectively removed from the container.
- the thickness of the liquid layer is remarkably thin, and therefore, the disadvantage that the quality of the content (for example, flavor) is reduced by mixing with the content filled in the container is effectively prevented.
- the liquid layer is not scraped off by the contents, and the lubricity with respect to the contents is stably maintained over a long period of time.
- this liquid layer is uniformly formed on the inner surface of the blow-molded container, specifically, the entire portion stretched by blowing, and therefore the lubricity with respect to the contents by such a liquid layer is uniform and uniform. Inconveniences such as contents remaining on a part of the container can be effectively avoided.
- a blow molded container having a liquid layer as described above is manufactured by blowing and blowing a blow fluid in a state where the liquid forming the liquid layer exists in the internal space of the container preform.
- blow fluid is blown in the presence of the liquid and shaped into the shape of the container, the liquid is stretched along with the stretching of the container wall while being pressed against the inner surface of the container by the blow pressure.
- the thin layer described above on the inner surface of the container, in particular, on the portion stretched by blow molding.
- the liquid layer is formed by spraying the liquid by spraying or immersing the container in the liquid, the thickness of the liquid layer is inevitably excessively thick. Since the liquid is stretched together with the container wall while being pressed against the container wall, the liquid becomes thin and uniform.
- the blow-molded container of the present invention basically forms a preform for the container by extrusion (extrusion molding) or injection (injection molding) of a molten resin (melt of a molding resin) as in a conventionally known method. Then, a blowing fluid is supplied into the preform maintained at a predetermined blow molding temperature and shaped into a container shape. However, in the present invention, the blowing fluid is supplied in a state where a liquid for forming a predetermined liquid layer exists in the space in the preform.
- 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.
- a preform for molding a direct blow molded container for food is integrally molded in a form in which the upper part of the unstretched portion serving as the mouth is closed for sterilization until the contents are filled. .
- the closed portion of the upper end of the preform is closed by closing the extruded pipe-shaped resin melt with a clamping die in which a narrow tube (syringe) for blowing fluid extends through the inside at the same time as pinching off the bottom. It is formed. Therefore, the closed portion is formed with pores of the thin tube even after the container is formed.
- the preform is not limited to a single layer structure, but may of course have a multilayer structure made of a blown thermoplastic resin.
- a preform having a multilayer structure is formed by co-injection or co-extrusion by a method known per se.
- Blow molding of a container preform having the above-described form is performed by placing a preform heated to a blow molding temperature (specifically, a glass transition temperature (Tg) or higher of the molding resin) in a blow mold,
- the blow fluid is supplied by inserting a blow fluid supply pipe into the preform. That is, the preform (particularly the portion excluding the mouth) is expanded by the blowing pressure of the blowing fluid, cooled by the blow mold, and shaped into a container shape.
- a parting line generated in the one shaped by the mold is formed on the outer surface of the shaped container.
- the heating to the blow molding temperature may be performed by reheating the one that has been cooled after the preform molding, or the reheating is omitted by using a preform in a heated state immediately after molding. You can also.
- reheating the one that has been cooled after the preform molding
- reheating is omitted by using a preform in a heated state immediately after molding. You can also.
- a pipe-shaped preform that is extruded and in a molten state is subjected to blow molding in a blow temperature region.
- the above-described blowing fluid is blown in a state where a predetermined liquid exists in the preform.
- any means can be adopted as long as the fluid is present in the inner space of the preform when the blowing fluid is blown, but generally, the blowing fluid is combined with the blowing fluid.
- a method of supplying a mist from a supply pipe for use, and a method of supplying the inner surface by coextrusion with a resin constituting the container are preferable.
- the liquid supplied into the preform is spread together with the preform while being pressed against the inner surface of the preform by the blow pressure.
- the blow pressure is usually in the range of 0.2 to 5 MPa.
- the blow-molded container is taken out from the blow mold, and the empty container is filled with the contents, and the mouth is closed with a cap or the like to be sold.
- the blow-molded container formed as described above has a liquid layer uniformly formed on the inner surface (particularly, the blown portion) of the container wall 1.
- FIG. 2 shows a state of an empty container immediately after molding of a food direct blow container to which the present invention is most preferably applied.
- this empty container is provided with a screw or the like at the top.
- the liquid layer 3 is formed on the inner surface of the blow part (that is, the stretched part having a bottom part formed so as to close the trunk part and the trunk part) having the mouth part 13 and continuing to the mouth part 13. Is formed.
- 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 empty container 10 is supplied to the user as it is, where the closed portion 17 is cut out and filled with the contents, and then the cap is fastened to the mouth and the container is sealed for sale.
- the Rukoto As described above, 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 liquid layer 3 is formed inside the empty container 10 whose upper portion is closed as described above. can do.
- the liquid is supplied by spraying or dipping, the liquid layer 3 cannot be formed in the empty container 10 as described above.
- a fluid substance that exhibits fluidity without exhibiting form retention is suitable.
