JP6209957B2 - Liquid-containing masterbatch - Google Patents

Description

  The present invention relates to a liquid-containing masterbatch, and more particularly, to a masterbatch used for molding a plastic molded body having a liquid layer on the surface.

  Plastics are widely used for various applications because they are easy to mold and can be easily molded into various forms. In particular, bottle-shaped olefin-based resin containers whose inner walls are formed of olefin-based resins such as low-density polyethylene are easy to squeeze out the contents, so that the contents of viscous slurry or paste such as ketchup It is suitably used as a container for containing things.

  For bottles containing viscous contents, the bottles may be stored in an inverted state so that the contents can be discharged quickly or used up to the end without remaining in the bottle. There are many. 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.

As a bottle satisfying such requirements, for example, 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.
In this multi-layered bottle, the innermost layer has excellent wettability to oily contents. As a result, when the bottle is inverted or tilted, the oily contents such as mayonnaise spread along the innermost surface. However, it can be discharged neatly without dropping and remaining attached to the inner wall surface of the bottle (the innermost layer surface).

  In addition, regarding a bottle for viscous non-oil content in which plant fibers such as ketchup are dispersed in water, Patent Document 2 or Patent Document 3 describes a saturated or unsaturated aliphatic amide as a lubricant in the innermost layer. There has been proposed a polyolefin resin bottle in which is blended.

  Patent Documents 1 to 3 mentioned 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. However, since 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.

From such a point of view, the present inventors have proposed a plastic container in which a liquid layer different from the content is formed on the inner surface in contact with the content (for example, Japanese Patent Application No. 2012-157744). . That is, in such a container, a liquid layer made of a liquid immiscible with the contents is formed on the inner surface, thereby successfully improving the slipperiness with respect to the contents as compared with a conventionally known one. By tilting or tilting the container, the contents can be quickly discharged out of the container without adhering to or remaining on the inner wall of the container.
The method for modifying the surface characteristics such as slipperiness by forming a liquid layer on the surface in this way is applicable not only to the form of the container but also to a molded body having a form such as a film. By appropriately selecting, the surface properties can be significantly modified.

  However, as described above, in the means of forming a liquid layer on the surface of a molded body such as a container to improve the surface characteristics, after the container is molded, a liquid other than the contents is immersed and sprayed on the inner surface of the container. Therefore, it is necessary to adopt a special liquid layer forming means that is applied by the above method, and therefore further improvement is necessary from the viewpoint of improving productivity.

For this reason, the inventors of the present invention have said that the inner surface of the container has a fluid content that is molded from a resin composition containing a liquid that is immiscible with the container contents (hereinafter referred to as a lubricating liquid) and a molding resin. The container for goods was proposed previously (Japanese Patent Application No. 2013-91244).
Such a container is manufactured by molding using the resin composition as a resin material for forming an inner surface. That is, after the molding, the lubricating liquid contained in the resin composition segregates on the inner surface of the container without performing any special treatment, whereby a layer of the lubricating liquid is automatically formed on the inner surface of the container. There is an advantage that the container can be manufactured with extremely high productivity.

  By the way, when a container is molded using the above-described lubricating liquid-containing resin composition, naturally, a master batch in the form of a pellet containing the lubricating liquid and a molding resin is used. That is, at the time of molding, if a resin composition is prepared by mixing a lubricating liquid and a molding resin each time, the efficiency is low and a tank or the like that contains a large amount of the lubricating liquid becomes necessary. Therefore, a pellet-shaped masterbatch containing the lubricating liquid at a high concentration is prepared in advance, and handling such as storage and transport is handled in the form of this masterbatch, and the masterbatch is molded with a molding resin during molding. The resin composition for forming the inner surface of the container is prepared by dilution, and molding into the container is performed.

  Therefore, the problem is the bleedability of the liquid from the masterbatch. That is, there is no problem when the concentration of the liquid contained in the master batch is thin (for example, 5% by mass or less), or when the viscosity of the liquid is very high (for example, the viscosity is 1 million centistokes or more) When the liquid concentration of the master batch is high or the liquid viscosity is low, the liquid bleeds from the master batch, making the pellets sticky and difficult to handle, or by diluting this by liquid bleeding. The present inventors have found that there is a problem that the liquid concentration becomes smaller than the target value when a resin composition for use is prepared. In particular, this tendency is remarkable when the molding resin mixed with the liquid is an olefin resin such as polyethylene or polypropylene used for molding a squeeze container or the like.

