JP2019099220A - Blow-molded container and package body - Google Patents

Abstract

To provide a blow-molded container having an excellent liquid draining property of a container inner layer.SOLUTION: A blow-molded container has a filling space to be filled with viscous liquid. The filling space is formed by a container inner layer made of thermoplastic resin composition. The thermoplastic resin composition includes thermoplastic resin and silicone resin, and a slip angle is 10° or more and 50° or less when 10 μL of water is dropped on a face forming the filling space of the container inner layer, at 25°C.SELECTED DRAWING: Figure 2

Description

  The present invention relates to blow molded containers and packages.

  Various techniques have been developed in the field of packaging containers in which conventional viscous contents are contained. Examples of this type of technology include the technology described in Patent Document 1. The document describes that the packaging container is made, for example, using biaxial stretch blow molding. Further, in the same document, non-adhesion treatment by spraying fine particles and the like is performed to the pouring channel of the contents, and at the same time, the container is provided with a suckback property, so that the liquid breakage due to the non-adhesion treatment It is described that the improvement of the water content can be dramatically improved, and the liquid dripping at the time of discharging the contents can be almost completely prevented.

JP, 2015-63315, A

The present inventor examined using the packaging container of patent document 1 as a packaging container of the viscous liquid containing a lipid and a protein. As a result, it was found that after the viscous liquid was discharged from the packaging container, the viscous liquid adhered and remained on the inner layer of the container forming the filling space of the packaging container. When the viscous liquid adheres to and remains in the inner layer of the container, there is a disadvantage such as a decrease in the self-supporting stability of the packaging container.
Then, this invention makes it a subject to provide the blow-molded container which is excellent in the liquid drainability of a container inner layer.

  The present inventor examined the inner layer of the container in order to improve the drainage of the inner layer of the blow molded container. As a result, the container inner layer is formed of a thermoplastic resin composition containing a thermoplastic resin and a silicone resin, and the sliding angle of the container inner layer is controlled so as to fall within a specific numerical range. The inventors have found that an excellent blow-molded container can be obtained and completed the present invention.

According to the invention
A blow molded container comprising a filling space for filling a viscous liquid, comprising:
The filling space is formed by a container inner layer made of a thermoplastic resin composition,
The thermoplastic resin composition comprises a thermoplastic resin and a silicone resin,
There is provided a blow-molded container having a sliding angle of not less than 10 ° and not more than 50 ° when 10 μl of water is dropped onto the surface of the inner layer of the container formed with the filling space at a temperature of 25 ° C.

Moreover, according to the present invention,
Said blow molded container,
And a lid.

  ADVANTAGE OF THE INVENTION According to this invention, the blow-molded container which is excellent in the liquid washout property of a container inner layer is provided.

It is sectional drawing of an example of the blow molding container which concerns on this embodiment. It is sectional drawing of an example of the blow molding container which concerns on this embodiment. It is sectional drawing of an example of the blow molding container which concerns on this embodiment.

  Hereinafter, the present embodiment will be described using drawings as appropriate. In all the drawings, the same components are denoted by the same reference numerals and the description thereof will be omitted.

  The blow molded container according to the present embodiment is a blow molded container provided with a filling space for filling a viscous liquid, wherein the filling space is formed by an inner layer of the container made of a thermoplastic resin composition, and the thermoplastic resin is The resin composition contains a thermoplastic resin and a silicone resin, and at a temperature of 25 ° C., a sliding angle is 10 ° or more and 50 ° or less when 10 μl of water is dropped on the surface of the inner layer of the container to form the filling space. is there.

  In the field of blow molded containers filled with a viscous liquid containing lipids and proteins, the present inventors have found that, in conventional blow molded containers, the viscous liquid is discharged in the container inner layer forming the filling space after discharging the viscous liquid. It was found that it adhered and remained. When the viscous liquid adheres to and remains in the inner layer of the container, for example, the self-standing stability of the packaging container, the appearance thereof, and the dischargeability of the viscous liquid are disadvantageously reduced.

Therefore, the present inventor examined a method for improving the drainage of the inner layer of the blow molded container. As a result, the container inner layer is formed of a thermoplastic resin composition containing a thermoplastic resin and a silicone resin, and the sliding angle of the container inner layer is controlled so as to fall within a specific numerical range. It has been found that an excellent blow molded container can be obtained.
The detailed mechanism is not clear, but the reason is guessed as follows. If the sliding angle of the container inner layer falls within a specific numerical range, it is presumed that the silicone resin is unevenly distributed on the surface forming the filling space of the container inner layer. This can improve the drainage of the viscous liquid.
From the above, it is presumed that the liquid repellency of the film for forming a packaging container according to the present embodiment can be improved, and the liquid draining property of the packaging container can be improved.

  Hereinafter, the blow molded container according to the present embodiment will be described in detail.