- Viscous pastes or slurry-like fluid substances for example, those having a viscosity at 25 ° C. of 100 mPa ⁇ s or more
- specifically makeup such as ketchup, aqueous glue, honey, various sauces, mayonnaise, milky lotion, etc.
- Liquids, liquid detergents, shampoos, rinses, conditioners and the like are suitable.
- the liquid layer 3 exhibits good slipperiness, even such a viscous fluid substance can be adhered and remained on the inner surface of the container by tilting or inverting the container. This is because it can be discharged quickly.
- the contents are squeezed out by squeezing the body portion, so that ketchup and mayonnaise are accommodated as the contents.
- liquid forming the liquid layer 3 a liquid that is immiscible with the contents (lubricating liquid) is used. If it is miscible with the contents, the lubricating liquid mixes with the contents, drops off from the inner surface of the container, and the liquid layer 3 collapses.
- a lipophilic liquid is used for the aqueous contents, and the oily contents are used.
- a liquid having a coverage F in the above-described range (0.35 or more) may be used as the lubricating liquid.
- the surface tension with respect to the inner surface of the container is significantly different from the surface tension with respect to the contents (interface tension between the content and the lubricating liquid). Is preferred.
- the above-mentioned lubricating liquid is preferably one that can be thinned on the inner wall of the container.
- the thickness E of the lubricating liquid can be reduced. Therefore, it is preferable that the capillary length ⁇ ⁇ 1 of the lubricating liquid and the contact angle ⁇ * of the lubricating liquid on the resin forming the inner surface of the container are small.
- the contact angle ⁇ * of the lubricating liquid on the resin forming the inner surface of the container is preferably 0 ° to 40 °, particularly 0 ° to 20 °.
- the molding temperature at the time of blow molding is usually higher than room temperature, it is possible to form a thin liquid layer corresponding to a wide range of viscosities as compared with spray coating methods and the like. It is. This is because most liquids have a lower liquid viscosity as the temperature is higher, and the liquid layer is easily formed by increasing the extensibility during blow molding.
- the viscosity (value at 23 ° C.) of the liquid used in the present invention is preferably 1 mPa ⁇ s to 1000 mPa ⁇ s, particularly 10 mPa ⁇ s to 500 mPa ⁇ s.
- the spray coating method can also be used to increase the temperature of the liquid and reduce the viscosity of the liquid.
- the container that forms the liquid layer is made of resin
- the resin is thermally deformed by spraying high-temperature liquid. Therefore, the applicable temperature is limited, and the viscosity of the liquid that can be used is limited.
- the present invention is extremely effective in that a thin liquid layer is formed on the inner surface of the blow molded container.
- such a lubricating liquid is preferably present as a liquid at the above-described blowing temperature (that is, a boiling point higher than the blowing temperature). That is, if the boiling point is lower than the blow temperature, the lubricating liquid volatilizes during blow molding, and even if it becomes liquid when the temperature is returned to room temperature, the thickness of the liquid layer 3 becomes uneven. This is because a portion where the liquid layer 3 is not formed is generated.
- a lubricating liquid for example, lubrication most suitably used for moisture-containing contents (for example, ketchup)
- the liquid include silicone oil, glycerin fatty acid ester, liquid paraffin, and edible oil.
- Particularly preferred are glycerin fatty acid esters represented by medium chain fatty acid triglycerides, glycerin trioleate and glycerin diacetomonooleate, liquid paraffin, and edible fats and oils. These are less likely to volatilize, are approved as food additives, and are also odorless and have the advantage of not compromising the flavor of the contents.
- oily contents water or a highly hydrophilic ionic liquid may be used, provided that the boiling point is within the above range.
- silicone oil, glycerin fatty acid ester, liquid paraffin, edible oils and fats are suitable for the emulsifying fluid material.
- the liquid layer 3 formed from the above-described lubricating liquid is a thin layer having an amount of 10 g / m 2 or less, preferably 8 g / m 2 or less. It is uniformly formed over the entire inner surface of. That is, in the present invention, since the liquid (lubricating liquid) is present inside the preform at the time of blow molding, such a thin liquid layer 3 is uniformly formed over the entire inner surface of the blown container. Is possible. That is, even if the thickness of the liquid layer 3 is made larger than the above range, the lubricity with respect to the contents thereof is not improved by an order of magnitude, but rather the lubricating liquid falls off due to the presence of an excessive amount of lubricating liquid. However, inconveniences such as liquid accumulation and mixing with the contents occur, but in the present invention, such inconveniences are effectively avoided.
- the amount of the liquid layer 3 should be in the range of 0.1 g / m 2 or more, particularly 0.3 g / m 2 or more, and most preferably 0.5 g / m 2 or more. This is because if the thickness is too thin, the thickness is uneven, and a portion where the liquid layer 3 is not present may be formed.
