JP6711083B2 - Container containing liquid containing alkylene glycol alkyl ether, method for storing liquid containing alkylene glycol alkyl ether, and container containing liquid containing alkylene glycol alkyl ether - Google Patents

Description

The present invention relates to a container containing a liquid containing an alkylene glycol alkyl ether, a method for storing a liquid containing an alkylene glycol alkyl ether, and a container containing a liquid containing an alkylene glycol alkyl ether.

Examples of containers for storing hydrocarbons and various chemicals include chemical bottles and fuel tanks for automobiles and small engines. Many of the metals and glasses that have been conventionally used as the material are being replaced by plastics. Compared to metal and glass, plastic is lighter in weight, does not require rust-prevention treatment, is hard to break, and has a high degree of freedom in shape.

Most of the above-mentioned applications use polyolefins such as high-density polyethylene (hereinafter sometimes abbreviated as “HDPE”) and have excellent mechanical strength, moldability, and economic efficiency, but are stored inside the container. However, there is a drawback that the articles are easily scattered into the atmosphere through the container wall.
Therefore, as a method for enhancing the barrier performance in a container made of polyolefin such as HDPE, a method of blending a polyamide resin such as nylon 6,66 or EVOH with a polyolefin together with an adhesive resin to produce a single layer container from the composition. Are known (for example, see Patent Documents 1 and 2). Also disclosed is a method of using polymeta-xylylene adipamide (hereinafter sometimes abbreviated as “N-MXD6”), which is superior to nylon 6,66 in barrier properties, in the blend single layer container ( See, for example, Patent Documents 3 and 4.

JP-A-55-121017 JP-A-58-209562 JP 2005-206806 A JP, 2007-177208, A

In Patent Documents 1 to 4, attention is paid to the problem that the barrier performance of the polyolefin container is low, and an object is to improve it. However, the present inventors have found a new problem that a container is deformed (dented) when a specific content, specifically, a liquid containing an alkylene glycol alkyl ether, is sealed and stored. In particular, if the storage temperature of the container filled with the contents is raised, the container may be more significantly deformed than the storage at room temperature. If the container is greatly deformed, the durability and storage performance of the container may be adversely affected, and the appearance may be deteriorated.
The present invention has been made in view of this new problem, and includes a container that can suppress container deformation even when a liquid containing an alkylene glycol alkyl ether is stored, and an alkylene glycol alkyl ether using the container. An object of the present invention is to provide a method for storing a liquid, and a container containing a liquid containing an alkylene glycol alkyl ether, the container containing a liquid containing the alkylene glycol alkyl ether in the container.

The present invention provides a container containing a liquid containing the following alkylene glycol alkyl ether, a method for storing a liquid containing the alkylene glycol alkyl ether, and a container containing a liquid containing the alkylene glycol alkyl ether.
<1>
A container for containing a liquid containing an alkylene glycol alkyl ether,
A polyolefin (A) 40 to 90% by mass, an acid-modified polyolefin (B) 3 to 30% by mass, and a barrier resin (C) 3 to 30% by mass, and a barrier in the resin composition. A container in which the photosensitive resin (C) is dispersed in layers.
<2>
The container according to <1>, wherein the alkylene glycol alkyl ether is diethylene glycol dialkyl ether.
<3>
The barrier resin (C) includes a diamine unit containing 70 mol% or more of metaxylylenediamine units, and a dicarboxylic acid unit containing 70 mol% or more of α,ω-linear aliphatic dicarboxylic acid units having 4 to 20 carbon atoms. The container according to <1> or <2>, which is a polyamide containing.
<4>
The container according to any one of <1> to <3>, wherein the container body has an average thickness of 0.5 mm or more.
<5>
The container according to any one of <1> to <4>, in which the volume change rate represented by the following formula (i) is less than 1%.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.)
<6>
A method for storing a liquid containing an alkylene glycol alkyl ether, comprising:
A polyolefin (A) 40 to 90% by mass, an acid-modified polyolefin (B) 3 to 30% by mass, and a barrier resin (C) 3 to 30% by mass, and a barrier in the resin composition. A method for storing, wherein the liquid is contained in a container in which the functional resin (C) is dispersed in layers.
<7>
The storage method according to <6>, wherein the alkylene glycol alkyl ether is diethylene glycol dialkyl ether.
<8>
The barrier resin (C) includes a diamine unit containing 70 mol% or more of metaxylylenediamine units, and a dicarboxylic acid unit containing 70 mol% or more of α,ω-linear aliphatic dicarboxylic acid units having 4 to 20 carbon atoms. The storage method according to <6> or <7>, which is a polyamide containing.
<9>
The storage method according to any one of <6> to <8>, wherein the container body has an average thickness of 0.5 mm or more.
<10>
The storage method according to any one of <6> to <9>, wherein the volume change rate represented by the following formula (i) is less than 1%.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.)
<11>
A container containing a liquid containing an alkylene glycol alkyl ether, the container containing a liquid containing an alkylene glycol alkyl ether,
The container comprises a resin composition containing 40 to 90% by mass of a polyolefin (A), 3 to 30% by mass of an acid-modified polyolefin (B), and 3 to 30% by mass of a barrier resin (C). A container containing a liquid containing an alkylene glycol alkyl ether, in which the barrier resin (C) is dispersed in a layer form.
<12>
The alkylene glycol alkyl ether-containing liquid-containing container according to <11>, wherein the alkylene glycol alkyl ether is diethylene glycol dialkyl ether.
<13>
The barrier resin (C) includes a diamine unit containing 70 mol% or more of metaxylylenediamine units, and a dicarboxylic acid unit containing 70 mol% or more of α,ω-linear aliphatic dicarboxylic acid units having 4 to 20 carbon atoms. A container containing a liquid containing an alkylene glycol alkyl ether according to <11> or <12>, which is a polyamide.
<14>
The alkylene glycol alkyl ether-containing liquid-containing container according to any one of <11> to <13>, wherein the container body has an average thickness of 0.5 mm or more.
<15>
The alkylene glycol alkyl ether-containing liquid-containing container according to any one of <11> to <14>, wherein the volume change rate represented by the following formula (i) is less than 1%.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.)