(Blow molded container)
The shape of the blow-molded container is not limited as long as it is a conventionally known shape formed by blow molding. Specific examples of the shape of the blow molded container include a tube shape, a bottle shape, and a tank shape. As a shape of a blow molding container, it is preferable that it is a tube shape among the said specific examples, for example. In the blow molded container according to the present embodiment, after the viscous liquid is discharged, the viscous liquid does not adhere to or remain in the inner layer of the container. When a viscous liquid adheres to the inner layer of a conventional tube-shaped blow-molded container, the self-supporting stability is deteriorated, the appearance is deteriorated, and the viscous liquid is discharged, depending on the remaining amount of the viscous liquid in the packaging container. There was a disadvantage of decreasing sex. The blow molded container according to the present embodiment is excellent in the ability to drain the viscous liquid of the inner layer of the container. Therefore, the problems described above do not occur, and the self-standing stability, the appearance, and the dischargeability can be made suitable regardless of the amount of viscous liquid remaining in the packaging container.

  As the tube-shaped blow-molded container, for example, one that can be reversibly deformed without breaking the layer structure and the volume of the filling space can be changed. Thereby, air can be selectively expelled from the filling space. By reducing the amount of air in the filling space, the deterioration of the viscous liquid to be filled can be suppressed.

As an example of the shape of the blow molded container which concerns on this embodiment, the tube-shaped blow molded container of FIG. 1 is shown. Hereinafter, based on FIG. 1, the blow molded container 10 which concerns on this embodiment is demonstrated.
In addition, the shape of the blow molded container which concerns on this embodiment is not limited to the shape of FIG. 1, It can be set as the shape according to the property of the viscous liquid with which it is filled, a sales form, a preservation method. The shape of the blow molded container may be, for example, the shape shown in FIG. 1 or the shape shown in FIG.

  The blow molded container 10 according to the present embodiment includes, for example, a screw portion 12 and a main body portion 14.

(Screw 12)
The screw portion 12 is a portion for fastening the lid portion. Here, the screw portion 12 is connected to, for example, the main body portion 14.
The shape of the screw portion 12 is not limited. For example, it is preferable that the shape is a male screw shape, that is, a shape in which a screw thread is present on the outer surface of the screw portion 12. This can prevent the viscous liquid from adhering to the thread.

(Body part 14)
The body portion 14 includes most of the filling space 20. The main body portion 14 is, for example, a portion filled with a viscous liquid and further supporting the blow molded container 10 itself.
Here, the main body portion 14 includes, for example, the discharge port 22 and the bottom portion 24.

(Filling space 20)
The filling space 20 is constituted by the container inner layer. The filling space 20 is formed, for example, inside the screw portion 12 and the main body portion 14. Moreover, the filling space 20 may be sealed, and may be provided with, for example, a discharge port 22 described later.

(Bottom 24)
The bottom portion 24 is a surface which becomes the bottom of the filling portion when the blow molded container is erected and allowed to stand. Here, the shape of the bottom portion 24 may be, for example, a curved shape in which the outer edge portion of the bottom portion is grounded as illustrated in FIG. 1. Also, the shape of the bottom portion 24 may be, for example, a planar shape. The shape of the bottom 24 is preferably, for example, a curved shape in which the outer edge of the bottom is in contact with the ground. As a result, even if the filling space is sufficiently filled with the viscous liquid and a load is applied to the bottom, the bottom can be prevented from bulging and the self-supporting stability being lowered.

(Discharge port 22)
The discharge port 22 is a port for discharging the viscous liquid from the filling space. Although the shape of the discharge port is not limited, for example, from the viewpoint of forming the screw portion 12, it is preferable to be circular.
Although the position of the discharge port 22 is not limited, for example, when the blow molded container stands upright, the central axis 40 of the blow molded container extending vertically from the center of the discharge port 22 passes through the bottom 24 Is preferred.

(Inner lid)
Here, the discharge port 22 may include, for example, an inner lid not shown. Here, the inner lid portion may be formed of, for example, a thermoplastic resin composition similar to that of the inner layer of the container, or may seal a sealing material formed of a polyolefin resin such as polyethylene or polypropylene. The shape of the inner lid is not limited, and can be appropriately set according to the composition and viscosity of the viscous liquid to be filled. Specific examples of the shape of the inner lid include a polygonal shape such as a star shape; a circular shape; and an oval shape such as an oval shape and an egg shape. For example, when the viscous liquid is a highly viscous liquid such as honey, starch syrup, mayonnaise, ketchup, or dressing, the shape of the discharge port is preferably star-shaped. Thereby, the dischargeability of the viscous liquid can be controlled. In the present embodiment, the oval shape has a symmetry axis at least one or more, does not intersect, is convex outward, and has a closed, curved shape on a plane. Show.

(Layer structure)
Hereinafter, the layer structure which comprises a blow molding container is demonstrated.
The layer structure of the blow-molded container according to the present embodiment may be, for example, a single-layer structure or a multi-layer structure, depending on the use of the blow-molded container.