- the thickness adjustment of the liquid layer 3 should just set the quantity of the lubricating liquid supplied at the time of blow molding to an appropriate range according to the magnitude
- the thickness of the liquid layer 3 of the blow molded container is determined by extracting the lubricating liquid forming the liquid layer 3 from the container with a solvent miscible with the lubricating liquid, and measuring the weight of the lubricating liquid. Is calculated as
- ⁇ is the water contact angle on the inner surface of the container
- ⁇ A is a water contact angle on the liquid layer
- ⁇ B is the water contact angle at the surface of the container where the liquid layer is not formed.
- the coverage F represented by is 0.35 or more. For example, when a body part of an empty container that is not filled with contents is cut into a size of 2 cm ⁇ 2 cm at any 10 locations, and the coverage rate F is measured, any coverage rate F is 0.35 or more. ing. That is, it can be seen from this that the thin liquid layer 3 is uniformly formed so as to cover the entire inner surface of the container.
- the container described above is formed of various thermoplastics, for example, polyester typified by polyethylene terephthalate, olefin resin, etc. as long as it can be molded into a container form, and is not limited to a single layer structure. As described above, it may have a multilayer structure.
- the container include bottles, cups, and pouches.
- a pouch is a container formed by using at least one film and heat-sealing the peripheral edge of the film.
- a film for forming a pouch is formed by an inflation method in which a resin is extruded from a disk-shaped die or a T-die method in which the resin is extruded from a T-die. The film to be molded may be stretched or unstretched.
- the olefin resin is formed of low density polyethylene, linear low density polyethylene, medium or high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, or the like.
- the olefin resin may be a random or block copolymer of ⁇ -olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene.
- a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and (meth) acrylic acid ester, a copolymer of ethylene and (meth) acrylic acid, and this (meth) acrylic acid are crosslinked with metal ions.
- the so-called ionomer resin may be used. Further, it may be a cyclic olefin copolymer disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2007-284066) described above.
- examples of polyester resins include polyethylene terephthalate, glycol-modified polyethylene terephthalate, polylactic acid, and polybutylene succinate.
- the multilayer structure is not particularly limited, for example, in a direct blow container, it is necessary that the entire thickness of the container wall is adjusted to a thickness that can secure squeeze characteristics.
- the innermost layer can be formed of the above-mentioned olefin-based resin, and a two-layer structure made of high-density polyethylene can be formed on the outer side.
- the intermediate layer in the multilayer structure is generally a gas barrier layer formed using a gas barrier resin such as an ethylene vinyl alcohol copolymer (saponified ethylene vinyl acetate copolymer) or an aromatic polyamide.
- a gas barrier resin such as an ethylene vinyl alcohol copolymer (saponified ethylene vinyl acetate copolymer) or an aromatic polyamide.
- it is most preferably formed using an ethylene vinyl alcohol copolymer. That is, by using a gas barrier resin as the resin for forming the intermediate layer, it is possible to impart oxygen barrier properties to the intermediate layer.
- ethylene vinyl alcohol copolymer exhibits particularly excellent oxygen barrier properties. Oxidative deterioration of the content due to permeation can be effectively suppressed, and excellent sliding properties can be maintained, and at the same time, excellent content preservation can be ensured.
- Suitable thicknesses for such gas barrier intermediate layers are generally in the range of 1 to 50 ⁇ m, in particular 9 to 40 ⁇ m.
- the gas barrier resin as described above is used as an intermediate layer, it is preferable to provide an intermediate layer via an adhesive resin layer in order to enhance adhesion with the inner and outer layers and prevent delamination. Thereby, the intermediate layer can be firmly fixed to the inner and outer layers.
- Adhesive resins used for forming such an adhesive resin layer are known per se.
- 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.
- a regrind layer can be formed by mixing scrap resin generated when the container is molded with an outermost layer forming resin of virgin.
- the amount of scrap resin is preferably about 10 to 60 parts by weight per 100 parts by weight of the virgin outermost resin.
- the thickness of such an outermost adjacent layer varies depending on the size of the packaging container, the type of contents, etc., but the total thickness of the container wall does not become more than necessary, and the scrap resin can be effectively used. In general, the thickness is set to about 20 to 400 ⁇ m.
- liquid layer coating amount Using a 500 g capacity bottle produced by the method described later, the liquid layer (lubricating liquid layer) formed on the inner surface of the container was recovered with 30 mL of a solvent (heptane) miscible with the lubricating liquid, After concentration using an evaporator, the residue was transferred to an evaporating 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 is, the thinner the liquid layer is formed on the inner surface of the container.
- a solvent heptane
- the density of the liquid necessary 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 Industry Co., Ltd.). Further, the viscosity of the lubricating liquid is a value measured at 23 ° C. using a tuning fork type vibration viscometer SV-10 (manufactured by A & D Co., Ltd.).
- Multi-layer bottles were prepared.
- the configuration of this bottle is as follows. Liquid layer / resin innermost layer / adhesive layer / gas barrier layer / adhesive layer / resin outermost layer Using the prepared bottle, measurement of the above-mentioned liquid coverage, measurement of liquid layer coverage, measurement of sliding speed of fluid content, and The bottle appearance was evaluated. The results are summarized in Table 1. Further, the bottle was molded without supplying the liquid, and the contact angle ⁇ * of the lubricating liquid on the resin forming the inner surface of the container was measured. The results are shown in Table 1.