According to the present invention, even if a liquid containing an alkylene glycol alkyl ether is hermetically stored in a container, the container deformation can be suppressed to be small. As a result, the durability and storage performance of the container and the appearance thereof can be stably maintained.

It is the photograph which cuts the container 1 obtained by manufacture example 1 perpendicular|vertical with respect to an axial direction, and expands the cross section.

Hereinafter, the present invention will be described in detail.
[Resin composition]
The container according to the present invention comprises a resin composition containing a polyolefin (A), an acid-modified polyolefin (B), and a barrier resin (C), and the barrier resin (C) is layered in the resin composition. It is dispersed.
Hereinafter, each of these components contained in the resin composition will be described in detail.

(Polyolefin (A))
Polyolefin (A) is a main material constituting a container. The polyolefin (A) used in the present invention is polyethylene represented by low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, propylene homopolymer, ethylene-propylene block copolymer, ethylene-propylene. Homopolymers of ethylene hydrocarbons having 2 or more carbon atoms such as polypropylene represented by random copolymers, 1-polybutene, 1-polymethylpentene, etc., homopolymers of α-olefins having 3 to 20 carbon atoms, carbon number Examples thereof include copolymers of 3 to 20 α-olefins, copolymers of 3 to 20 carbons α-olefins and cyclic olefins, and the like.

Melt flow rate (MFR) is a typical index of melt viscosity and molecular weight of polyolefin. The polyolefin (A) used in the present invention has, for example, a melt flow rate (MFR) of 0.01 to 10 (g/10 minutes). The optimum range of the MFR of the polyolefin (A) varies depending on the container manufacturing method. For example, when the container is manufactured by the direct blow method, the MFR is 0.01 to 1 (g/10 minutes). It is preferably in the range of 0.02 to 0.9 (g/10 minutes), and more preferably 0.05 to 0.9 (g/10 minutes). The MFR is a value measured according to JIS K7210.
The molding processing temperature of the present invention is higher than that during the molding processing of the polyolefin alone, and the barrier resin (C) generally has a higher density than the polyolefin. Therefore, in the case of the direct blow method, the barrier resin (C The polyolefin blended with) tends to have a larger drawdown during the molding process, as compared with a polyolefin made of only polyolefin. Therefore, in the present invention, by setting the MFR of the polyolefin (A) to 1 (g/10 minutes) or less, it is possible to suppress the occurrence of drawdown during the molding process by the direct blow method, and further to obtain the obtained container. The thickness accuracy of is excellent. Further, when the MFR of the polyolefin (A) is 0.01 (g/10 minutes) or more, the melt viscosity becomes a viscosity suitable for molding, and also the barrier property in the resin composition constituting the obtained container. As a result of the resin (C) being dispersed well, it is possible to obtain a container having excellent barrier performance. In addition, the performance of suppressing the deformation of the container when the liquid containing the alkylene glycol alkyl ether is hermetically stored in the container (hereinafter, also simply referred to as “deformation suppressing performance”) tends to be high.
The polyolefin (A) is not particularly limited, but its melting point (ATm) is, for example, 100 to 180°C, preferably 125 to 170°C.

The polyolefin (A) is preferably polyethylene or polypropylene of the above, and more preferably high density polyethylene (HDPE) is used. The high density polyethylene (HDPE) is polyethylene having a density of 0.942 g/cm ³ or more. and a, preferably its density, 0.97 g / cm ³ or less, more preferably 0.945~0.96g / cm ^3. Polyethylene has sufficient crystallinity due to its high density, and the content can be stored regardless of the type of the content stored in the container. Further, when the density is 0.97 g/cm ³ or less, the polyolefin (A) does not become brittle like glass and can exhibit practical strength as a container.
These polyolefins may be used alone as the polyolefin (A) constituting the container or may be used as a mixture of two or more kinds, but a high density polyethylene simple substance is most preferable.

(Acid-modified polyolefin (B))
The acid-modified polyolefin (B) used in the present invention is a product obtained by graft-modifying a polyolefin with an unsaturated carboxylic acid or an anhydride thereof, and is generally widely used as an adhesive resin. As the polyolefin, the same ones as listed above for the polyolefin (A) are used, preferably polypropylene and polyethylene are used, and more preferably polyethylene is used. The acid-modified polyolefin (B) is preferably a polyolefin obtained by modifying the same type of polyolefin as the polyolefin (A) used. That is, if the polyolefin (A) is polyethylene, the acid-modified polyolefin (B) is preferably polyethylene modified with acid, and if the polyolefin (A) is polypropylene, the acid-modified polyolefin (B) is acid-modified polypropylene. Is preferred.
Specific examples of unsaturated carboxylic acids or anhydrides thereof include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, butenylsuccinic acid, and These acid anhydrides are mentioned. Among them, maleic acid and maleic anhydride are preferably used. As a method of graft-copolymerizing the above-mentioned unsaturated carboxylic acid or its anhydride with polyolefin to obtain an acid-modified polyolefin, various conventionally known methods can be used. For example, a method in which a polyolefin is melted with an extruder or the like and a graft monomer is added to copolymerize it, or a method in which a polyolefin is dissolved in a solvent and a graft monomer is added to copolymerize Examples thereof include a method of adding a graft monomer and performing copolymerization.