(Container inner layer)
The blow molded container according to the present embodiment comprises at least an inner container layer made of a thermoplastic resin composition. The filling space in which the viscous liquid is filled is formed by the inner vessel layer.
The thermoplastic resin composition contains a thermoplastic resin and a silicone resin.

(Thermoplastic resin)
Specifically as a thermoplastic resin, polyolefin resin, a polyester resin, a fluorine resin, etc. are mentioned. As the first thermoplastic resin, one or more of the above specific examples can be used in combination.
Specific examples of the polyolefin resin include polyethylene (PE) such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (mLLPE), etc .; polypropylene (PP); Polyvinyl alcohol (PVA); ethylene-vinyl acetate copolymer (EVA); ethylene-methyl acrylate copolymer (EMA); ethylene-acrylic acid copolymer (EAA); ethylene-methyl methacrylate copolymer (EMMA) Ethylene-ethyl acrylate copolymer (EEA); ethylene-methacrylic acid copolymer (EMAA); ionomer resin; ethylene-vinyl alcohol copolymer (EVOH); norbornene-ethylene copolymer and the like. As polyolefin resin, it can be used combining 1 type, or 2 or more types among the said specific examples.
Specific examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like. As a polyester resin, it can be used combining 1 type, or 2 or more types among the said specific examples.
Specific examples of the fluorine-based resin include polymers of monomers such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride and perfluoroalkyl vinyl ether, or two or more monomers. A copolymer etc. are mentioned.
As a thermoplastic resin, it is preferable to use a polyolefin resin among the said specific examples, for example. Thereby, the blow molded container can exhibit suitable mechanical properties. When the silicone resin contained in the thermoplastic resin composition is a polyolefin-silicone copolymer, although the detailed mechanism is not clear, the polyolefin-derived structural unit of the polyolefin-silicone copolymer, and the thermoplastic resin It is speculated that it interacts with the polyolefin which is Thus, by stretching the parison or preform, the structural unit derived from the silicone of the polyolefin-silicone copolymer can be unevenly distributed on the innermost surface of the inner layer of the container, that is, the surface that forms the filling space.

(Silicone resin)
As the silicone resin, for example, a polyolefin-silicone copolymer is preferably used. As the polyolefin-silicone copolymer, for example, one containing a structural unit represented by the following general formula (1) can be used.

（Ａは、ポリオレフィンに由来する構造単位であり、
Ｂは下記一般式（Ｂ１）で示す構造単位を含む。）

(A is a structural unit derived from polyolefin,
B contains a structural unit represented by the following general formula (B1). )

（上記式（Ｂ１）において、ｎは整数である。）

(In the above formula (B1), n is an integer.)

In the said General formula (1), A is a structural unit originating in polyolefin.
Although A is not limited, for example, it can be a structural unit derived from polyolefin. Here, the structural unit derived from polyolefin indicates a structure in which hydrogen is removed from a bond that is bonded to another structural unit in the polyolefin.
Specific examples of the polyolefin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers of (e.g., random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. For example, polyethylene or polypropylene is preferably used as the polyolefin. Thereby, the compatibility of the silicone resin and the first thermoplastic resin can be improved.

In the general formula (1), B includes the structural unit represented by the general formula (B1).
In the film for forming a packaging container according to the present embodiment, the sliding angle falls within a specific numerical range when the structural unit of (B1) is unevenly distributed on the surface of the film for forming a packaging container.

  As an example of the silicone resin which concerns on this embodiment, the thing of the structure represented by following formula (P1) to (P4) is mentioned.

（上記式（Ｐ１）において、ｍは１以上の整数である。）

(In the above formula (P1), m is an integer of 1 or more.)

（上記式（Ｐ２）において、ｍ、ｌは１以上の整数である。）

（上記式（Ｐ３）において、ｍは１以上の整数である。）

(In the above formula (P2), m and l are integers of 1 or more.)

(In the above formula (P3), m is an integer of 1 or more.)

（上記式（Ｐ４）において、ｍ、ｌ、ｏ、ｐは１以上の整数である。）

(In the above formula (P4), m, l, o and p are integers of 1 or more.)

  Examples of commercially available silicone resins having a structure of the above general formula (1) and in which A is polyethylene or polypropylene include BY27-201, BY27-201C, and BY27-202H manufactured by Toray Dow Corning. .

(Other ingredients)
The thermoplastic resin composition may contain, in addition to the thermoplastic resin and the silicone resin, other additives such as a filler, an antioxidant, a surfactant, and a mold release agent.
The representative components will be described below.