- Example 2 Except for changing the supply amount of the liquid layer material covering the innermost surface of the container, a multi-layer bottle of 5 types and 6 layers (including liquid layer) was prepared by the same procedure and the same material as in Example 1. With bottles produced, the measurement of the liquid coverage of the foregoing, the measurement of the liquid layer coverage, sliding velocity measurements fluid contents, and the bottle appearance evaluated, for the further contact angle of the lubricating liquid theta *, Example 1 was performed. The results are summarized in Table 1.
- the modified polyethylene and ethylene vinyl alcohol copolymer for gas barrier layer formation are supplied to the 30 mm extruder B in the form of pellets, respectively, and medium chain fatty acid triglyceride is supplied by a pump as a liquid layer material covering the innermost surface of the parison.
- the molten parison was extruded from a multilayer die head having a temperature of 210 ° C., and 5 types and 6 layers (including a liquid layer) having an inner volume of 500 g and a weight of 22 g were obtained by a known direct blow molding method at a mold temperature of 22 ° C. and a blow pressure of 0.7 MPa Multi-layer bottles were prepared.
- the configuration of this bottle is as follows. Liquid layer / resin innermost layer / adhesive layer / gas barrier layer / adhesive layer / resin outermost layer In the same manner as in Example 1, using the prepared bottle, measurement of the liquid coverage, measurement of the liquid layer coverage, and bottle The appearance was evaluated, and the contact angle ⁇ * of the lubricating liquid was also the same as in Example 1. The results are summarized in Table 1.
- PETG polyethylene terephthalate
- MFR low-density polyethylene
- modified polyolefin for forming the adhesive layer in the 30 mm extruder A
- Multilayer bottles of 4 types and 4 layers (including liquid layer) having an internal volume of 500 g and a weight of 22 g were prepared by a known direct blow molding method at 0.7 MPa.
- the configuration of this bottle is as follows. Liquid layer / resin innermost layer / adhesive layer / resin outermost layer Using the prepared bottle, in the same manner as in Example 1, the above-described liquid coverage measurement, liquid layer coverage measurement, and bottle appearance evaluation were performed. The contact angle ⁇ * of the lubricating liquid was also the same as in Example 1. The results are summarized in Table 1.
- Example 5 Using an injection molding machine (NN75JS, manufactured by Niigata Steel), dry-treated polyethylene terephthalate (PET) resin was injection molded at a barrel set temperature of 280 ° C and a cycle time of 30 seconds, and weighed 24g (for 500 mL PET bottles) An amorphous preform consisting of a single PET layer was molded.
- N75JS polyethylene terephthalate
- a medium chain fatty acid triglyceride is applied to the inner surface of the preform as a liquid layer forming material, and the preform temperature is 100 degrees and the blow pressure is 3.5 MPa.
- the measurement of the liquid coverage, the measurement of the liquid layer coverage, and the bottle appearance evaluation were performed in the same manner as in Example 1, and the contact angle ⁇ * of the lubricating liquid was also determined in Example 1. As well as. The results are summarized in Table 1.
- the configuration of this bottle is as follows. Resin innermost layer / adhesive layer / gas barrier layer / adhesive layer / resin outermost layer
- the closed portion of the molded bottle mouth was cut, and the inner surface of the bottle was coated with medium chain fatty acid triglyceride by spray coating. After coating, the mouth portion was held downward for 3 minutes to remove excess medium chain fatty acid triglyceride present on the inner surface of the bottle.
- measurement of the above-mentioned liquid coverage, measurement of the liquid layer coverage, measurement of the contact angle ⁇ * of the lubricating liquid on the resin forming the inner surface of the container, measurement of the sliding speed of the fluid content, and the bottle Appearance evaluation was performed. The results are summarized in Table 1.
