DE112022005761T5 - SQUEEZER CONTAINER - Google Patents

Abstract

[R ist eine Alkylengruppe mit 1 bis 4 Kohlenstoffatomen, und R¹ bis R¹⁸ sind jeweils unabhängig voneinander ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen.]

Provided is a squeeze container having an oxygen barrier layer formed from an active energy ray curable composition containing an alicyclic epoxy compound represented by the following formula (1).

[R is an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]

Description

TECHNICAL AREA

One embodiment of the present invention relates to a squeeze container.

BACKGROUND

Conventionally, a container that allows contents (examples: drugs, quasi-drugs, cosmetics), such as a liquid or cream contained in the container, to be squeezed out by squeezing a flexible container from the outside is called a squeeze container and is widely used.

When the contents contained in the squeeze container come into contact with atmospheric oxygen, desirable properties of the contents may be affected, for example by deterioration, and a barrier layer, such as an oxygen barrier layer, may be formed in the squeeze container to prevent such deterioration of the contents.

As a container in which such a barrier layer is formed, for example, a barrier tube container described in Patent Literature 1 is known.

CITATION LIST

Patent literature

Patent Literature 1: JP H11-321895 A

SUMMARY OF THE INVENTION

However, the conventional squeeze container in which the barrier layer is formed still leaves room for improvement in terms of oxygen barrier properties, and there is also still room for improvement in terms of adhesion between the main body of the squeeze container as a base material and the barrier layer.

An embodiment of the present invention provides a squeeze container having an oxygen barrier layer having excellent adhesion to a main body of the squeeze container and excellent oxygen barrier properties.

SOLUTION TO THE PROBLEM

As a result of intensive studies, the present inventors have completed the present invention according to the following embodiments.

1. [1] Quetschbehälter mit einer Sauerstoffbarriereschicht, gebildet aus einer mit aktiver Energiestrahlung härtbaren Zusammensetzung, enthaltend eine durch nachstehende Formel (1) dargestellte alicyclische Epoxyverbindung.
   
   [R ist eine Alkylengruppe mit 1 bis 4 Kohlenstoffatomen, und R¹ bis R¹⁸ sind jeweils unabhängig voneinander ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen.]
2. [2] Der Quetschbehälter gemäß [1], in welchem die mit aktiver Energiestrahlung härtbare Zusammensetzung ein weichheitsverleihendes Mittel enthält.
3. [3] Der Quetschbehälter gemäß [2], in welchem das weichheitsverleihende Mittel Polycaprolactontriol ist.
4. [4] Der Quetschbehälter gemäß [2] oder [3], in welchem ein Molekulargewicht des weichheitsverleihenden Mittels 1000 oder weniger beträgt.
5. [5] Der Quetschbehälter gemäß einem beliebigen von [2] bis [4], in welchem ein Gehalt des weichheitsverleihenden Mittels 7 bis 20 Masse-%, bezogen auf 100 Masse-% von einem nichtflüchtigen Gehalt der mit aktiver Energiestrahlung härtbaren Zusammensetzung, beträgt.
6. [6] Der Quetschbehälter gemäß einem beliebigen von [1] bis [5], in welchem eine Dicke der Sauerstoffbarriereschicht 5 bis 10 µm beträgt.

The embodiments of the present invention are as follows.

1. [1] A squeeze container having an oxygen barrier layer formed from an active energy ray curable composition containing an alicyclic epoxy compound represented by the following formula (1).
   
   [R is an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]
2. [2] The squeeze container according to [1], in which the active energy radiation curable composition contains a softening agent.
3. [3] The squeeze container according to [2], in which the softening agent is polycaprolactone triol.
4. [4] The squeeze container according to [2] or [3], in which a molecular weight of the softening agent is 1000 or less.
5. [5] The squeeze container according to any one of [2] to [4], in which a content of the softening agent is 7 to 20 mass% based on 100 mass% of a nonvolatile content of the active energy ray-curable composition.
6. [6] The squeeze container according to any one of [1] to [5], in which a thickness of the oxygen barrier layer is 5 to 10 µm.