For example, with respect to a masterbatch containing a liquid component, 5% polyglycerin fatty acid ester (liquid component) is added to polyethylene or polypropylene in the example of Patent Document 4, and a masterbatch pellet is produced by an extrusion molding machine. It describes that a film was formed by extruding a master batch pellet with a polyethylene or polypropylene resin pellet. However, in Patent Document 4, since the concentration of polyglycerin, which is a liquid component, is as low as 5%, the molding resin composition formed from this master batch has a considerably low concentration (Example of Patent Document 4). In any case, it is limited to 1.5% or less), and a molding resin composition containing a liquid component at a high concentration cannot be prepared.
In the example of Patent Document 5 (see paragraph [0022]), a master pellet comprising 600 g of polyamide resin, 400 g of polydimethylsiloxane (liquid component) having a viscosity of 1 million centistokes and 60 g of carboxyl group-containing polyorganosiloxane. Is disclosed. In this patent document 5, although polydimethylsiloxane which is a liquid component is contained at a high concentration, the viscosity of this liquid component is extremely high and cannot be applied to a low viscosity liquid such as glycerin ester.

JP 2007-284066 A JP 2008-222291 A JP 2009-214914 A Japanese Patent Publication No.43-8605 JP-A-6-200151

Therefore, an object of the present invention is a liquid-containing masterbatch, in which the viscosity of the contained liquid is low, and even when the liquid is contained at a high concentration, the bleeding of the liquid is effective over a long period of time. It is to provide a liquid-containing masterbatch that is suppressed and a method of using the same.
Another object of the present invention is to provide a liquid-containing masterbatch suitably used for molding a plastic molded body having a liquid layer on its surface and a method for using the same.

According to the present invention, the liquid (B) having a viscosity (23 ° C.) of 1000 mPa · s or less is dispersed in the matrix resin (A) having a glass transition point of 35 ° C. or higher, and the matrix resin (A) Is a cyclic olefin-based resin, the liquid (B) is any one of glycerin fatty acid ester, liquid paraffin or edible oil and fat, and the liquid (B) is 10 to 70 per 100 parts by mass of the matrix resin (A). There is provided a masterbatch for use in forming containers characterized by being present in parts by weight .
In the master batch of the present invention,
(1) The liquid (B) has a viscosity of 100 mPa · s or less,
(2) The liquid (B) is present at 15 to 65 parts by mass per 100 parts by mass of the matrix resin (A),
Is preferred.

According to the present invention , the liquid (B) having a viscosity (23 ° C.) of 1000 mPa · s or less is dispersed in the matrix resin (A) having a glass transition point of 35 ° C. or higher. There is provided a method for using a masterbatch comprising the steps of mixing the masterbatch with a molding resin having a glass transition point of less than 35 ° C. and molding the mixture.
In such a method,
(3) The matrix resin (A) in the masterbatch is a cyclic olefin resin, and the molding resin is an acyclic olefin resin.
Is desirable.

The masterbatch of the present invention can effectively suppress bleeding over a long period of time while containing a low viscosity liquid (B) having a viscosity of 1000 mPa · s or less as a liquid component. As is apparent, the liquid (B) can be contained up to 67 parts by mass (about 40% by mass per masterbatch) per 100 parts by mass of the matrix resin (A), and about 3 months. The bleeding of the liquid (B) can be effectively prevented over a long period of time.
That is, in the present invention, since a resin having a glass transition point (Tg) of 35 ° C. or higher is used as the matrix resin (A), the low-viscosity liquid (B) is near room temperature in a normal storage environment. It is in a state of being confined in a glassy resin. As a result, even when a large amount of the low-viscosity liquid (B) is dispersed, the bleeding can be effectively avoided over a long period of time. For example, in polyethylene and polypropylene whose glass transition point (Tg) is considerably lower than 35 ° C., the restraint between molecules is loose and the molecules are easy to move around room temperature. Therefore, this was used as the matrix resin (A). In some cases, the dispersed liquid (B) easily slips between the molecules, and as a result, bleeding occurs.