- Container wall 3 Liquid layer 10: Empty container 13: Mouth 15: Blow molding part 17: Blocking part
Abstract
Description
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。
しかしながら、本発明者等の研究によると、このような組成物から形成された容器では、ソースなどの流動性内容物に対する滑り性を高めるには至っていないことが判った。
しかしながら、これらの容器は、内容物との滑り性を高めるために形成される液層を薄く且つ均一に形成することが困難であるという問題や、内面を形成する樹脂に多量の液体を混合する必要があるといった問題があり、さらなる改善が必要である。即ち、特願2012-199236号の容器では、容器を成形後、内容物が接触する部分にスプレー等の手段で液体を施すため、形成される液層が必要以上に厚くなり過ぎてしまい、結果、かかる液体の内容物への移行などが問題となるおそれがある。一方、特願2013-23468号の容器では、成形用樹脂に液体を混合して成形が行われるが、容器内面に形成された液層は、内層を形成するブレンド樹脂からのブリードアウトで形成されるため、内層を形成する樹脂層にはブリードしない液体が残ってしまい、無駄になるといった問題があった。
かかる本発明の容器においては、
(1)前記液層は、ブロー温度よりも高い沸点を有している液体により形成されていること、
(2)最内層を形成する樹脂上における前記液体の接触角θ*が40度以下であること、
(3)前記液層は、ブロー成形部分の内面全体わたって、下記式(1):
F=(cosθ-cosθB)/(cosθA-cosθB) (1)
式中、θは、容器内面での水接触角であり、
θAは、前記液層上での水接触角であり、
θBは、液層が形成されていない容器面での水接触角である、
で表される被覆率Fが0.35以上となるように形成されていること、
(4)口部が閉じられた状態に一体成形され且つ前記液層が内面に形成されていること、
が好適である。
前記プリフォーム内空間に液体が存在する条件下でブロー用流体を吹き込むことを特徴とする方法が提供される。
上記の製造方法において、
1)前記液体は、ブロー用流体と共に、前記プリフォーム内空間に供給されること、
或いは
2)前記液体が、容器用プリフォームの内面を被覆した状態でブロー用流体を吹き込むこと、
が好ましい。
本発明のブロー成形容器は、基本的には、従来公知の方法と同様、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。ただ、本発明においては、該プリフォーム内の空間に所定の液層を形成するための液体が存在する状態でブロー用流体が供給されることとなる。
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。
また、プリフォーム上端の閉塞部分は、押し出されてきたパイプ状の樹脂溶融物を、底部のピンチオフと同時に、ブロー流体用の細管(シリンジ)が内部を通って伸びている締め型によって閉じることにより形成される。従って、この閉塞部には、容器成形後にも該細管の空孔が形成されている。
尚、ブロー成形温度への加熱は、プリフォーム成形後、一旦冷却されたものを再加熱することにより行ってもよいし、成形直後の加熱状態にあるプリフォームを用いることにより再加熱を省略することもできる。一般に、通常のダイレクトブロー成形では、押し出されて溶融状態にあるパイプ形状のプリフォームを、ブロー温度領域でブロー成形に供される。
このようにして成形されるブロー成形容器の内面には、液体の層が、容器の内面(延伸される部分)の全体にわたって薄く均一に形成されることとなる。
成形後、ブロー成形容器は、ブロー型から取り出され、この空容器には、内容物が充填され、キャップ等により口部を閉じて販売に供されることとなる。
以上のようにして形成されるブロー成形容器は、図1に示されているように、容器壁1の内面(特にブローされている部分)に液体の層が全体にわたって均一に形成されている。
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。
E=2κ-1sin(θ*/2) (2)
本発明では、潤滑液の厚みEを薄くできるものが好ましいため、潤滑液の毛管長κ-1、および容器内面を形成する樹脂上における潤滑液の接触角θ*が小さいものが好ましい。特に、容器内面を形成する樹脂上における潤滑液の接触角θ*としては、0度乃至40度、特に0度乃至20度であることが好適である。
スプレーコート法でも、同様に液体の温度を高くし、液体の粘度を下げる方法が考えられるが、液層を形成させる容器が樹脂製の場合、高温の液体を吹きつけることにより、樹脂が熱変形してしまうため、適用できる温度が制限され、用いることのできる液体の粘度は限定的となる。また、スプレーコート法で容器内面に形成する液層を薄くさせる場合、吹き付ける液体の微粒化が必須であるが、低粘度でない液体の微粒化は容易ではなく、薄い液層を形成することが困難であることは公知の通りである。
このような観点からも、ブロー成形容器内面に薄い液層を形成させる点において、本発明は極めて有効である。
また、油性の内容物に対しては、沸点が上記範囲内であることを条件として、水あるいは親水性の高いイオン液体等が挙げられる。
さらに、乳化系の流動性物質に対しては、シリコーンオイル、グリセリン脂肪酸エステル、流動パラフィン、食用油脂などが好適である。
また、ブロー成形容器の液層3の厚みは、容器から液層3を形成する潤滑液を、潤滑液と混和性の溶剤で抽出し、その重さを測定することにより、単位面積あたりの重さとして算出される。