ADVANTAGEOUS EFFECTS OF THE INVENTION

According to an embodiment of the present invention, it is possible to provide a squeeze container having an oxygen barrier layer that is excellent in adhesion to a squeeze container main body and has an excellent oxygen barrier property.

BRIEF DESCRIPTION OF THE DRAWINGS

• 1 is a schematic view illustrating an example of a side view of a squeeze container (or a squeeze container main body) according to an embodiment of the present invention.

DESCRIPTION OF THE EMBODIMENTS

Squeeze container

A squeeze container (hereinafter also referred to as the "present container") according to an embodiment of the present invention has an oxygen barrier layer formed of an active energy ray curable composition containing an alicyclic epoxy compound represented by formula (1) below, and specifically, has a squeeze container main body (squeeze container before formation of an oxygen barrier layer) and the oxygen barrier layer formed on the outer side thereof.

The present container need only contain the squeeze container main body and the oxygen barrier layer, but may also contain conventionally known layers if necessary.

Examples of the conventionally known layer include a printed layer (e.g., a digital ink layer) for displaying contents or for design purposes, for example. The printed layer is usually formed on at least a part of the oxygen barrier layer (a side of the oxygen barrier layer opposite to the squeeze container main body).

Incidentally, a conventionally known layer such as an adhesive layer or the like may be provided between the squeeze container main body and the oxygen barrier layer, but according to an embodiment of the present invention, since the present container in which the squeeze container main body and the oxygen barrier layer are in sufficiently close contact can be obtained even without such a layer, it is preferable that such a layer is not provided, for example, in view of the manufacturing cost, the ease of manufacturing the present container.

The application of the present container is not specifically limited, and examples thereof include applications such as the use, storage, transport or other of: pharmaceutical products, quasi-pharmaceutical products, cosmetics, food, materials for construction, civil engineering or agriculture, and others in a liquid, creamy or other state. Applications for the use, storage, transport or other of liquid foundations, creams, facial foams or others are particularly preferred.

Oxygen barrier layer

The oxygen barrier layer is not specifically limited as long as it is a layer formed from an active energy ray-curable composition containing an alicyclic epoxy compound represented by the following formula (1).

The oxygen barrier layer may be formed in two or more layers on the squeeze container main body, but the oxygen barrier layer formed on the squeeze container main body is preferably one layer in consideration of the adhesion between the squeeze container main body and the oxygen barrier layer and the squeezing properties of the present container to be achieved.

The thickness of the oxygen barrier layer is preferably 5 to 10 µm from the viewpoint of, for example, sufficiently preventing the permeation of oxygen, and preferably 5 to 7 µm from the viewpoint of easily achieving an excellent balance between an oxygen barrier property and a crushing property of the present container.

The thickness of the oxygen barrier layer formed on the squeeze container main body is usually substantially uniform, but the thickness of the oxygen barrier layer may optionally change according to the location where the oxygen barrier layer is formed.

The oxygen barrier layer may be formed only on at least a part of the squeeze container main body, and may be formed only on a part of the squeeze container main body required to suppress the permeation of oxygen, but is usually formed on the entire surface of the squeeze container main body (the entire surface of a body part of the following squeeze container main body or the entire surface excluding a mouth part of the following squeeze container main body).

Composition curable with active energy radiation

The active energy ray curable composition (hereinafter also referred to as the "present composition") is not specifically limited as long as it contains an alicyclic epoxy compound represented by the following formula (1).

Since the present composition is an active energy ray curing composition, an oxygen barrier layer can be easily formed even when a squeeze container main body having lower heat resistance is used as the squeeze container main body.