The greatest advantage of the present invention is that a cyclic olefin-based resin can be used as the matrix resin (A).
That is, the cyclic olefin resin is highly compatible with acyclic olefin resins such as polyethylene and polypropylene, and is finely dispersed in these acyclic olefin resins. However, flexible containers such as squeeze bottles suitable for squeezing viscous contents are mainly formed using the above-mentioned non-cyclic olefin resin, and in such flexible containers, By forming a predetermined liquid layer on the inner surface, it is possible to improve the slipperiness with respect to the viscous contents and to remarkably improve the discharge property.
As understood from the above description, according to the master batch of the present invention in which a cyclic olefin resin is used as the matrix resin (A) and a predetermined liquid is dispersed, the master batch is converted into an acyclic olefin resin ( For example, by mixing with polyethylene), a molding resin composition containing a sufficient amount of liquid to form a liquid layer can be prepared. By molding using such a molding resin composition, the inner surface Thus, a container having a liquid layer can be obtained, and the effect of improving the surface characteristics by the liquid can be maximized.

Schematic which shows the representative example of the container shape | molded using the masterbatch of this invention.

<Master batch>
The masterbatch of the present invention has a structure in which the liquid (B) is dispersed in the matrix resin (A).

Matrix resin (A);
In the master batch of the present invention, a resin having a glass transition point (Tg) of 35 ° C. or higher is used as the matrix resin (A). That is, when the glass transition point is low, the binding force between molecules near room temperature is weak. Therefore, when the master batch is stored near room temperature, the liquid (B) dispersed therein during storage is easily bleeding. As a result, stickiness is caused and handling thereof becomes difficult, the amount of the liquid (B) dispersed therein is greatly limited, and the viscosity is also limited to a large one.
Moreover, since the glass transition point of the masterbatch formed using the matrix resin (A) having the glass transition point as described above is dispersed in the liquid (B) described later, the glass of the matrix resin (A) Lower than the transition point. This is because the binding force between molecules becomes weak due to the presence of the liquid (B). Accordingly, in order to prevent bleeding of the liquid (B), the glass transition point of the matrix resin (A) is higher, for example, preferably 50 ° C. or higher, whereby the liquid (B) is dispersed. The glass transition point in the state of the masterbatch can be increased to further increase the binding force between the molecules of the matrix resin, and the bleeding prevention effect of the liquid (B) can be further enhanced.

As such a matrix resin (A) , a resin having a glass transition point in the above range is selected from cyclic olefin resins .
That is, the cyclic olefin-based resin can be molded into various forms by itself, and as described above, it is used for molding a flexible container such as a squeeze bottle that contains viscous contents. Master batches that are excellent in compatibility with non-cyclic olefin resins (polyethylene, polypropylene, etc.) and are used as matrix resins are mixed (diluted) with such non-cyclic olefin resins. This is because it can be used as a resin composition for container molding.

Such a cyclic olefin resin is known, and for example, an amorphous or low crystalline copolymer (COC) of an acyclic olefin and a cyclic olefin is representative.
As the above-mentioned acyclic olefin, ethylene is preferable, but in addition, carbon number such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl 1-pentene, 1-decene, etc. 3 to 20 α-olefins are each used alone or in combination with ethylene.

  As the cyclic olefin, basically, an aliphatic hydrocarbon compound having an ethylenically unsaturated bond and a bicyclo ring (for example, cyclohexene) is representative, but a bridging group (for example, a methylene group or the like) is formed inside the cyclohexene ring. A bicyclo ring having an ethylene group) or an aliphatic hydrocarbon having a polycyclic structure in which an aliphatic ring is further bonded to the bicyclo ring is also suitable.

（１）
式中、Ｚは、メチレン基またはエチレン基である。 Such an aliphatic hydrocarbon compound having a polycyclic structure is represented by the following formula (1).

(1)
In the formula, Z is a methylene group or an ethylene group.

ビシクロ［２．２.１］ヘプト−２−エン

トリシクロ［４.４．０.１^２．５］−３−ウンデセン

テトラシクロ［４．４.０．１^２．５.１^７．１０］−３
−ドデセン

ペンタシクロ［８．４.０．１^２.５．１.^９．１２.
０^８．１３］−３−ヘキサデセン

ペンタシクロ［６．６.１．１^３.６．０.^２．７.
０^９．１４］−４−ヘキサデセン Specific examples of the aliphatic hydrocarbon compound having the polycyclic structure include the following.

Bicyclo [2.2.1] hept-2-ene

Tricyclo [4.4.0.1 ^2.5 ] -3-undecene

Tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3
-Dodecene

Pentacyclo [8.4.0.1 ^2.5 . 1. ^9.12 .
0 ^8.13 ] -3-hexadecene

Pentacyclo [6.6.1.1 ^3.6 . 0. ^2.7.
0 ^9.14 ] -4-hexadecene

Of course, the cyclic olefin is not limited to the above-mentioned ones. For example, the aliphatic olefin in the formula (1) may have one or more substituents such as an alkyl group on the aliphatic ring. No. 3,893,650 may be used.
That is, in the present invention, the cyclic olefin resin is a copolymer of the above-mentioned cyclic olefin and acyclic olefin, and the glass transition point is within the above-described range by adjusting the copolymerization ratio and the degree of polymerization. It is suitably used as (A).