(Filler)
Specifically, an inorganic filler or an organic filler can be used as the filler.
Specific examples of the inorganic filler include fused and crushed silica, fused spherical silica, crystalline silica, secondary aggregated silica, and silica such as fine powder silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide And metal compounds such as aluminum hydroxide, magnesium hydroxide and titanium white; talc; clay; mica; glass fibers and the like. As an inorganic filler, it can be used combining 1 type, or 2 or more types among the said specific examples.
Specific examples of the organic filler include fine particles of a fluorine-based resin, fine particles of organosilicone, and fine particles of polyethylene. As an organic filler, it can be used combining 1 type, or 2 or more types among the said specific examples.

(Antioxidant)
As the antioxidant, one or more selected from phenolic antioxidants, phosphorus antioxidants and thioether antioxidants can be used.
Specific examples of phenolic antioxidants include pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), 3,9-bis {2- (3) -(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro (5,5) undecane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 1, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-methylphenol, , 6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3 5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis ((3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 4,4′-thiobis (6-tert-) Butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-) t-Butyl-6-butylphenol), 2, -2'-methylenebis (4-ethyl-6-t-butylphenol), bis (3,3-bis (4-hydride) Xyl-3-t-butylphenyl) butyric acid) glycol ester, 4,4'-butylidene bis (6-t-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-t-) Butylphenol), 2,2'-ethylidenebis (4-s-butyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis (2-tert-Butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl) terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxyl -4-tert-Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5- Tris ((3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl) isocyanurate, tetrakis (methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane , 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl)- 2,4-8,10-tetraoxaspiro [5,5] undecane-bis (β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), triethylene glycol bis (β- (3 -T-Butyl-4-hydroxy-5-methylphenyl) propionate), 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2, 2, '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (6- (1-methylcyclohexyl) -4 -Methylphenol), 4,4'-Butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis (2- (3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy) 1 1,1-Dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-bis ( 3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-thiobis (6-tert-butyl-2-methylphenol), 2,5-di-tert-butylhydroquinone 2,5-di-t-amyl hydroquinone, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl-6- 1-methylcyclohexyl, styreneated phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol and the like.
Specific examples of phosphorus-based antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl phosphite ), Tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis -(2,6-dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (mixed mono and di nonyl phenyl phosphite) , Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4- 4 And methoxycarbonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite and the like.
Specific examples of thioether-based antioxidants include dilauryl-3,3'-thiodipropionate and bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butyl And phenyl) sulfide, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate and the like.
As an antioxidant, it can be used combining 1 type, or 2 or more types among the said specific examples.

(Surfactant)
The surfactant is not limited, and a known surfactant can be selected according to the type of thermoplastic resin.
Specific examples of the surfactant include polyhydric alcohol fatty acid esters such as polyglycerin fatty acid ester and diglycerin fatty acid ester; and polyoxyethylene compounds.

(Release agent)
The release agent is not limited, and a known release agent can be selected according to the type of thermoplastic resin.
Specific examples of the mold release agent include natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax and oxidized polyethylene wax; higher fatty acids such as zinc stearate; and metal salts thereof; paraffin and the like. As a mold release agent, it can be used combining 1 type, or 2 or more types among the said specific examples.

The lower limit value of the content of the silicone resin in the thermoplastic resin composition is, for example, preferably 0.01 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of the total solid components of the thermoplastic resin composition. The content is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more. Thus, the silicone resin can be uniformly present on the surface of the container inner layer forming the filling space by blow molding.
In addition, the upper limit value of the content of the silicone resin in the thermoplastic resin composition may be, for example, 20 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass of the total solid components of the thermoplastic resin composition. It is also good. As a result, the silicone resin tends to be unevenly distributed on the surface forming the filling space of the inner layer of the container. Moreover, when the layer structure of a blow molded container is a multilayer, it is preferable also from a viewpoint to which the adhesiveness of a container inner layer and another layer improves.

In the innermost layer of the container inner layer according to the present embodiment, that is, the surface forming the filling space, the upper limit of the sliding angle when dropping 10 μl of water to the container inner layer is 50 ° or less, for example 45 ° or less Is preferably 40 ° or less. Thereby, silicone resin can be unevenly distributed on the surface which forms the filling space of a container inner layer. When the silicone resin is a polyolefin-silicone copolymer, structural units derived from the hydrosilane of the polyolefin-silicone copolymer can be unevenly distributed on the surface of the inner layer of the container to form the filling space. Therefore, it is possible to improve the ability of the blow molded container of the present embodiment to drain the viscous liquid.
In the innermost layer of the container according to the present embodiment, the lower limit of the sliding angle when 10 μl of water is dropped in the inner layer of the container may be, for example, 10 ° or more, or 15 ° or more, 20 ° or more It may be Thereby, the blow molded container can control the discharge property of the viscous liquid and can suppress the disadvantage that the viscous liquid is discharged unexpectedly and in a large amount.
In the present embodiment, the sliding angle indicates a sliding angle evaluated by the dynamic sliding method. In the present embodiment, the dynamic sliding method can be performed by the following method.
First, the surface that forms the filling space of the blow molded container is exposed. As a method of taking out the surface which forms the filling space, for example, a blow molded container is cut open and the surface which forms the filling space of the container inner layer is taken out in a plane. Next, the pedestal is allowed to rest on a plane, and then the surface forming the filling space of the inner layer of the container is allowed to rest on the pedestal. The angle between the plane at this time and the pedestal is 0 °. Next, 10 μl of water is dropped onto the surface of the inner layer of the container forming the filling space. Next, by tilting the pedestal, the angle between the plane and the pedestal is increased. Here, the angle between the flat surface and the pedestal when the water drop starts to slide down the surface forming the filling space of the inner layer of the container is shown as the sliding angle. In addition, the measurement temperature of a sliding angle shall be 25 degreeC.
Here, for observation of water droplets, measurement can be performed using a commercially available contact angle meter such as Drop Master DA-501 manufactured by Kyowa Interface Science Co., Ltd.