F=(cosθ-cosθB)/(cosθA-cosθB) (1)
式中、θは、容器内面での水接触角であり、
θAは、前記液層上での水接触角であり、
θBは、液層が形成されていない容器面での水接触角である、
で表される被覆率Fが0.35以上となっている。例えば、内容物が充填されていない空容器の胴部を任意の10か所で2cm×2cmの大きさに切り取り、その被覆率Fを測定すると、何れの被覆率Fも0.35以上となっている。即ち、このことから、前述した薄い液層3は、容器の内面全体を被覆するように均一に形成されていることが判る。
また、容器の形態としては、ボトル、カップ、パウチなどが挙げられる。パウチとは、少なくとも1枚以上のフィルムを使用し、フィルムの周縁部をヒートシールすることにより作成される容器である。パウチ形成用のフィルムは、樹脂を円盤状のダイから押し出すインフレーション法やTダイから押し出すTダイ法により成形される。成形されるフィルムは、延伸、未延伸であってもよい。
例えば、オレフィン系樹脂としては、低密度ポリエチレン、直鎖低密度ポリエチレン、中或いは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-ペンテンなどにより形成される。勿論、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-オレフィン同志のランダムあるいはブロック共重合体等であってもよい。さらには、エチレンと酢酸ビニルの共重合体、エチレンと(メタ)アクリル酸エステルとの共重合体、エチレンと(メタ)アクリル酸との共重合体およびこの(メタ)アクリル酸が金属イオンで架橋されたいわゆるアイオノマー樹脂であってもよい。また、前述した特許文献1(特開2007-284066号)に開示されている環状オレフィン系共重合体であってもよい。
一方、ポリエステル系樹脂としては、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタレート、ポリ乳酸、ポリブチレンサクシネートなどが挙げられる。
例えば、シャンプーやコンディショナー等のボトルに使用する場合においては、最内層を上記のオレフィン系樹脂により形成し、その外側に高密度ポリエチレンからなる2層構造とすることができる。
このようなガスバリア中間層の好適な厚みは、一般に1乃至50μm、特に9乃至40μmの範囲である。
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容器(ボトル)の成形に用いた樹脂等は次の通りである。
後述の方法で成形した容量500gのボトルの胴部の任意の10点から20mm×20mmの試験片を切り出した。23℃50%RHの条件下、固液界面解析システムDropMaster700(協和界面化学(株)製)を用い、試験片の内層が上になるように固定し、3μLの純水を試験片にのせ、水接触角θを測定した。得られた水接触角を用いて、下記式(1)より、ボトル内面の潤滑液の被覆率Fを求めた。
F=(cosθ-cosθB)/(cosθA-cosθB) (1)
式中、θは、容器内面での水接触角であり、
θAは、前記液層を被覆した容器内面上での水接触角であり、
θBは、液層が形成されていない容器内面での水接触角である、
潤滑液の被覆率Fを求めるにあたり、θAとθBの値として、下記水接触角の値を用いた。
θB:100.1°(高圧法低密度ポリエチレン(MFR=0.3)
単独での値)
θB:93.5°(環状オレフィン系共重合体単独での値)
θB:72.0°(グリコール変性ポリエチレンテレフタレート単
独での値)
θB:65.8°(ポリエチレンテレフタレート単独での値)
θA:80.3°(中鎖脂肪酸トリグリセライドの液膜上での値)
後述の方法で作製した容量500gのボトルを用いて、容器内面に形成された液層(潤滑液層)を、潤滑液と混和性の溶剤(ヘプタン)30mLで回収し、エバポレーターを用いて濃縮した後、残留物を蒸発皿へ移し取り、液層成分の重さを求めた。得られた重さを容器内面の面積で除し、ボトル内面における液層被覆量(g/m2)とした。この値が小さい程、容器内面には薄い液層が形成されている。
後述の方法において、液層を形成せずに各種層構成の容器(ボトル)を成形した。成形したボトルの胴部から20mmx70mmの試験片を切り出した。23℃50%RHの条件下、固液界面解析システムDropMaster700(協和界面化学(株)製)を用い、試験片の内層が上になるように固定し、2μLの潤滑液を試験片にのせ、容器内面を形成する樹脂上における潤滑液の接触角θ*を測定した。
この値が小さい程、潤滑液の薄膜化に適していることを示している。
後述の方法で作製した容量500gのボトルの胴部から20mmx70mmの試験片を切り出した。23℃50%RHの条件下、固液界面解析システムDropMaster700(協和界面化学(株)製)を用い、試験片の内層が上になるように固定し、70mgの流動性内容物を試験片にのせ、45°の傾斜角における滑落挙動をカメラで撮影し、滑落挙動を解析し、移動距離-時間のプロットから滑落速度を算出した。この滑落速度を滑落性の指標とした。前記滑落速度の値が大きい程、内容物の滑落性が優れている。用いた流動性内容物は下記の通りである。なお、内容物の粘度として、音叉型振動式粘度系SV-10((株)エー・アンド・デイ製)を用いて25℃で測定した値も共に示す。
用いた流動性内容物;
キユーピーハーフ(キユーピー(株)製、粘度=1260mPa・s)
ケチャップ(カゴメ(株)製、粘度=1050mPa・s)
お好みソース(オタフクソース(株)製、粘度=560mPa・s)
後述の方法で作製したボトルにおいて、ボトル内面における潤滑液の液溜まりの有無を目視にて評価した。液溜まりが発生しなかったものを○、液溜まりが発生したものを×とした。液溜まりが発生しないものが良好なボトルである。