The present composition is preferably a cationically polymerizable active energy ray curable composition, and is preferably a solvent-free active energy ray curable composition from the viewpoint that the effects of the present invention are more conspicuous and an oxygen barrier layer having desirable physical properties can be easily formed on, for example, the squeeze container main body. Moreover, by using the cationically polymerizable active energy ray curable composition, even when the printed layer (particularly, the digital ink layer) is formed on the oxygen barrier layer to be formed, it is possible to use the components constituting the printed layer which migrate to the squeeze container main body and further the components which pass through the squeeze container main body and migrate to the inner surface of the squeeze container main body (migration).

Alicyclic epoxy compound

The present composition contains an alicyclic epoxy compound represented by the following formula (1).

The alicyclic epoxy compounds contained in the present composition may be of one kind or of two or more kinds.

[R is an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]

Examples of R include a methanediyl group, a 1,2-ethanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,1-ethanediyl group, a 2,2-propanediyl group, a 1,2-propanediyl group, and a 1,1-dimethyl-1,2-ethanediyl group. Among these groups, a methanediyl group and a 1,2-ethanediyl group are preferred, and a methanediyl group is more preferred.

R ¹ to R ¹⁸ each independently contain, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an i-propyl group and a t-butyl group, and among these groups, a hydrogen atom and a methyl group are preferred, and a hydrogen atom is more preferred.

As the alicyclic epoxy compound represented by the above formula (1), a compound obtained by synthesis according to a conventionally known method may be used, or a commercially available product may be used.

In the case where the present composition does not contain the following softening agent, the content of the alicyclic epoxy compound represented by the above formula (1) in the present composition is preferably 98 to 99.5 mass% based on 100 mass% of the nonvolatile content of the present composition, for example, from the viewpoint of easily obtaining an oxygen barrier layer which has excellent oxygen barrier properties and excellent adhesion to a squeeze container main body and in which cracks are almost not generated.

In the case where the present composition contains the following other components, particularly the following softening agent, the content of the alicyclic epoxy compound represented by the above formula (1) in the present composition is preferably 79.5 to 92.5 mass% based on 100 mass% of the non-volatile content of the present composition, for example, from the viewpoint of easily achieving an excellent balance between the oxygen barrier properties, the adhesion to a squeeze container main body and the squeeze properties of the container in question.

The non-volatile portion of the present composition refers to components other than the solvent and dispersant in the present composition.

Additional components

The present composition may also contain components other than the alicyclic epoxy compound represented by the above formula (1) as needed, as long as the effects of the present invention are not impaired.

Examples of the other components include an active energy ray-curable compound other than the alicyclic epoxy compound represented by the above formula (1), a softening agent (plasticizer), a polymerization initiator, an antioxidant, an ultraviolet absorber, a surfactant, an antistatic agent, a flame retardant, a lubricant, a pigment (for example, an extender pigment, a color pigment), a dye, a silane coupling agent, a sensitizer, an antifoaming agent, a thickener, a leveling agent, a polymerization inhibitor, an antiseptic/antifungal agent, a pH adjusting agent, and a solvent/dispersant.

One type of these additional components may be used independently, or two or more types of them may be used.

The total content of these other components is preferably 50% by mass or less, based on 100% by mass of the non-volatile content of the present composition.

Preferably, the present composition contains, among the other components, in particular an emollient.

When the present composition contains such a softening agent, the present container having excellent squeezability can be easily obtained.

The softening agent is preferably a compound having an ester bond (-COO-), and examples thereof include acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and glyceryl triacetate; phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethyl phthalylethyl glycolate, isodecyl phthalate, diundecyl phthalate and diisoundecyl phthalate; aliphatic monobasic acid esters such as butyl oleate; aliphatic dibasic acid esters such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis(2-(2-butoxyethoxy)ethyl) adipate, bis(2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, diethyl succinate, dioctyl adipate and isodecyl succinate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol esters; trimellitic acid esters such as tris(2-ethylhexyl) trimellitate; ricinoleic acid esters such as methyl acetyl ricinoleate; pyromellitic acid esters; polyesters obtained by reacting dibasic acids and dihydric alcohols; poly(meth)acrylic acid esters such as poly(meth)acrylic acid alkyl esters; Polyester polyols such as polycaprolactone triol and polycaprolactone diol; acetylated monoglycerides such as glyceryl diacetomonolaurate; and epoxides such as epoxidized soybean oil, epoxidized linseed oil and benzyl epoxy stearate.