In the present embodiment, for example, it is possible to control the value of the sliding angle by appropriately selecting the material and the like in the thermoplastic resin composition constituting the container inner layer. Among the above-mentioned factors, it is important to select the content of silicone resin in the thermoplastic resin composition and the type of silicone resin as factors to control the value of sliding angle.
The detailed mechanism is not clear, but by appropriately setting the above factors, a packaging container formed by blow molding, that is, when a parison or a preform is blow-stretched in the case of making a blow molded container, It is presumed that a silicone resin having lower molecular mobility than a thermoplastic resin can be unevenly distributed on the surface forming the filling space of the inner layer of the container. Thereby, the silicone resin is unevenly distributed on the surface forming the filling space of the inner layer of the container.

(Other layers)
When the layer structure of the blow molded container according to this embodiment is a multilayer structure, layers other than the inner layer of the container may be provided. Specific examples of the layer other than the inner layer of the container include a gas barrier layer, an oxygen absorbing layer, a deodorizing layer, an adhesive layer, an impact resistant layer and the like.
The representative layers will be described below.

(Gas barrier layer)
The layer structure of the blow molded container according to the present embodiment may include, for example, a gas barrier layer. Thereby, the storage property of the viscous liquid can be improved.
The material for forming the gas barrier layer is not limited, and conventionally known materials can be used. Specifically, the first resin composition containing an ethylene-vinyl alcohol copolymer and the like can be mentioned as the formation of the gas barrier layer. By this, it is possible to improve the oxygen barrier property and to suppress the deterioration of the viscous liquid by oxidation.

(Oxygen absorption layer)
The layer structure of the blow molded container according to the present embodiment may include, for example, an oxygen absorbing layer. Thereby, the storage property of the viscous liquid can be improved.
It does not limit as a material which forms an oxygen absorption layer, A conventionally well-known material can be used. Specifically as a material which forms an oxygen absorption layer, the 2nd resin composition etc. which contain resin containing a hydroxyl group, a polyene type polymer, and a transition metal catalyst etc. are mentioned.
Here, as a resin provided with a hydroxyl group, an ethylene-vinyl alcohol copolymer etc. are mentioned specifically ,.
Specific examples of polyene polymers include polybutadiene, polyisoprene, natural rubber, nitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene-diene rubber and the like.
Specific examples of the transition metal catalyst include inorganic salts such as iron, cobalt, nickel, copper, silver, tin, titanium, zirconium, vanadium, chromium, manganese, and organic salts.
Here, as the inorganic salt, specifically, halides such as chloride; oxy salts of sulfur such as sulfate; oxyacid salts of nitrogen such as nitrate; phosphorus oxy salts such as phosphate; silicate etc It can be mentioned.
Moreover, as an organic salt, carboxylate, a sulfonate, a phosphonate etc. are specifically mentioned.

(Deodorant layer)
The layer structure of the blow molded container according to the present embodiment may include, for example, a deodorizing layer. As a result, it is possible to capture the odor caused by the oxidation of the viscous liquid, the storage environment of the blow molded container, and the oxygen absorbing layer, and to suppress the unpleasant smell from being imparted to the viscous liquid.
It does not limit as a material which forms a deodorizing layer, A conventionally well-known material can be used. Specifically as a material which forms a deodorizing layer, the 3rd resin composition containing the thermoplastic resin used for the container inner layer mentioned above and a deodorizing component is mentioned.
Here, specific examples of the deodorizing component include activated carbon, silica gel, zeolite, activated clay, activated aluminum oxide, magnesium silicate, aluminum silicate, hydrotalcite and the like.

(Adhesive layer)
The layer structure of the blow molded container according to the present embodiment may include, for example, an adhesive layer. This can enhance the adhesion between the layers.
The material for forming the adhesive layer is not limited, and conventionally known materials can be used. Specifically as a material which forms an adhesive layer, the 4th resin composition containing graft modified olefin resin graftedly modified with maleic anhydride is mentioned. Here, as an olefin resin, polyethylene, a polypropylene, an ethylene-alpha olefin copolymer etc. are mentioned specifically ,.