In the present invention, the acid-modified polyolefin (B) has a role of adhering the polyolefin (A) and the barrier resin (C). Then, in the resin composition constituting the container of the present invention, it is considered that the barrier resin (C) such as the metaxylylene group-containing polyamide is in a chemical bonding state with the acid-modified substituent of the acid-modified polyolefin (B). As a result, the barrier resin (C) is present in the vicinity of the acid-modified polyolefin (B), and the adhesive strength changes depending on the difference in acid modification rate.
An acid value is mentioned as an index of the acid modification rate of the acid-modified polyolefin (B), and the acid value in the present invention is measured according to the method described in JIS K0070. In the present invention, the acid value of the acid-modified polyolefin (B) is preferably 2 to 30 mg/g.
When the acid value of the acid-modified polyolefin (B) is 2 mg/g or more, the adhesiveness between the polyolefin (A) and the barrier resin (C) in the resin composition becomes good, and voids or the like occur at the adhesive interface between the two. It gets harder. Therefore, the barrier performance and mechanical strength of the obtained container are likely to be good, and cracking of the container when dropped is unlikely to occur. In addition, the deformation suppressing performance tends to be high.
Further, when the acid value of the acid-modified polyolefin (B) is 30 mg/g or less, the acid-modified polyolefin (B) and the barrier resin (C) are less likely to be localized, and the container molded by the direct blow method is In this case, it is possible to prevent unevenness on the inner surface and uneven thickness, and it is easy to improve the barrier performance and mechanical strength. In addition, the deformation suppressing performance tends to be high.
From the above viewpoints, the acid value of the acid-modified polyolefin (B) is more preferably 3 to 20 mg/g.

Further, since the barrier resin (C) is generally a relatively hard material, cracks and peeling easily occur at the interface when a shock is applied to the container, and the strength, barrier performance, chemical resistance, and deformation suppression of the container are suppressed. May impair performance. Therefore, it is effective to use, as the acid-modified polyolefin (B) used in the present invention, one having a relatively low density and a relatively soft property.
From such a viewpoint, the density of the acid-modified polyolefin (B) used in the present invention is preferably 0.89 to 0.96 g/cm ³ , and more preferably 0.90 to 0.945 g/cm ³ . It is particularly preferably 0.91 to 0.93 g/cm ³ . When the density of the acid-modified polyolefin (B) is 0.89 g/cm ³ or more, the compatibility with the polyolefin (A) will be good, and the adhesiveness with the barrier resin (C) will be improved, and the container will be improved. Has excellent strength, barrier performance, chemical resistance performance, and deformation suppression performance. When the density of the acid-modified polyolefin (B) is 0.96 g/cm ³ or less, the acid-modified polyolefin (B) has an appropriate softness, so that the strength and the barrier are improved even when the container is impacted. It is possible to prevent the deterioration of the performance, the chemical resistance performance, and the deformation suppression performance.

Further, as the MFR of the acid-modified polyolefin (B) used in the present invention, it is preferable to use one having a high melt viscosity from the viewpoints of molding processing stability and container strength retention, which is based on the method described in JIS K7210. The measured value is preferably 0.1 to 10 (g/10 minutes), more preferably 0.1 to 8 (g/10 minutes), and further preferably 0.2 to 3 (g/10 minutes). ).
The acid-modified polyolefin (B) is not particularly limited, but its melting point (BTm) is, for example, 110 to 180° C., preferably about 115 to 170° C.

(Barrier resin (C))
The barrier resin (C) used in the present invention is a resin having a better barrier property than the polyolefin (A), and specific examples thereof include ethylene-vinyl alcohol copolymer resin and polyamide.
Examples of the polyamide include polyamide containing a metaxylylene group, nylon 6, nylon 66, nylon 666, nylon 610, nylon 11, nylon 12, and the like. Among these, metaxylylene group-containing polyamides, nylon 6, nylon 666, and the like are preferable, and metaxylylene group-containing polyamides are particularly preferable from the viewpoint of easily improving the barrier performance and the deformation suppressing performance.

The metaxylylene group-containing polyamide contains a diamine unit and a dicarboxylic acid unit, and the diamine unit has a unit derived from metaxylylenediamine (metaxylylenediamine unit). The diamine unit constituting the metaxylylene group-containing polyamide is preferably 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% of the metaxylylenediamine unit from the viewpoint of barrier properties, chemical resistance performance and deformation suppression performance. Contains more than mol%.
In the metaxylylene group-containing polyamide, as the compound capable of forming a diamine unit other than the metaxylylenediamine unit, a diamine having an aromatic ring such as paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4- Fats such as diamine having an alicyclic structure such as bis(aminomethyl)cyclohexane, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, 2-methyl-1,5-pentanediamine, polyoxyalkyleneamine, and polyetherdiamine. Examples thereof include group diamines, but the present invention is not limited thereto.