Liquid (B);
The liquid (B) dispersed in the matrix resin (A) is a liquid layer in which the liquid (B) is deposited on the surface when the master batch is mixed with a molding resin to produce a molded body. And the liquid layer causes surface characteristics corresponding to the type of the liquid (B) to be expressed on the surface of the molded body. Accordingly, the liquid (B) has a boiling point that does not volatilize at atmospheric pressure, for example, a boiling point of 100 ° C. or higher, and is selected according to the surface characteristics to be imparted to the surface of the molded body.

  By the way, in the present invention, the liquid (B) must be a low viscosity liquid having a viscosity (23 ° C.) of 1000 mPa · s or less, preferably 500 mPa · s or less, more preferably 100 mPa · s. That is, a high-viscosity liquid has little bleeding tendency and can be dispersed in a large amount in the matrix resin regardless of the glass transition point of the matrix resin. However, a low-viscosity liquid having the above viscosity has a high bleeding tendency, This is because it is difficult to disperse in a large amount unless the matrix resin (A) having the high glass transition point described above is used.

  For example, in the present invention, the low-viscosity liquid (B) is blended in the master batch in an amount of 10 to 70 parts by weight, particularly 15 to 65 parts by weight, per 100 parts by weight of the matrix resin. That is, in the present invention, even when the low-viscosity liquid (B) is blended in such a large amount, bleeding can be stably prevented over a long period of time, and after storage until mixing with other resins. Inconveniences such as stickiness and poor handling due to bleeding can be effectively avoided.

The type of the liquid (B) described above is not particularly limited as long as the viscosity is in the above range and is any of glycerin fatty acid ester, liquid paraffin, and edible oil and fat. Depending on the surface characteristics imparted to the surface of the molded body to be molded and the usage form of the molded body, an appropriate one can be used .
Furthermore, when the molded body is a container and it is intended to increase the slipperiness with respect to the viscous contents, the liquid (B) used is immiscible with the contents and does not mix with the contents. The one is selected. If it is miscible with the contents, the liquid exposed on the inner surface of the container mixes with the contents and falls off the inner surface of the container, making it difficult to impart the desired surface properties. It is.

<Preparation and use of masterbatch>
In the master batch of the present invention described above, a predetermined amount of the matrix resin (A) and the liquid (B) described above is supplied to, for example, a kneading part of an extruder, kneaded, melt-extruded, and the molten extrudate is pelletized. And is used as a pellet of a predetermined size through storage, transportation or sale. That is, it is effectively prevented that the liquid (B) bleeds immediately after the production until it is used and the pellets become sticky.
In addition, as described above, the glass transition point of the master batch obtained in this manner is lower than the glass transition point of the matrix resin (A) because the liquid (B) is blended. The difference in the glass transition point between the master batch and the matrix resin (A) is determined by the glass transition point of the matrix resin (A), the type of liquid (B), and the blending amount. In the present invention, when these are set so that the glass transition point difference is 20 ° C. or higher, the matrix resin (A) has a higher glass transition point and the liquid (B) by the matrix resin (A). It is preferable in that it can exhibit the bleeding prevention property to the maximum.

  The pellets of the master batch are used particularly for molding a molded body having a liquid layer formed from the liquid (B) on the surface. That is, this master batch pellet is kneaded with a molding resin (diluted resin), a kneaded product containing the liquid (B) at a predetermined concentration is prepared, and the kneaded product is molded into a predetermined shape by using the kneaded product. A molded body is obtained. In addition, when the molded body is composed of a multilayer structure, this master batch pellet is used not only for forming a liquid layer on the surface but also for adjusting the concentration of the liquid component in any layer in the multilayer structure. It can also be used by mixing with a resin (diluted resin).

  The molding resin to be mixed with the master batch pellet is not particularly limited as long as it can be uniformly mixed with the matrix resin (A), but in the present invention, a resin different from the matrix resin (A), in particular, glass. It is preferable to use a resin having a transition point of less than 35 ° C. as the molding resin. That is, a resin having a glass transition point of 35 ° C. or more like the matrix resin (A) can suppress bleeding of the low-viscosity liquid (B). Therefore, the resin is molded using such a resin having a low glass transition point. If it is carried out, it is difficult to cause bleeding, so that it is difficult to form a liquid layer on the surface of the obtained molded body, and there is a possibility that the surface characteristics of the liquid (B) cannot be fully exhibited.