(Shock resistant layer)
The layer structure of the blow molded container according to the present embodiment may include, for example, an impact resistant layer. Thus, even when the blow molded container is subjected to rapid deformation or a large load, breakage of the blow molded container can be suppressed.
It does not limit as a material which forms an impact-resistant layer, A conventionally well-known material can be used. Specifically as a material which forms an impact-resistant layer, the 5th resin composition containing polyolefin resin among thermoplastics used for a container inner layer mentioned above is mentioned.

(Packaging body)
Next, a package according to the present embodiment will be described.
The package according to the present embodiment includes the above-described blow molded container 10 and a lid.
In the package according to the present embodiment, the inside of the filling space 20 can be filled with, for example, a viscous liquid.

(Lid material)
The lid can be made of, for example, a resin material.
Here, as the lid member, for example, a threaded portion that can be fastened to the screw portion 12 is formed.
For example, the lid may include a hinge and a top surface that can be opened and closed through the hinge. Thereby, the dischargeability of the viscous liquid can be controlled instead of the above-mentioned inner lid. In addition, the package which concerns on this embodiment may be equipped with an inner cover part and a cover material, for example.

  In addition, as a modification of this embodiment, the diameter of a lid material is large, for example, and the aspect which can leave a blow molding container still so that a lid material may be touched on a plane is mentioned. That is, for example, as shown in FIG. 3, the blow molded container of the modified example is capable of leaving the blow molded container in the opposite direction to that shown in FIG. Even in such a mode, the blow molded container according to the present embodiment is excellent in liquid breakability, and does not have disadvantages such as a decrease in the self-supporting stability of the packaging container, a decrease in the appearance, and a decrease in the dischargeability of the viscous liquid. It is suitable for filling a thick liquid.

(Viscous liquid)
The viscous liquid according to the present embodiment is a viscous liquid. Hereinafter, the viscous liquid according to the present embodiment will be described.

The lower limit value of the viscosity of the viscous liquid can be suitably used, for example, in the case of 0.01 Pa · s or more under the conditions of a temperature of 25 ° C. and a shear rate of 1 [1 / sec]. Even in the case of 10 Pa · s or more, it can be suitably used. Even in the case of 50 Pa · s or more, it can be suitably used. Even in the case of 100 Pa · s or more, it can be suitably used. . The blow molded container according to the present embodiment can improve the drainage property even for a viscous liquid having a lower limit value or more achieved. Thereby, it can use suitably also for the filling of the viscous liquid of the high viscosity which can not be filled with the conventional blow molding container.
Further, the upper limit value of the viscosity of the viscous liquid may be, for example, 5000 Pa · s or less, 2000 Pa · s or less, or 1000 Pa · s under conditions of a temperature of 25 ° C. and a shear rate of 1 [1 / sec]. It may be as follows, may be 500 Pa · s or less, and may be 300 Pa · s or less. Basically, the lower the viscosity of the viscous liquid, the better the blow molded container can exhibit a better drainage.
In the present embodiment, the viscosity of the viscous liquid can be measured, for example, using a rheometer (for example, ARES-2KFRTN1-FCO-HR manufactured by TA Instruments Co., Ltd.).

The viscous liquid may contain, for example, a lipid or a protein, and may contain a lipid and a protein. The inclusion of the lipid and protein improves the viscosity of the viscous liquid and further improves the affinity to the filling space of the conventional blow molded container. As a result, the container inner layer of the conventional blow molded container has a disadvantage that the viscous liquid is not easily drained. On the other hand, the filling space of the blow-molded container according to the present embodiment is advantageous from the viewpoint of being able to exhibit excellent liquid drainage even for viscous liquids containing lipids and proteins.
Here, when the viscous liquid contains a lipid or a protein, the viscous liquid further contains, for example, a solvent. Thereby, the viscous liquid is constituted by dispersing the lipid or protein in the solvent. Specifically, water, oil and the like can be mentioned as the solvent.

  The viscous liquid may be, for example, an O / W emulsion or a W / O emulsion, and is preferably an O / W emulsion. The blow molded container according to the present embodiment is preferable from the viewpoint of being able to express a suitable liquid breakage property even when the viscous liquid is the above-mentioned emulsion. In addition, the filling space of the blow-molded container according to the present embodiment can exhibit suitable drainage performance for both oil and water components. Thereby, it can use suitably from a viewpoint which the inconvenience that the component of an emulsion isolate | separates does not occur easily.