From the viewpoint of crystallinity, the dicarboxylic acid unit constituting the metaxylylene group-containing polyamide preferably has an α,ω-aliphatic dicarboxylic acid unit of 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more. Including.
Examples of the compound constituting the α,ω-aliphatic dicarboxylic acid unit include suberic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, etc., but in view of barrier properties, chemical resistance performance, deformation suppression performance and crystallinity. Therefore, adipic acid and sebacic acid are preferably used.
Examples of the compound capable of forming a dicarboxylic acid unit other than the α,ω-aliphatic dicarboxylic acid unit include alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. Examples thereof include aromatic dicarboxylic acids such as orthophthalic acid, xylylenedicarboxylic acid, and naphthalenedicarboxylic acid, but are not limited thereto.
Among these, isophthalic acid and 2,6-naphthalenedicarboxylic acid can easily obtain a polyamide having excellent barrier performance, chemical resistance, and deformation suppression performance without inhibiting the polycondensation reaction during the production of the metaxylylene group-containing polyamide. It is preferable because it can be obtained. When the metaxylylene group-containing polyamide has a dicarboxylic acid unit derived from isophthalic acid and/or 2,6-naphthalenedicarboxylic acid, the dispersibility of the metaxylylene group-containing polyamide in the resin composition and the barrier performance, chemical resistance, and deformation of the container From the viewpoint of suppression performance, the content of dicarboxylic acid units derived from isophthalic acid and/or 2,6-naphthalenedicarboxylic acid is preferably 20 mol% or less, more preferably 15 mol% or less, and further preferably 15 mol% or less of all dicarboxylic acid units. It is preferably 10 mol% or less.

Further, in addition to the diamine unit and the dicarboxylic acid unit, as a copolymer unit constituting the metaxylylene group-containing polyamide, lactams such as ε-caprolactam and laurolactam, aminocaproic acid, and amino within a range that does not impair the effects of the present invention. A compound such as an aliphatic aminocarboxylic acid such as undecanoic acid or an aromatic aminocarboxylic acid such as p-aminomethylbenzoic acid can be used as a copolymerization unit. The proportion of these copolymer units in the metaxylylene group-containing polyamide is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 15 mol% or less.

The metaxylylene group-containing polyamide is produced by a melt polycondensation method (melt polymerization method). For example, there is a method in which a nylon salt composed of a diamine and a dicarboxylic acid is heated in the presence of water under pressure and polymerized in a molten state while removing added water and condensed water. It is also produced by a method in which a diamine is directly added to a molten dicarboxylic acid and polycondensation is performed. In this case, in order to keep the reaction system in a uniform liquid state, diamine is continuously added to the dicarboxylic acid, during which the reaction system is heated so that the reaction temperature does not fall below the melting point of the oligoamide and polyamide to be produced. , Polycondensation proceeds.

A phosphorus atom-containing compound may be added to the polycondensation system of the metaxylylene group-containing polyamide in order to obtain the effect of promoting the amidation reaction and the effect of preventing coloration during polycondensation.
As the phosphorus atom-containing compound, dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylphosphonous acid, Sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, ethyl phenylphosphonate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, phenylphosphonate Examples thereof include diethyl, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, and pyrophosphorous acid. Among these, sodium hypophosphite, potassium hypophosphite, metal hypophosphite such as lithium hypophosphite is highly effective in accelerating the amidation reaction, and is also preferably used because it is also excellent in coloring prevention effect. Of these, sodium hypophosphite and calcium hypophosphite are particularly preferable, but the phosphorus atom-containing compound usable in the present invention is not limited to these compounds.

The addition amount of the phosphorus atom-containing compound to be added to the polycondensation system of the metaxylylene group-containing polyamide is preferably in terms of phosphorus atom concentration in the metaxylylene group-containing polyamide from the viewpoint of preventing the coloring of the metaxylylene group-containing polyamide during polycondensation. It is 1 to 500 ppm, more preferably 5 to 450 ppm, and further preferably 10 to 400 ppm.

It is preferable to add an alkali metal compound or an alkaline earth metal compound in combination with the phosphorus atom-containing compound in the polycondensation system of the metaxylylene group-containing polyamide. In order to prevent the coloring of the metaxylylene group-containing polyamide during polycondensation, it is necessary to allow the phosphorus atom-containing compound to be present in a sufficient amount, but also to adjust the amidation reaction rate, an alkali metal compound or an alkaline earth metal compound. It is preferable to coexist.
For example, alkali metal/alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide, and lithium acetate. , Sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate, and other alkali metal/alkaline earth metal acetate salts, etc., but not limited to these compounds You can
When an alkali metal compound or an alkaline earth metal compound is added to the polycondensation system of a metaxylylene group-containing polyamide, the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound is preferably 0.5 to 2 0.0, more preferably 0.6 to 1.8, still more preferably 0.7 to 1.5. By setting the addition amount of the alkali metal compound or the alkaline earth metal compound within the above range, it becomes possible to suppress the gel formation while obtaining the effect of promoting the amidation reaction by the phosphorus atom-containing compound.

The metaxylylene group-containing polyamide obtained by melt polycondensation is once taken out and pelletized. The obtained pellets may be dried or solid-phase polymerized to further increase the degree of polymerization. As a heating device used in drying or solid-state polymerization, a rotary drum type heating device called a continuous heating and drying device, a tumble dryer, a conical dryer, a rotary dryer or the like, and a rotary blade inside a so-called Nauta mixer are used. Although a conical heating device provided with is preferably used, known methods and devices can be used without being limited thereto. Especially in the case of performing solid phase polymerization of polyamide, a rotating drum type heating device in the above-mentioned device can seal the system and facilitate polycondensation in a state in which oxygen causing coloring is removed. Preferably used from

As a preferred example of the barrier resin (C) in the present invention, a diamine unit containing 70 mol% or more of metaxylylenediamine units and an α,ω-linear aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms are used. A polyamide containing a dicarboxylic acid unit in an amount of at least mol% is included.