Among them, polyester polyols are preferred, and polycaprolactone triol is preferred from the viewpoint that, for example, the present squeeze container has an excellent balance among oxygen barrier properties, adhesion to the squeeze container main body, and squeezing properties.

The molecular weight of the softening agent is preferably 1,000 or less, more preferably 850 or less, and still more preferably 550 or less from the viewpoint that, for example, a solvent-free composition having excellent coatability on the squeeze container main body can be easily obtained and that the present container has an excellent balance among oxygen barrier property, adhesion to the squeeze container main body, and squeezing property, the lower limit of which is not specifically limited but is, for example, 300.

In the case where the present composition contains a softening agent, the content of the softening agent is preferably 7 to 20 mass%, and more preferably 9 to 15 mass%, based on 100 mass% of the nonvolatile content of the present composition, for example, from the viewpoint of easily obtaining the present container having an excellent balance between oxygen barrier properties, adhesion to a squeeze container main body, and squeezing properties.

Squeeze container main body

The squeeze container main body is not specifically limited as long as it is a flexible container capable of squeezing out the object stored in the container by external pressure.

The shape of the squeeze container main body is not particularly limited and may be the shape of a conventionally known squeeze container, and examples thereof include a squeeze container including a head portion having a mouth part 1 and a shoulder part 3 and a body part 2 (a part to be squeezed when the present container is squeezed) connected to the mouth part 1, as shown in 1 illustrated.

A preferred example of the shape of the squeeze container main body is a tube container.

The squeeze container main body is preferably a squeeze container main body made of a thermoplastic resin which contains a thermoplastic resin.

The thermoplastic resin preferably contains polyethylene, and more preferably contains low density polyethylene. That is, the squeeze container main body is preferably a squeeze container main body made of polyethylene, and more preferably a squeeze container main body made of low density polyethylene.

The polyethylene may be a biomass-derived resin or a fossil fuel-derived resin and is preferably an injection-moldable resin.

The thermoplastic resin contained in the squeeze container main body may be a single type or two or more types.

The squeeze container main body may contain additives such as stabilizers such as an antioxidant, a heat resistance stabilizer, a light resistance stabilizer and a weather resistance stabilizer, an ultraviolet scattering agent, an antiskid agent, an antifogging agent, a colorant, a dispersant, a filler, an antistatic agent, a lubricant, a softener, a plasticizer and a processing aid as long as the effects of the present invention are not impaired, as necessary.

The squeeze container main body may contain one of these additives alone, or may contain two or more of these additives.

The squeeze container main body is not particularly limited, but is preferably an injection-molded squeeze container main body formed by injection molding, for example, from the viewpoint that a desirably shaped squeeze container main body can be easily formed.

In the case where the squeeze container main body is a 1 illustrated, the squeeze container main body is preferably an injection-molded squeeze container main body in which the head portion and the body part are integrally molded. In that case, the tube container main body can be formed, for example, by welding the end of the body part on the side opposite to the head portion.

The thickness of the body part of the squeeze container main body can be appropriately selected according to a desirable application, but is preferably 1.0 mm or less, more preferably 0.5 to 1.0 mm, and even more preferably 0.5 to 0.9 mm from the viewpoint that the present container can be easily squeezed when the present container is used by squeezing to contents, and that the present container with excellent flexibility can be easily obtained, for example.

The squeeze container main body containing a polyethylene is preferable because the squeeze container main body can be easily manufactured into an injection-molded squeeze container main body whose body part has such a thickness, and further becomes an injection-molded squeeze container main body having excellent moldability, flexibility and stress crack resistance even if the body part has such a thickness.