Even when the viscous liquid contains a lipid (oil and fat), the blow-molded container according to the present embodiment can exhibit excellent flowability.
The lower limit value of the content of the lipid in the viscous liquid may be, for example, 10 parts by mass or more, 30 parts by mass or more, or 50 parts by mass or more, based on 100 parts by mass of the entire viscous liquid. It may be 70 parts by mass or more, or 75 parts by mass or more. The blow molded container according to the present embodiment can exhibit suitable liquid drainage even when the content of the lipid in the viscous liquid is as large as the above lower limit value or more.
The upper limit value of the content of the lipid in the viscous liquid may be, for example, 99 parts by mass or less, or 95 parts by mass or less based on 100 parts by mass of the entire viscous liquid.

As a viscous liquid, specifically, milk, syrup, fruit juice, concentrated coffee, soup stock, seasoning liquid such as a pot paste; soy sauce, sauce, ketchup, mayonnaise, mayonnaise-like seasoning, dressing, starch syrup, honey etc. Oils such as salad oil, olive oil, lard and beef tallow; Toiletries such as detergent and bleach; Cosmetics such as skin cosmetics and hair cosmetics; Machine oils such as engine oils and lubricating oils. As described above, even when the viscous liquid contains a protein or a lipid, the blow-molded container according to the present embodiment can exhibit a suitable drainage property.
When a mayonnaise or mayonnaise-like seasoning is used as the viscous liquid among the above specific examples, for example, the blow-molded container according to the present embodiment exhibits suitable liquid breakage and according to the present embodiment when mayonnaise is used. The blow molded container can further exhibit a suitable drainage property.
In the present embodiment, mayonnaise refers to a Japanese agricultural and forestry standard which satisfies the definitions and standards defined in Articles 2 and 3 of the Japanese agricultural and forest standard of dressing. Moreover, compared with the said mayonnaise, mayonnaise-like seasonings are less than 65% of fat-and-oil content, and show what does not satisfy | fill the standard of mayonnaise.

(Production method of blow molded container)
Next, a method of manufacturing a blow molded container will be described.
The blow molded container can be produced, for example, by blow molding a parison or a preform.

  The shape of the parison and the preform will be described. When the layer structure of the blow molded container is a single layer, for example, the parison or preform may be formed of the above-described thermoplastic resin composition. In addition, when the layer structure of the blow-molded container is a multilayer, for example, a resin composition that forms a plurality of layers such that the above-described thermoplastic resin composition becomes the innermost layer of the multilayer, that is, the layer forming the filling space. The parisons or preforms may be formed such that the objects are arranged concentrically and the layer thickness of each is substantially constant over the entire circumference.

  The method of blow molding is not limited, and can be performed using a conventionally known method. Specific examples of the blow molding method include direct blow molding, injection blow molding, and injection blow stretch molding.

  As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to the said embodiment, The structure can also be changed in the range which does not change the summary of this invention.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the description of these examples.
First, the raw material component used in order to form the container inner layer of each Example and each comparative example is demonstrated.

(Thermoplastic resin)
・ Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., G202)
・ Polypropylene (manufactured by Sumitomo Chemical Co., Ltd., W101)
・ Norbornene-ethylene copolymer (manufactured by Polyplastics Co., Ltd., 8007F-04)

(Silicone resin)
· Polyolefin-silicone copolymer (manufactured by Toray Dow Corning, BY27-201C)

  Next, blow molded containers of each example and comparative example will be described.

Example 1
As a blow molded container of Example 1, a blow molded container provided with an impact resistant layer and a container inner layer in this order from the outside was produced.
First, raw material components shown in Table 1 below were prepared as a thermoplastic resin composition for forming an inner layer of a container. Further, polyethylene (Ube Maruzen, F222NH) for forming an impact resistant layer was prepared.
Then, using two extruders, polyethylene for forming the impact resistant layer and the thermoplastic resin composition for forming the container inner layer are arranged concentrically in order from the outermost layer from the multilayer die head Then, a multilayer molten parison was extruded, and a blow molded container having the shape shown in FIG. 1 was obtained by a known direct blow molding method. This was used as the blow molded container of Example 1. In the blow molded container of Example 1, the layer structure was reversibly deformed without being broken and the volume of the filling space could be changed.

(Examples 2 to 3, Comparative Example 1)
A blow molded container of Examples 2 to 3 and Comparative Example 1 was produced in the same manner as in Example 1 except that the raw material components of the thermoplastic resin composition forming the inner layer of the container were changed to those of Table 1 below. did.

(Slip angle)
The sliding angle of the blow molded container of each example and comparative example 1 was evaluated. The evaluation method is described in detail below.
First, the blow molded container was cut open, and then the test piece constituted by the impact resistant layer and the container inner layer forming the filling space was taken out. The test piece was a flat film. Next, the pedestal was allowed to stand on a plane, and then the surface forming the filling space of the inner layer of the container was allowed to stand on the pedestal. The angle between the plane at this time and the pedestal is 0 °. Next, 10 μl of water was dropped onto the surface of the inner layer of the container forming the filling space. Next, by tilting the pedestal, the angle between the plane and the pedestal was increased. Here, the angle between the flat surface and the pedestal was evaluated as the sliding angle when the water drop started to slide down the surface forming the filling space of the container inner layer. The measurement temperature of the sliding angle was 25 ° C. The evaluation results are shown in Table 1 below.
A contact angle meter (Drop Master DA-501, manufactured by Kyowa Interface Science Co., Ltd.) was used for observation of water droplets.