高圧法低密度ポリエチレン(LDPE)
MFR;0.3g/10min
密度;0.92g/cm3
環状オレフィン系共重合体
(COC、エチレン・テトラシクロドデセン共重合体)
Tg;80℃
密度;1.02g/cm3
グリコール変性ポリエチレンテレフラレート(PETG)
Tg;80℃
密度;1.27g/cm3
<最外層形成用樹脂>
高圧法低密度ポリエチレン(LDPE)
MFR;0.4g/10min
<接着剤層形成用樹脂>
無水マレイン酸変性ポリエチレン
変性ポリオレフィン
<ガスバリア層形成用樹脂>
エチレンビニルアルコール共重合体
(密度1.20g/cm3、Tg60℃)
<潤滑液>
中鎖脂肪酸トリグリセライド
表面張力(23℃);28.8mN/m
粘度(23℃);33.8mPa・s
沸点:210℃以上
引火点:242℃(参考値)
尚、潤滑液の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。なお、液体の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。また、潤滑液の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。
50mm押出機に最内層用の低密度ポリエチレン(MFR=0.3)、40mm押出機に最外層用の低密度ポリエチレン(MFR=0.4)、30mm押出機Aに接着剤層用の無水マレイン酸変性ポリエチレン、30mm押出機Bにガスバリア層形成用のエチレンビニルアルコール共重合体を、それぞれペレットの形態で供給し、さらにパリソンの最内面を被覆する液層材料として中鎖脂肪酸トリグリセライドをポンプにより供給し、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20℃、ブロー圧0.7MPaにて公知のダイレクトブロー成形法により内容量500g、重量24gの5種6層(液層含む)の多層ボトルを作製した。このボトルの構成は次の通りである。
液層/樹脂最内層/接着層/ガスバリア層/接着層/樹脂最外層
作製したボトルを用い、前述の液体被覆率の測定、液層被覆量の測定、流動性内容物の滑落速度測定、およびボトル外観評価を行った。結果を表1にまとめて示す。
また、液体を供給せずボトルを成形し、容器内面を形成する樹脂上における潤滑液の接触角θ*の測定を行った。結果を表1に示す。
容器の最内面を被覆する液層材料の供給量を変更した以外は実施例1と同様の手順・同一の材料で5種6層(液層含む)の多層ボトルを作製した。
作製したボトルを用い、前述の液体被覆率の測定、液層被覆量の測定、流動性内容物の滑落速度測定、およびボトル外観評価を行い、さらに潤滑液の接触角θ*についても、実施例1と同様に行った。結果を表1にまとめて示す。
40mm押出機に最内層用の環状オレフィン系共重合体(COC)、50mm押出機に最外層用の低密度ポリエチレン(MFR=0.4)、30mm押出機Aに接着剤層用の無水マレイン酸変性ポリエチレン、30mm押出機Bにガスバリア層形成用のエチレンビニルアルコール共重合体を、それぞれペレットの形態で供給し、さらにパリソンの最内面を被覆する液層材料として中鎖脂肪酸トリグリセライドをポンプにより供給し、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22℃、ブロー圧0.7MPaにて公知のダイレクトブロー成形法により、内容量500g、重量22gの5種6層(液層含む)の多層ボトルを作製した。このボトルの構成は次の通りである。
液層/樹脂最内層/接着層/ガスバリア層/接着層/樹脂最外層
作製したボトルを用い、実施例1と同様にして、前述の液体被覆率の測定、液層被覆量の測定、およびボトル外観評価を行い、さらに潤滑液の接触角θ*についても、実施例1と同様に行った。結果を表1にまとめて示す。
40mm押出機に最内層用のグリコール変性ポリエチレンテレフタレート(PETG)、50mm押出機に最外層用の低密度ポリエチレン(MFR=0.4)、30mm押出機Aに接着剤層形成用の変性ポリオレフィンを、それぞれペレットの形態で供給し、さらにパリソンの最内面を被覆する液層材料として中鎖脂肪酸トリグリセライドをポンプにより供給し、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22℃、ブロー圧0.7MPaにて公知のダイレクトブロー成形法により内容量500g、重量22gの4種4層(液層含む)の多層ボトルを作製した。このボトルの構成は次の通りである。
液層/樹脂最内層/接着層/樹脂最外層
作製したボトルを用い、実施例1と同様にして、前述の液体被覆率の測定、液層被覆量の測定、およびボトル外観評価を行い、さらに潤滑液の接触角θ*についても、実施例1と同様に行った。結果を表1にまとめて示す。
射出成形機(NN75JS、新潟鐵工所製)を使用し、乾燥処理済みのポリエチレンテレフタレート(PET)樹脂をバレル設定温度280℃、サイクルタイム30秒にて射出成形し、重量24g(500mLPETボトル用)のPET単層からなる非晶プリフォームを成形した。
作製したボトルを用い、実施例1と同様にして、前述の液体被覆率の測定、液層被覆量の測定、およびボトル外観評価を行い、さらに潤滑液の接触角θ*についても、実施例1と同様に行った。結果を表1にまとめて示す。
50mm押出機に最内層用の低密度ポリエチレン(MFR=0.3)、40mm押出機に最外層の低密度ポリエチレン(MFR=0.4)、30mm押出機Aに接着剤層の無水マレイン酸変性ポリエチレン、30mm押出機Bにガスバリア層形成用のエチレンビニルアルコール共重合体を、それぞれ、ペレットの形態で供給し、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20℃、ブロー圧0.7MPaにて公知のダイレクトブロー成形法により内容量500g、重量24gの4種5層の多層ボトルを作製した。このボトルの構成は次の通りである。