The water content of the metaxylylene group-containing polyamide used in the present invention is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.4% by mass, and further preferably 0.01 to 0% by mass. It is 0.3% by mass. By setting the water content of the metaxylylene group-containing polyamide to 0.5% by mass or less, it is possible to prevent evaporation of water during molding and generation of bubbles in the molded body. On the other hand, the lower the water content, the higher the viscosity in the softened state and the easier it becomes to maintain the layered dispersed state, but by setting it to 0.001% or more, the drying time during the production of the metaxylylene group-containing polyamide is shortened. Can prevent coloring and heat deterioration.

There are several indicators of the degree of polymerization of the metaxylylene group-containing polyamide, but the relative viscosity is generally used. The relative viscosity of the metaxylylene group-containing polyamide used in the present invention is preferably 1.5 to 4.5, more preferably 2.0 to 4.2, and further preferably 2.5 to 4.0. As the relative viscosity of the meta-xylylene group-containing polyamide becomes higher, it becomes more difficult to compatibilize with the polyolefin (A), and it becomes easier to form a layered dispersion state. However, if an attempt is made to increase the relative viscosity of the metaxylylene group-containing polyamide, the polymerization time becomes long and the production cost increases. By setting the relative viscosity of the metaxylylene group-containing polyamide within the above range, a good layered dispersion state can be formed, and the manufacturing cost can be kept low.
The relative viscosity as used herein is determined by dissolving 0.2 g of polyamide in 20 mL of 96% sulfuric acid, dropping time (t) measured at 25° C. with a Canon Fenske viscometer, and 96% sulfuric acid itself measured in the same manner. Is the ratio of the fall time (t ₀ ) of
Relative viscosity=t/t ₀

Melt viscosity is used as an index other than the above for the degree of polymerization of the metaxylylene group-containing polyamide. Generally, there is a correlation between the relative viscosity and the melt viscosity, but when the metaxylylene group-containing polyamide contains a large amount of water, hydrolysis may proceed during melting and the melt viscosity may decrease. The melt viscosity of the metaxylylene group-containing polyamide used in the present invention is preferably 100 to 2000 Pa·s, more preferably 150 to 1900 Pa·s, in the range of water content of 0.001 to 0.5 mass %. It is preferably 200 to 1800 Pa·s.
The melt viscosity referred to here is such that a metaxylylene group-containing polyamide was melted in a barrel set at 260° C. with a capillary rheometer and then passed through a capillary having a diameter of 1 mm and a length of 10 mm at a shear rate of 100 sec ⁻¹ . It is a value at the time.

The metaxylylene group-containing polyamide used in the present invention has a free volume of preferably 0.045 to 0.060 nm ³ , more preferably a free volume determined by a positron annihilation method, from the viewpoint of barrier properties, deformation suppressing performance, and physical properties. It is 0.046 to 0.059 nm ³ , and more preferably 0.047 to 0.058 nm ³ . The free volume of the metaxylylene group-containing polyamide varies depending on the branching of the molecular chain and the presence of foreign matter, but when it is within the above range, various compounds are difficult to permeate and the physical properties are good. Further, the free volume of the metaxylylene group-containing polyamide varies depending on the crystallinity, but the free volume referred to here is such that the heating crystallization calorific value of the metaxylylene group-containing polyamide during DSC measurement is in the range of 20 to 40 J/g. It is a value in the state in.

When the barrier resin (C) used in the present invention is a crystalline resin, its melting point (CTm) is usually 150 to 250° C., preferably 190 to 245° C. Is.
The melting point (CTm) of the barrier resin is higher than the melting point (ATm) of the polyolefin (A), and the melting point difference (CTm-ATm) is preferably 20 to 150° C., more preferably 50. ~120°C. In the present invention, by increasing the melting point difference between the component (C) and the component (A) in this way, the production method described below can be more appropriately carried out.
Similarly, the melting point (CTm) of the barrier resin (C) is higher than the melting point (BTm) of the acid-modified polyolefin (B), and the difference in melting point (CTm-BTm) is preferably 20 to 150°C. , And more preferably 50 to 120°C.

Further, in the metaxylylene group-containing polyamide used in the present invention, a component having a number average molecular weight of 1000 or less measured by GPC is preferably 2% by mass or less, more preferably 1. It is 5 mass% or less, more preferably 1 mass% or less.

(Compounding ratio of each material)
The compounding ratio of each material constituting the container of the present invention is 40 to 90% by mass of polyolefin (A) and 3 to 30% by mass of acid-modified polyolefin (B) with respect to the total amount of the resin composition forming the container. The barrier resin (C) is 3 to 30% by mass. The polyolefin (A) is preferably 50 to 90% by mass, the acid-modified polyolefin (B) is 3 to 25% by mass, the barrier resin (C) is 3 to 25% by mass, and more preferably the polyolefin (A) is 60. To 90% by mass, the acid-modified polyolefin (B) is 5 to 20% by mass, and the barrier resin (C) is 5 to 20% by mass. However, the total of the three components (A) to (C) does not exceed 100% by mass. By setting the compounding ratio of each material in the above range, the barrier performance, chemical resistance performance and deformation suppressing performance of the container can be efficiently improved, and the strength reduction of the container can be minimized. The container of the present invention preferably comprises three components, a polyolefin (A), an acid-modified polyolefin (B), and a barrier resin (C).