  Further, as the kneading means and the molding means, appropriate means can be adopted depending on the physical properties (for example, melt flow rate) of the resin, but the low viscosity liquid (B) is kneaded with the solid matrix resin (A). Therefore, the kneading of the two is preferably performed by melt kneading in a kneading part in a molding machine such as an extruder, and the molding means is preferably extrusion molding or extrusion blow molding (direct blow molding). Applied. Such means can effectively avoid the dispersion of the liquid (B) at the time of kneading or molding, and further the influence of the presence of the liquid (B) on the molding (for example, adhesion of the liquid to the molding, etc.) Because it can be ignored.

  In the present invention, it is particularly preferable to use a masterbatch in which the above-described cyclic olefin-based resin is used as the matrix resin (A), and further to use an acyclic olefin-based resin as the molding resin. That is, the cyclic olefin resin is highly compatible with the acyclic olefin resin, and moreover, the acyclic olefin resin such as high, medium or low density polyethylene, linear low density polyethylene, polypropylene, poly 1- Butene, poly-4-methyl-1-pentene, copolymers of ethylene or propylene and other α-olefins, and the like are suitably used for forming flexible containers such as squeeze containers for extracting viscous contents. This is because when the master batch of the present invention is used for molding such a flexible container, the surface characteristics of the liquid layer of the liquid (B) can be utilized to the maximum.

FIG. 1 shows an example of a typical direct blow bottle as such a flexible container.
This bottle is generally indicated by 10 in FIG. 1, and includes a neck portion 11 provided with a thread, a trunk wall 15 connected to the neck portion 11 through a shoulder portion 13, and a bottom closing the lower end of the trunk wall 15. After having a wall 17 and filling such a bottle 10 with viscous contents, a metal foil 19 such as an aluminum foil is applied to the upper end opening of the neck 11 by heat sealing, and a predetermined cap 20 is attached. By doing so, it is used as a packaging bottle. In such a packaging bottle, the cap 20 is opened, the metal foil 19 to which the sealing material is applied is peeled off, the bottle 10 is tilted or inverted, and the container wall 15 is squeezed as necessary to take out the container contents. Is done.

That is, the master batch of the present invention is used for molding the container as described above. For example, the master batch pellet containing the cyclic olefin-based resin as the matrix resin (A) is used for molding the container. The resulting kneaded product is kneaded with an acyclic olefin resin and used as a resin composition for forming an inner layer, and appropriately used in combination with a gas barrier resin, an acyclic olefin resin for forming an outer layer, or an adhesive resin. A multi-layer parison is formed by simultaneous simultaneous melt extrusion, followed by a known blow molding to obtain the target bottle 10. In such a bottle 10, the inner surface layer contains the liquid (B) described above. Therefore, after the bottle 10 is molded, the liquid (B) gradually segregates on the inner surface to form a liquid layer. Further, the slipperiness with respect to the contents is improved, and by the tilting or inversion of the bottle 10 or the squeeze of the body wall 15, it is possible to effectively avoid the contents remaining on the inner surface and quickly discharge the contents. It is.
Moreover, the masterbatch of the present invention contains a large amount of the liquid (B). For this reason, the concentration of the liquid (B) in the molding resin composition for forming the inner layer is high (for example, 3 to 20). Mass%, particularly 3 to 15 mass%, most preferably 4 to 10 mass%), and the improvement of slipperiness due to the liquid layer of the liquid (B) can be exhibited stably.

In addition, the content accommodated in the bottle 10 is determined by the type of the liquid (B) or the type of the liquid (B) is determined by the type of the content as understood from the above description. Become.
For example, such contents include a viscous paste or a slurry-like flowable substance, for example, a viscosity of 100 cps or more at 23 ° C., specifically, ketchup, aqueous glue, honey, various sauces, mayonnaise, Cosmetic liquids such as emulsions, liquid detergents, shampoos, rinses, conditioners and the like are preferably used.
Among these, in the case of water-containing ones, for example, ketchup, any of the above-described glycerin fatty acid ester, liquid paraffin, and edible fats and oils can be suitably used as the liquid (B). Glycerin fatty acid esters represented by medium chain fatty acid triglycerides, glycerin trioleate and glycerin diacetomonooleate, liquid paraffin, and edible oils and fats are hard to volatilize, are approved as food additives, and are odorless. There is also an advantage that the flavor of the contents is not impaired.
For emulsified contents such as mayonnaise, a liquid having a property of having time for emulsification is suitable. Those having such properties are those having a relatively high molecular weight among these .