(Drainage)
The drainage property of the blow molded container of each example and comparative example 1 was evaluated. The evaluation method is described in detail below.
First, the blow molded container was cut open, and then a test piece constituted by the impact resistant layer and the inner container layer forming the filling space was cut out. The test piece was a flat film, and the size of the test piece was 100 mm long × 50 mm wide. Next, 2 g of a viscous liquid was placed on one end of a test piece placed on a flat surface. The test piece was then stood upright with the viscous liquid end on top. When the test piece is erected vertically, gravity causes the viscous liquid to fall along the test piece and eventually travel a length of 100 mm to reach the other end. The test piece was stood vertically, and the distance of movement within a predetermined time was taken as the evaluation result of the drainage property. In addition, viscous liquid 1-4 mentioned later used evaluation of the liquid discharge property. In addition, about the viscous liquid 1, predetermined time was 3 minutes. In addition, for the viscous liquids 2 to 3 which are less likely to drain than the viscous liquid 1, the predetermined time is set to 60 minutes. Moreover, about the viscous liquid 4 with a low viscosity, predetermined time was 1 minute. The evaluation results are shown in Table 1 below. The unit of the evaluation result is mm. As the numerical value of the evaluation result is larger, the drainage property is better, and the viscous liquid does not adhere to or remain in the filling space of the blow molding container.

In the evaluation of the drainage property, the following viscous liquids were used.
Viscous liquid 1: By dispersing 0.8 g of protein and 22.5 g of lipid in water, 30 g of viscous liquid which is an O / W emulsion was prepared and used as viscous liquid 1. The viscous liquid contained 75 parts by mass of lipid per 100 parts by mass of the viscous liquid.
Viscous liquid 2: By dispersing 0.8 g of protein and 7.5 g of lipid in water, 30 g of viscous liquid as an O / W emulsion was prepared and used as viscous liquid 2. The viscous liquid had a lipid content of 25 parts by mass with respect to 100 parts by mass of the viscous liquid.
Viscous liquid 3: 30 g of viscous liquid was prepared by dispersing 0.5 g of protein in water, and used as viscous liquid 3. The viscous liquid contained no lipids.
Viscous liquid 4: 30 g of liquid lipid was used as the viscous liquid 4.

In addition, the viscosity of the viscous liquid was measured using a rheometer (manufactured by TA Instruments, ARES-2KFRTN1-FCO-HR). The measurement conditions were a temperature of 25 ° C. and a shear rate of 1 [1 / sec].
The viscosity of the viscous liquid 1 was 200 Pa · s. The viscosity of the viscous liquid 2 was 50 Pa · s. The viscosity of the viscous liquid 3 was 3 Pa · s. The viscosity of the viscous liquid 4 was 65 mPa · s.

  As shown in Table 1 above, it was confirmed that the blow-molded container of the example is superior to the blow-molded container of the comparative example in terms of the liquid drainability of the inner layer of the container.

DESCRIPTION OF SYMBOLS 10 blow molding container 12 screw part 14 main-body part 20 filling space 22 discharge port 24 bottom part 40 central axis

Claims (8)

A blow molded container comprising a filling space for filling a viscous liquid, comprising:
The filling space is formed by a container inner layer made of a thermoplastic resin composition,
The thermoplastic resin composition comprises a thermoplastic resin and a silicone resin,
The blow molded container having a sliding angle of 10 ° or more and 50 ° or less when 10 μl of water is dropped onto the surface of the inner layer of the container formed with the temperature at 25 ° C. A blow molded container according to claim 1, wherein
Content of the said silicone resin in the said thermoplastic resin composition is a blow molded container which is 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of all the solid components of the said thermoplastic resin composition. The blow molded container according to claim 1 or 2, wherein
The blow molded container, wherein the silicone resin is a polyolefin-silicone copolymer. A blow molded container according to any one of the preceding claims, wherein
The blow molded container, wherein the thermoplastic resin is one or more selected from the group consisting of a polyolefin resin, a polyester resin, and a fluorine-based resin. The blow molded container according to any one of claims 1 to 4, wherein
The blow molded container, wherein the viscous liquid comprises a lipid or a protein. The blow molded container according to any one of claims 1 to 5, wherein
The viscosity of the said viscous liquid is a blow molded container which is 0.01 Pa.s or more and 5000 Pa.s or less on the conditions of temperature 25 degreeC, and a shear rate of 1 [1 / sec]. A blow molded container according to any one of the preceding claims, wherein
The blow molded container is in the form of a tube. A blow molded container according to any one of claims 1 to 7;
And a cover material.

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