(Other ingredients)
In the resin composition, in addition to the three components of the polyolefin (A), the acid-modified polyolefin (B) and the barrier resin (C), various materials can be blended within a range that does not impair the effects of the present invention. .. For example, ionomers; various modified polyethylenes such as ethylene-ethyl acrylate copolymers and ethylene-methyl acrylate copolymers; polystyrenes; various polyesters such as polyethylene terephthalate; styrene-butadiene copolymers and hydrogenated products thereof; various thermoplastic elastomers. Etc. may be added.
Further, additives such as antioxidants, matting agents, heat resistance stabilizers, weather resistance stabilizers, UV absorbers, nucleating agents, plasticizers, flame retardants, antistatic agents, anti-coloring agents, lubricants, gelation inhibitors, etc., Clays such as layered silicates and additives such as nanofillers may be added. Each of these additives may be added to the molding machine in a state of being premixed with one or more of the components (A), (B) and (C).

Further, the resin composition may contain purge scraps and burrs generated in the manufacturing process of the container, and a reused resin obtained by crushing a resin solid product that has become a defective product in the obtained container. The mixing ratio of the reused resin should be 60% by mass or less as the content in the composition in order to minimize deterioration of deformation suppressing performance, deterioration of barrier performance, deterioration of strength of container, and deterioration of color tone. Is preferable, more preferably 50% by mass or less, and further preferably 40% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more. When a reuse resin is mixed as a partial substitute for the polyolefin used, the content of the barrier resin (C) in the container may increase. Also in that case, in order to prevent the strength of the molded product from being greatly reduced, the reuse resin is blended so as to have the above-mentioned blending ratio of the components (A), (B) and (C).

[container]
The container of the present invention can have any shape as long as it can contain a liquid containing an alkylene glycol alkyl ether. Specific examples thereof include a bottle shape, a tank shape, and a drum shape, but are not limited thereto. The average thickness of the body of the container is preferably 0.5 mm or more from the viewpoint of the barrier property of the container, the chemical resistance performance, the deformation suppressing performance, and the strength. Further, from the viewpoint of reducing the weight and cost of the container, it is preferably 5.0 mm or less, more preferably 2.5 mm or less, and further preferably 1.5 mm or less. The average thickness of the body of the container is measured by the method described in Examples.

Further, the barrier resin (C) is dispersed in layers in the resin composition, and the dispersed barrier resin (C) may partially and continuously form a continuous phase. It is preferable that the barrier resin (C) dispersed in a layered state is in a dispersed state such that it is present alternately with other resin components in the thickness direction of the container wall. Further, it is preferable that the barrier resin (C) is arranged in a larger amount outside the center of the thickness of the container wall.
The container of the present invention preferably has a single-layer structure consisting of only a layer formed of a resin composition containing the above components (A) to (C), but the above components (A) to (C) are included. It may have a multi-layer structure in which one or more layers other than the layer formed from the resin composition containing the same are combined.

[Method of manufacturing container]
The container of the present invention is produced from the resin composition described above by using a molding machine, and by extruding the resin composition from the molding machine, the barrier resin (C) is dispersed in a layered form in the resin composition. You can get a good container. The molding machine includes a single-screw extruder, a die head, and a communication section that sends the resin composition from the single-screw extruder to the die head.
The container of the present invention is preferably manufactured by the direct blow method. Further, the die head may be composed of either a straight die or a cross head die, but is preferably composed of a cross head die.
As one embodiment of the production method of the present invention, the method described in paragraphs [0043] to [0059] of WO 2015/037459 is referred to.

[Liquid containing alkylene glycol alkyl ether]
The liquid containing the alkylene glycol alkyl ether according to the present invention may be composed of only the alkylene glycol alkyl ether, or may be a composition containing the alkylene glycol alkyl ether. The present inventors have found a new problem that the container is deformed when a liquid containing an alkylene glycol alkyl ether is hermetically stored in a conventional polyolefin container, and such a problem may occur in any contents. is not.
In the present invention, the amount of the alkylene glycol alkyl ether in the liquid is not particularly limited, but the deformation suppressing performance becomes more obvious as the content of the alkylene glycol alkyl ether increases. For example, when the content of the alkylene glycol alkyl ether in the liquid is 10% by mass or more, the deformation suppression performance is clearly expressed, and when the content is 30% by mass or more, the deformation suppression performance is more clearly expressed, and 50% by mass. If it is at least %, the manifestation of the deformation suppressing performance is more clear.

Examples of the alkylene glycol alkyl ether include alkylene glycol monoalkyl ether and alkylene glycol dialkyl ether.
As the alkylene glycol monoalkyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene Examples thereof include glycol monomethyl ether and dipropylene glycol monoethyl ether.

As the alkylene glycol dialkyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene Examples thereof include glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

Among the compounds of the above-mentioned alkylene glycol alkyl ethers, the expression of the deformation suppressing performance is particularly clear in the diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether.

[Method for storing liquid containing alkylene glycol alkyl ether]
In the method for storing a liquid containing an alkylene glycol alkyl ether of the present invention, the liquid containing an alkylene glycol alkyl ether is contained in the container of the present invention described above. Since the container of the present invention is excellent in deformation suppressing performance with respect to alkylene glycol alkyl ether, even if a liquid containing alkylene glycol alkyl ether is put in the container and sealed, the container can be stored without being greatly deformed. The liquid containing the alkylene glycol alkyl ether stored by the storage method of the present invention is as described above.