樹脂最内層/接着層/ガスバリア層/接着層/樹脂最外層
成形したボトル口部の閉塞部を切り、スプレーコート法により中鎖脂肪酸トリグリセライドをボトル内面に被覆した。コートした後、口部を下向きにして3分間保持しボトル内面に存在する余分な中鎖脂肪酸トリグリセライドを除去した。
作製したボトルを用い、前述の液体被覆率の測定、液層被覆量の測定、容器内面を形成する樹脂上における潤滑液の接触角θ*の測定、流動性内容物の滑落速度測定、およびボトル外観評価を行った。結果を表1にまとめて示す。
比較例1と同様の手順で4種5層の多層ボトルを作製した。このボトルの構成は次の通りである。
樹脂最内層/接着層/ガスバリア層/接着層/樹脂最外層
成形したボトルの内面を液体で被覆せずに、流動性内容物の滑落速度測定、およびボトル外観評価を行った。結果を表1にまとめて示す。
これらのことから、本発明においては、ボトル内面への液層形成において、被覆率を下げることなく、液層を薄くすることが可能であると言える。
流動性内容物の滑落速度に関して、液層を形成していない比較例2では、いずれの内容物に対しても滑落速度の値が小さく、滑落性が悪いことが分かるが、液層を形成したものでは、いずれの内容物に対しても滑落速度の値が10倍以上の値となっており、滑落性が優れていることが分かる。
ボトル外観評価について、液層を被覆していない比較例2、および液層被覆量が10g/m2以下と小さい実施例1~5では液溜まりが発生しなかったが、液層被覆量が44g/m2と大きい比較例1では液溜まりが発生した。このことから、液溜まりの発生を抑制するためには、ボトル内面の被覆量を小さくすることが必要であることが分かる。
以上の結果より、ボトル内面に10g/m2以下の薄い液層を形成することにより、ボトル内面に液溜まりが発生せずに、かつ、滑落性に優れたボトルを提供できることが明らかになった。
3:液層
10:空容器
13:口部
15:ブロー成形部
17:閉塞部
Claims (10)
- 10g/m2以下の量の液層が延伸されている部分の内面全体にわたって形成されていることを特徴とするブロー成形容器。
- 前記液層は、ブロー温度よりも高い沸点を有している液体により形成されている請求項1に記載のブロー成形容器。
- 最内層を形成する樹脂上における前記液体の接触角θ*が40度以下である請求項2に記載のブロー成形容器。
- 前記液層を形成する液体の粘度が、1乃至1000mPa・s(23℃)である請求項2記載のブロー成形容器。
- 前記液層は、ブロー成形部分の内面全体にわたって、下記式(1):
F=(cosθ-cosθB)/(cosθA-cosθB) (1)
式中、θは、容器内面での水接触角であり、
θAは、前記液層上での水接触角であり、
θBは、液層が形成されていない容器面での水接触角であ
る、
で表される被覆率Fが0.35以上となるように形成されている請求項1に記載のブロー成形容器。 - 口部が閉じられた状態に一体成形され且つ前記液層が内面に形成されている請求項1に記載のブロー成形容器。
- 前記液層は、ブロー成形部分の内面全体にわたって、下記式(1):
F=(cosθ-cosθB)/(cosθA-cosθB) (1)
式中、θは、容器内面での水接触角であり、
θAは、前記液層上での水接触角であり、
θBは、液層が形成されていない容器面での水接触角であ
る、
で表される被覆率Fが0.35以上となるように形成され、
口部が閉じられた状態に一体成形され且つ前記液層が内面に形成されている請求項3に記載のブロー成形容器。 - 溶融樹脂の押出し或いは射出により成形された容器用プリフォームの内部にブロー用流体を吹き込んで容器形状に賦形することによりブロー成形容器を製造する方法において、
前記プリフォーム内空間に液体が存在する条件下でブロー用流体を吹き込むことを特徴とする請求項1のブロー成形容器を製造する方法。 - 前記液体が、ブロー用流体と共に、前記プリフォーム内空間に供給される請求項8に記載の方法。
- 前記液体が、容器用プリフォームの内面を被覆した状態でブロー用流体を吹き込むことを特徴とする請求項8記載の方法。
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JP5713154B1 (ja) | 2015-05-07 |
EP2990176B1 (en) | 2018-08-01 |
KR102107494B1 (ko) | 2020-05-07 |
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CN105142879A (zh) | 2015-12-09 |
KR101847101B1 (ko) | 2018-04-10 |
CN105142879B (zh) | 2017-10-27 |
KR20170126013A (ko) | 2017-11-15 |
ES2687568T3 (es) | 2018-10-26 |
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PL2990176T3 (pl) | 2018-12-31 |
KR20150135456A (ko) | 2015-12-02 |
EP2990176A4 (en) | 2016-12-07 |
US20160039557A1 (en) | 2016-02-11 |
JP6222022B2 (ja) | 2017-11-01 |
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