  The form of the container is not limited to the direct blow bottle shown in FIG. 1, but a cup or cup shape, a bottle shape, a bag shape (pouch), a syringe shape, an acupoint shape, a tray shape, etc., if necessary. , Can have various forms, and may be stretch-molded.

The excellent characteristics of the masterbatch of the present invention will be described in the following experimental examples.
In addition, the resin etc. which were used for the measurement method of various characteristics, physical properties, etc. which were performed by the following experiment examples, preparation of a masterbatch, and shaping | molding of a container (bottle) are as follows.

1. Master batch stability evaluation A master batch (master pellet) prepared by the method described below is placed in a glass bottle and stored in an environment of 22 ° C. and 60% RH for a predetermined period of time. Evaluated. The case where no liquid oozing was observed was marked with ◯, and the case where liquid oozing was observed was marked with x.

2. Evaluation of bottle moldability using a masterbatch Masterbatch (liquid-containing resin composition) pellets prepared by the method described below are mixed with high-pressure low-density polyethylene as a resin for forming the innermost layer of a multilayer bottle, and known direct blow molding A multilayer bottle was molded at a die head temperature of 210 ° C. by the method. The layer structure of this bottle is as follows.
Innermost layer / adhesive layer / gas barrier layer / adhesive layer / outermost layer When a bottle was formed, the case that could be formed without any problem was indicated as ◯, and the case where the problem occurred was indicated as ×.

3. Glass transition point measurement The matrix resin for master batch preparation and the glass transition point of the master batch pellet produced were measured using a differential scanning calorimeter (Diamond DSC manufactured by PERKIN ELMER).
About 10 mg each was prepared as a sample, scanned from 25 ° C. to −30 ° C. at a temperature decrease rate of 10 ° C./min, held at −30 ° C. for 5 minutes, and from 30 ° C. to 200 ° C. at a temperature increase rate of 10 ° C. / The glass transition point of each matrix resin and the master batch was determined from the profile obtained when scanning was performed at min. Those whose glass transition point could not be observed in this range were determined to be -30 ° C or lower.

<Matrix resin for masterbatch preparation>
Cyclic olefin resin A (COC-A, ethylene-tetracyclododecene copolymer)
MFR; 15 g / 10 min (260 ° C., 2.16 Kg)
Density: 1.02 g / cm ³
Glass transition point (Tg); 67 ° C
Cyclic olefin resin B (COC-B, ethylene-tetracyclododecene copolymer)
MFR; 30 g / 10 min (260 ° C., 2.16 Kg)
Density: 1.02 g / cm ³
Glass transition point (Tg); 74 ° C
Cyclic olefin resin C (COC-C, ethylene-tetracyclododecene copolymer)
MFR; 15 g / 10 min (260 ° C., 2.16 Kg)
Density: 1.04 g / cm ³
Glass transition point (Tg); 128 ° C
High pressure low density polyethylene (LDPE)
MFR; 0.3 g / 10 min (190 ° C., 2.16 Kg)
Density: 0.922 g / cm ³
Glass transition point (Tg); -30 ° C or less

<Liquid>
Medium chain fatty acid triglyceride (MCT)
Surface tension: 28.8 mN / m (23 ° C.)
Viscosity: 33.8 mPa · s (23 ° C)
Boiling point: 210 ° C or higher Flash point: 242 ° C (reference value)
In addition, the surface tension of the liquid used the value measured at 23 degreeC using the solid-liquid interface analysis system DropMaster700 (made by Kyowa Interface Science Co., Ltd.). In addition, the density of the liquid required for the liquid surface tension measurement used the value measured at 23 degreeC using the density specific gravity meter DA-130 (made by Kyoto Electronics Industry Co., Ltd.). Further, the viscosity of the lubricating liquid showed a value measured at 23 ° C. using a tuning fork type vibration viscometer SV-10 (manufactured by A & D Co., Ltd.).

<Resin for bottle molding>
(Base material for innermost layer formation)
Low density polyethylene (LDPE)
MFR; 0.3g / 10min
Density: 0.92 g / cm ³
(Outermost layer forming material)
Low density polyethylene (LDPE)
MFR; 0.3g / 10min
(Adhesive layer forming material)
Acid anhydride-modified polyethylene (gas barrier layer forming material)
Ethylene vinyl alcohol copolymer (ethylene content: 32 mol%, density 1.19 g / cm ³ , Tg 61 ° C.)