[Container containing liquid containing alkylene glycol alkyl ether]
The alkylene glycol alkyl ether-containing liquid-containing container of the present invention contains the liquid containing the alkylene glycol alkyl ether in the container of the present invention described above. That is, the container containing the alkylene glycol alkyl ether-containing liquid of the present invention includes, as its constituent elements, the liquid containing the alkylene glycol alkyl ether and the above-mentioned container. Since the container of the present invention is excellent in the deformation suppressing performance with respect to the alkylene glycol alkyl ether, the durability and storage performance of the liquid container containing the alkylene glycol alkyl ether of the present invention and the appearance thereof are stably maintained. The liquid containing the alkylene glycol alkyl ether contained in the container containing the alkylene glycol alkyl ether-containing liquid of the present invention is as described above.

As described above, according to the present invention, even if the liquid containing the alkylene glycol alkyl ether is hermetically stored in the container, the container deformation can be suppressed to be small. Therefore, the volume change rate of the container before and after the sealed storage can be made small, and the volume change rate represented by the following formula (i) is preferably less than 1%.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Various evaluations in Examples and the like were performed by the following methods.

(1) MFR (g/10 minutes) of polyolefin (A) and acid-modified polyolefin (B)
Using a melt indexer manufactured by Toyo Seiki Seisakusho, the melt flow rate was measured according to JIS K7210 at a temperature and load based on Appendix B, that is, at 190° C. and 2.16 kgf.

(2) Density (g/cm ³ ) of polyolefin (A) and acid-modified polyolefin (B)
A single-layer sheet having a thickness of about 1 mm was formed using a sheet forming machine including an extruder, a T-die, a cooling roll, a take-up machine and the like. Then, a test piece measuring 50 mm in length and 50 mm in width was cut from the sheet, and the true specific gravity was determined by a true specific gravity meter.

(3) Acid value of acid-modified polyolefin (B) (mg/g)
The measurement was performed by neutralization titration according to JIS K0070. 1 g of the acid-modified polyolefin was precisely weighed and dissolved in 100 mL of xylene with stirring at about 120°C. After completely dissolved, a phenolphthalein solution was added, and neutralization titration was performed using a 0.1 mol/L potassium hydroxide ethanol solution whose accurate concentration was previously determined. From the dropping amount (T), the factor (f) of 0.1 mol/L potassium hydroxide ethanol solution, 1/10 (5.611) of the formula weight of 56.11 of potassium hydroxide, and the mass (S) of the acid-modified polyolefin. The acid value was calculated by the following formula.
Acid value=T×f×5.611/S

(4) Relative Viscosity of Barrier Resin (C) (Metaxylylene Group-Containing Polyamide) 0.2 g of metaxylylene group-containing polyamide was precisely weighed and dissolved in 20 mL of 96% sulfuric acid at 20 to 30° C. with stirring. After completely dissolving, 5 ml of the solution was immediately taken in a Canon Fenske viscometer, left for 10 minutes in a constant temperature layer at 25° C., and then a dropping time (t) was measured. Further, the fall time (t ₀ ) of 96% sulfuric acid itself was measured under the same conditions. The relative viscosity was calculated from t and t ₀ by the following formula.
Relative viscosity=t/t ₀
(5) Melting point of polyolefin (A), acid-modified polyolefin (B), and barrier resin (C) Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60), under a nitrogen stream. Then, the sample is melted from room temperature to 280° C. at a heating rate of 10° C./min, the measurement sample is rapidly cooled using liquid nitrogen, and the temperature is again raised from room temperature to 280° C. at a rate of 10° C./min. Was measured. Then, the temperature at the top of the melting peak was read from the obtained chart.
(6) Thickness of container body The thickness of the container body produced in Examples and Comparative Examples was measured as follows.
The thickness at the position at a height of 10 mm from the bottom of the container was measured in four directions (0°, 90°, 180°, 270°) using a magnetic thickness gauge (manufactured by Olympus Co., Ltd., trade name: “MAGNAMIKE8500”). Was measured, and the average value was used as the thickness of the container body.
(7) Barrier performance of container After various liquids were put into the container prepared in Production Example, the mouth opening was heat-sealed with an aluminum foil laminated film, and a cap was attached, and the total mass was measured and recorded. Then, the container in which the liquid was sealed was stored in a hot air dryer at 60° C., the total mass was recorded every 24 hours, and this was continued for 3 days. The amount of mass reduction corresponds to the amount of permeation. The amount of mass reduction per day at this time was defined as the transmittance (g/bottle·day).
(8) Volume change rate Add 400 ml of water to a 1000 ml graduated cylinder, and immerse the container before and after the barrier performance measurement (the one where the mouth opening is heat-sealed with aluminum foil laminated film and further capped) in the graduated cylinder. The volume before and after container deformation was calculated from the volume increment. The volume change rate was calculated by the following formula (i).
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.)

<Used polyolefin (A)>
Nippon Polyethylene Co., Ltd., high-density polyethylene, trade name: Novatec HD HB420R, MFR = 0.2 g/10 minutes, density = 0.956 g/cm ³ , melting point = 133°C.

<Used acid-modified polyolefin (B)>
Mitsui Chemicals, Inc., acid-modified polyethylene, trade name: Admer AT1000, MFR=1.8 g/10 min (190° C., 2.16 kgf), density=0.927 g/cm ³ , acid value=9.5 mg/ g, melting point=123° C.

<Used barrier resin (C)>
Mitsubishi Gas Chemical Co., Inc., polymeta-xylylene adipamide, trade name: MX Nylon S6121, relative viscosity=3.5, melting point=237° C.