The length of the squeeze container main body can be appropriately selected according to a desirable application, and is preferably 10 cm or more, more preferably 10 to 20 cm.

The squeeze container main body containing a polyethylene is preferable because the squeeze container main body can be easily manufactured into an injection-molded squeeze container main body whose body part has such a length, and further becomes an injection-molded squeeze container main body excellent in moldability, flexibility and stress crack resistance even if the body part has such a length.

Manufacturing process of the present container

For example, the present container can be manufactured by providing the present composition on a squeeze container main body and irradiating the present composition with an active energy ray to cure the present composition.

Examples of the method for applying the present composition to the squeeze container main body include a method for applying the present composition to the squeeze container main body by a known coating method such as a roll coater, a curtain coater or various types of printing, and a method for applying the present composition to the squeeze container main body by dipping the squeeze container main body in the present composition.

Alternatively, the present composition may be coated on a support to form a film, and then the film may be transferred to the squeeze container main body.

Before the present composition is applied to the squeeze container main body, the squeeze container main body may be subjected to a treatment such as a corona discharge treatment, a flame treatment, an ultraviolet treatment, a radio frequency treatment, a glow discharge treatment, an active plasma treatment or a laser treatment.

Examples of the active energy radiation include light radiation such as far ultraviolet radiation, ultraviolet radiation, near ultraviolet radiation and infrared radiation; electromagnetic waves such as X-rays and γ-rays; electron radiation, proton radiation, neutron radiation, for example. Among them, ultraviolet and/or electron radiation are preferred because they cause less damage to the squeeze container main body, for example.

The irradiation time depends on the light intensity, the thickness of the oxygen barrier layer to be formed and the composition present, but is usually about 0.1 to 10 seconds.

Once the present composition has cured, heating may be applied if necessary to promote polymerization.

EXAMPLES

An embodiment of the present invention will now be described in more detail by way of examples, but the present invention is not limited thereto.

[Example 1]

A surface (outer surface) of a container (injection-molded container in which head and body are integrally formed, with a 1 illustrated shape, thickness of the body part: 0.7 mm, A low-density polyethylene (LDPE) main body (length of body part: 18 cm) was subjected to corona discharge treatment (distance between electrodes: 5 mm, number of revolutions: 60 rpm, treatment time: 1 second) to obtain a squeeze container main body having a wetting tension of 72 dynes as measured with a wetting tension test mixture (manufactured by FUJIFILM Wako Pure Chemical Corporation).

A 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate was coated on the corona discharge treated surface of the obtained squeeze container main body using a roll coater so that the thickness of the resulting oxygen barrier layer was 7 μm, and ultraviolet rays were irradiated using a UV exposure device (metal halide lamp) so that the integrated light amount was 531 mJ/cm ² (intensity: 1710 mW/cm ² , irradiation distance: 65 mm, number of revolutions: 50 rpm, irradiation power: 120 W, irradiation time: 3 seconds), thereby preparing a squeeze container having an oxygen barrier layer.

[Example 2]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 1, except that a composition obtained by previously mixing 100 parts by mass of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 14 parts by mass of polycaprolactone triol (molecular weight: 300) was used instead of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate of Example 1.

[Example 3]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that polycaprolactone triol (molecular weight: 550) was used instead of polycaprolactone triol (molecular weight: 300) in Example 2.

[Example 4]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that polycaprolactone triol (molecular weight: 850) was used instead of polycaprolactone triol (molecular weight: 300) in Example 2.

[Example 5]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that the oxygen barrier layer was formed such that the thickness of the oxygen barrier layer of Example 2 was 5 µm.

[Example 6]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that the oxygen barrier layer was formed such that the thickness of the oxygen barrier layer of Example 2 was 10 µm.

[Example 7]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that the amount of polycaprolactone triol (molecular weight: 300) used in Example 2 was changed to 11 parts by mass.

[Example 8]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that the amount of polycaprolactone triol (molecular weight: 300) used in Example 2 was changed to 17 parts by mass.