<Experimental example 1>
Using the cyclic olefin resin A (COC-A) as the matrix resin for preparing the masterbatch and the medium chain fatty acid triglyceride (MCT) as the liquid, respectively, so that COC-A: MCT = 100: 25 (parts by mass) Then, using a twin-screw kneading extruder (ULTNano05 manufactured by Technobel Co., Ltd.), melt-kneading was performed under the condition of a cylinder temperature of 200 ° C. to prepare a master batch pellet A (MB-A).
The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed.
Moreover, the glass transition point of the produced master batch pellet A was measured.
Furthermore, a master bottle pellet A (MB-A) mixed with low density polyethylene in a weight ratio of 1: 3 is used as the innermost layer forming resin, a multilayer bottle is molded, and the bottle moldability is evaluated. It was. Molding was possible without problems. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

<Experimental example 2>
Cyclic olefin resin A (COC-A): medium batch fatty acid triglyceride (MCT) = 100: 42 (parts by mass) Master batch pellet B using a twin-screw kneading extruder under the same conditions as in Experimental Example 1 (MB-B) was produced. The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed.
Moreover, the glass transition point of the produced master batch pellet B was measured.
Furthermore, using a master batch pellet B (MB-B) mixed with low density polyethylene so as to have a weight ratio of 1: 5 as a resin for innermost layer formation, a multilayer bottle is molded in the same manner as in Experimental Example 1, The bottle moldability was evaluated. Molding was possible without problems. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

<Experimental example 3>
Cyclic olefin-based resin B (COC-B): medium-chain fatty acid triglyceride (MCT) = 100: 25 (part by mass) Master batch pellet C using a twin-screw kneading extruder under the same conditions as in Experimental Example 1 (MB-C) was produced. The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed.
Moreover, the glass transition point of the produced master batch pellet C was measured.
Furthermore, a master bottle pellet C (MB-C) mixed with low density polyethylene in a weight ratio of 1: 3 is used as the innermost layer forming resin, a multilayer bottle is molded, and the bottle moldability is evaluated. It was. Molding was possible without problems. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

<Experimental example 4>
Cyclic olefin resin B (COC-B): Master batch pellet D using a twin-screw kneading extruder under the same conditions as in Experimental Example 1 except that medium-chain fatty acid triglyceride (MCT) = 100: 42 (parts by mass) (MB-D) was produced. The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed.
Moreover, the glass transition point of the produced master batch pellet D was measured.
Furthermore, a master bottle pellet D (MB-D) mixed with low density polyethylene in a weight ratio of 1: 5 is used as the innermost layer forming resin, a multilayer bottle is molded, and the bottle moldability is evaluated. It was. Molding was possible without problems. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

<Experimental example 5>
Cyclic olefin-based resin B (COC-B): medium-chain fatty acid triglyceride (MCT) = 100: 67 (parts by mass) Master batch pellet E using a twin-screw kneading extruder under the same conditions as in Experimental Example 1 (MB-E) was produced. The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed.
Further, a master bottle pellet E (MB-E) mixed with low density polyethylene in a weight ratio of 1: 7 is used as the innermost layer forming resin, a multilayer bottle is molded, and the bottle moldability is evaluated. It was. Molding was possible without problems. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

<Experimental example 6>
Cyclic olefin-based resin C (COC-C): medium-chain fatty acid triglyceride (MCT) = 100: 42 (parts by mass), and a twin-screw kneading extruder under the same conditions as in Experimental Example 1 except that the cylinder temperature was 220 ° C. Was used to prepare a master batch pellet F (MB-F). The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed.
Moreover, the glass transition point of the produced master batch pellet F was measured.
Furthermore, a master bottle pellet F (MB-F) mixed with low density polyethylene in a weight ratio of 1: 5 is used as the innermost layer forming resin, a multilayer bottle is molded, and the bottle moldability is evaluated. It was. Molding was possible without problems. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

<Experimental example 7>
Cyclic olefin resin B (COC-B): Master batch pellet G using a twin-screw kneading extruder under the same conditions as in Experimental Example 1 except that medium-chain fatty acid triglyceride (MCT) = 100: 11 (parts by mass) (MB-G) was produced. The prepared pellets were stored for 3 months, and then the stability of the master batch was evaluated. No oozing of liquid to the pellet surface was observed. The results are summarized in Table 1.