Production Example 1 (Production of Container 1)
Diameter=50 mm, L/D=25, length ratio of supply section/compression section/measurement section=33/33/33%, compression ratio=2.5 single screw extruder with full flight screw inserted, adapter, Using a single-layer direct blow container molding machine equipped with a cylindrical die with a parison controller (die head; width of the narrowest part of the die hole: 1 mm), a die, a mold clamping machine, a cooler, etc. Was molded. From the extruder hopper, the mixed pellets obtained by dry blending at the ratio of polyolefin (A)/acid-modified polyolefin (B)/barrier resin (C)=80/10/10 (mass %) were put into a single-screw extruder. The parison was extruded from a cylindrical die at a screw rotation speed of 30 rpm, and a container with an internal volume of 350 ml, an average thickness of the body portion of 1 mm, and a container mass of 37 g was molded by the direct blow method. At that time, the cylinder temperature of the extruder was set to C1/C2/C3=180/190/230° C., the temperature of the adapter was set to 240° C., and the temperature of the die head was set to 240° C. Note that C1, C2, and C3 are the cylinder temperatures of the parts corresponding to the supply part, the compression part, and the metering part, respectively.
The container obtained in Production Example 1 is cut in the horizontal direction, and a photograph showing an enlarged cross section thereof is shown in FIG. The dispersed state of the barrier resin (C) on the container wall was observed by staining with iodine tincture.

Production Example 2 (Production of Container 2)
A container 2 was produced in the same manner as in Production Example 1 except that only the polyolefin (A) was used and the acid-modified polyolefin (B) and the barrier resin (C) were not mixed.

Examples 1-2 and Comparative Examples 1-2
Diethylene glycol dimethyl ether or diethylene glycol ethyl methyl ether was placed in the obtained containers 1 and 2, and the barrier performance and volume change rate of the containers were evaluated. The specific combinations of container and contents and the evaluation results are shown in Table 1 below.

Claims (12)

A container for containing a liquid containing an alkylene glycol alkyl ether,
A polyolefin (A) 40 to 90% by mass, an acid-modified polyolefin (B) 3 to 30% by mass, and a barrier resin (C) 3 to 30% by mass, and a barrier in the resin composition. Resin (C) is dispersed in layers ,
The alkylene glycol alkyl ether is diethylene glycol dimethyl ether,
Polyolefin (A) is high density polyethylene, the barrier resin (C) is Ru Ah with m-xylylene group-containing polyamide, container. The barrier resin (C) includes a diamine unit containing 70 mol% or more of metaxylylenediamine units, and a dicarboxylic acid unit containing 70 mol% or more of α,ω-linear aliphatic dicarboxylic acid units having 4 to 20 carbon atoms. The container according to claim 1 , wherein the container is a polyamide. The container according to claim 1 or 2 , wherein the container body has an average thickness of 0.5 mm or more. Volume change rate represented by the following formula (i) is less than 1%, container of any of claims 1-3.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.) A method for storing a liquid containing an alkylene glycol alkyl ether, comprising:
A polyolefin (A) 40 to 90% by mass, an acid-modified polyolefin (B) 3 to 30% by mass, and a barrier resin (C) 3 to 30% by mass, and a barrier in the resin composition. The liquid is contained in a container in which the volatile resin (C) is dispersed in a layered form, and the alkylene glycol alkyl ether is diethylene glycol dimethyl ether,
Polyolefin (A) is high density polyethylene, the barrier resin (C) is Ru Ah with m-xylylene group-containing polyamide, preservation method. The barrier resin (C) includes a diamine unit containing 70 mol% or more of metaxylylenediamine units, and a dicarboxylic acid unit containing 70 mol% or more of α,ω-linear aliphatic dicarboxylic acid units having 4 to 20 carbon atoms. The storage method according to claim 5 , wherein the storage method is polyamide. The storage method according to claim 5 , wherein the container body has an average thickness of 0.5 mm or more. Volume change rate represented by the following formula (i) is less than 1%, storage method according to any one of claims 5-7.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.) A container containing a liquid containing an alkylene glycol alkyl ether, the container containing a liquid containing an alkylene glycol alkyl ether,
The container comprises a resin composition containing 40 to 90% by mass of a polyolefin (A), 3 to 30% by mass of an acid-modified polyolefin (B), and 3 to 30% by mass of a barrier resin (C). In which the barrier resin (C) is dispersed in layers ,
The alkylene glycol alkyl ether is diethylene glycol dimethyl ether,
Polyolefin (A) is high density polyethylene, the barrier resin (C) is Ru Ah with m-xylylene group-containing polyamide, alkylene glycol alkyl ether containing liquid-filled container. The barrier resin (C) includes a diamine unit containing 70 mol% or more of metaxylylenediamine units, and a dicarboxylic acid unit containing 70 mol% or more of α,ω-linear aliphatic dicarboxylic acid units having 4 to 20 carbon atoms. The container containing a liquid containing an alkylene glycol alkyl ether according to claim 9 , wherein the container is a polyamide containing. The alkylene glycol alkyl ether-containing liquid-containing container according to claim 9 or 10 , wherein the container body has an average thickness of 0.5 mm or more. Volume change rate represented by the following formula (i) is less than 1%, alkylene glycol alkyl ether containing liquid-filled container according to any of claims 9-11.
(A−B)/A×100 Formula (i)
(A represents the volume of the container before containing the liquid containing the alkylene glycol alkyl ether, and B is the volume of the container after storing the container containing the liquid containing the alkylene glycol alkyl ether in an atmosphere of 60° C. for 72 hours. Represents.)