<Experimental Example 8>
Experimental Example 1 except that high-pressure low-density polyethylene (LDPE) was used as the matrix resin for preparing the masterbatch and medium-chain fatty acid triglyceride (MCT) was used as the liquid, and LDPE: MCT = 100: 11 (parts by mass). Master batch pellets H (MB-H) were produced using a twin-screw kneading extruder under the same conditions as those described above. The stability of the master batch was evaluated using the prepared pellets. From one day after the preparation of the pellets, liquid oozing to the pellet surface was observed. After 3 months, the liquid ooze had progressed remarkably.
Also, master batch pellets H (MB-H) mixed with low density polyethylene at a weight ratio of 1: 1 are used as the innermost layer forming resin, a multilayer bottle is molded, and bottle moldability is evaluated. It was. Since the mixed resin blocked in the hopper and the discharge amount was not stable, stable molding was difficult. Further, an MCT oil film was formed on the inner surface of the molded bottle. The results are summarized in Table 1.

From Table 1, in Experimental Example 8 in which 11 parts by mass of liquid was blended with respect to 100 parts by mass of matrix resin (matrix resin (liquid not blended)) having a glass transition point of less than 35 ° C., the results of the stability evaluation of the masterbatch From the above, exudation of the blended liquid occurs remarkably, whereas 11 to 67 parts by mass of the liquid with respect to 100 parts by mass of the matrix resin having a glass transition point of 35 ° C. or higher of the matrix resin (no liquid blended). In the blended experimental examples 1 to 7, it can be seen from the results of the stability evaluation of the master batch that the blended liquid can be prevented from exuding.
Also, from the results of bottle moldability evaluation, the master batches of Experimental Examples 1 to 7 produced using a resin having a glass transition point of 35 ° C. or higher of the matrix resin (no liquid blended) could be molded without problems. On the other hand, in Experimental Example 8 produced using a resin having a glass transition point of less than 35 ° C. of the matrix resin (liquid is not blended), the liquid oozes out to the pellet surface, and thus mixed in the hopper. The resulting low density polyethylene and blocking occurred, the discharge amount was not stable, and molding was difficult.

  From the above, in order to obtain a masterbatch containing a liquid in which exudation was prevented over a long period of time, a resin having a glass transition point of 35 ° C. or higher in a state where the liquid is not blended, It can be said that it is effective to disperse the liquid. Furthermore, it became clear that this masterbatch can be used without any particular problem in extrusion molding.

<Discussion>
From the results of glass transition point measurement, it was found that the glass transition point of the master batch (liquid-containing resin composition) was lower than the glass transition point of the matrix resin before liquid blending. This decrease in the glass transition point can be interpreted as the compounded liquid is compatible or partially compatible in the matrix resin. In the present invention, it is possible to contain a maximum of 67 parts by mass of liquid in 100 parts by mass of the matrix resin of the master batch. This is because the liquid component is compatible or partially compatible in the matrix resin. Is presumed to play an important role. In addition, the glass transition point in the state of the master batch (liquid-containing resin composition) is 35 ° C. or more, and since it is in a glass state at room temperature, the liquid component dispersed in the matrix oozes out. It is inferred that this is effectively prevented.

10: Bottle 11: Neck 13: Shoulder 15: Body wall 17: Bottom 19: Metal foil 20: Cap

Claims (5)

In the matrix resin (A) having a glass transition point of 35 ° C. or higher, a liquid (B) having a viscosity (23 ° C.) of 1000 mPa · s or less is dispersed ,
The matrix resin (A) is a cyclic olefin resin,
The liquid (B) is any one of glycerin fatty acid ester, liquid paraffin or edible oil and fat, and the liquid (B) is present at 10 to 70 parts by mass per 100 parts by mass of the matrix resin (A). Masterbatch used for forming containers . The masterbatch according to claim 1, wherein the liquid (B) has a viscosity of 100 mPa · s or less. The masterbatch according to claim 1 or 2, wherein the liquid (B) is present at 15 to 65 parts by mass per 100 parts by mass of the matrix resin (A). A master batch in which a liquid (B) having a viscosity (23 ° C.) of 1000 mPa · s or less is dispersed in a matrix resin (A) having a glass transition point of 35 ° C. or higher is molded with a glass transition point of less than 35 ° C. A method for using a masterbatch, comprising a step of mixing with a resin for molding and molding the mixture.   The use method according to claim 4, wherein the matrix resin (A) in the master batch is a cyclic olefin resin, and the molding resin is an acyclic olefin resin.

Images