[Example 9]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 2 except that dibutyl phthalate (molecular weight: 278) was used instead of polycaprolactone triol (molecular weight: 300) in Example 2.

[Comparison example 1]

The squeeze container main body before corona discharge treatment (squeeze container without oxygen barrier layer) used in Example 1 was used as it was.

[Comparison example 2]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 1 except that urethane acrylate (Forseed No. 300 M [manufactured by CHUGOKU MARINE PAINTS, LTD.]) was used instead of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate of Example 1.

[Comparison example 3]

A squeeze container having an oxygen barrier layer was prepared in the same manner as in Example 1 except that EVOH containing an inorganic layer filler (Ecostage GB [manufactured by SAKATA INX CORPORATION]) was used instead of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate of Example 1.

Oxygen barrier property (oxygen cut ratio)

The oxygen barrier property (oxygen cut ratio) of the squeeze container having the oxygen barrier layer prepared in each of the Examples and Comparative Examples was measured as follows.

In a nitrogen-filled glove box, a mouth part and a hem part (an end part of the body part 2 in 1 on a side opposite to the mouth part 1) of the squeeze container was sealed with aluminum, and the squeeze container, in which the interior was filled with nitrogen, was sealed.

$$\begin{array}{l}\text{k}=\left(\mathrm{21,0}\times {\text{Peakfl}\ddot{\text{a}}\text{che von N}}_2\text{ in Luft}\right)/(\mathrm{78,1}\times \text{Peakfl}\ddot{\text{a}}\text{che von}\\ {\text{O}}_2\text{ in Luft})\end{array}$$

$$\begin{array}{l}\text{Sauerstoffvolumen }\left[{\text{cm}}^{\text{3}}\right]\text{ im Quetschbeh}\ddot{\text{a}}\text{lter}=\\ \text{Sauerstoffkonzentration }\left[\%\right]\times {10}^{-2}\times \text{Volumen }\left[{\text{cm}}^{\text{3}}\right]\text{ des}\\ \text{Quetschbeh}\ddot{\text{a}}\text{lters}\end{array}$$

$$\begin{array}{l}\text{Sauerstoffdurchl}\ddot{\text{a}}\text{ssigkeit }\left[{\text{cm}}^3/\text{Tag}/\text{Verpackung}\right]=\text{Steigung der}\\ \text{N}\ddot{\text{a}}\text{herungskurve der }\ddot{\text{U}}\text{bergangskurve des Sauerstoffvolumens im}\\ \text{Quetscbeh}\ddot{\text{a}}\text{lter}\end{array}$$

$$\begin{array}{l}\text{Oxygen-Cut-Verh}\ddot{\text{a}}\text{ltnis }\left[\%\right]=\{1-(\text{Sauerstoffdurchl}\ddot{\text{a}}\text{ssigkeit}\\ \text{des Quetschbeh}\ddot{\text{a}}\text{lters mit}\\ \text{Sauerstoffbarriereschicht}/\text{Sauerstoffdurchl}\ddot{\text{a}}\text{ssigkeit des}\\ \text{Quetschbeh}\ddot{\text{a}}\text{lters aus Vergleichsbeispiel 1})\}\times 100\end{array}$$

This squeeze container was stored in a thermo-hygrostat at 23°C and 50% RH, and thereafter, the squeeze container of Comparative Example 1 was taken out from the thermo-hygrostat four times every two days, and for the squeeze containers having an oxygen barrier layer prepared in Examples and Comparative Examples other than Comparative Example 1, the squeeze container was taken out from the thermo-hygrostat four times every one week, the oxygen concentration inside each squeeze container was measured by gas chromatography (Clarus 680, manufactured by PerkinElmer Inc.), and the oxygen cut ratio was calculated by the following formula. The results are shown in Table 1. The oxygen cut ratio described in Table 1 is an average value of oxygen cut ratios measured using six squeeze containers each having an oxygen barrier layer prepared in each of the Examples and Comparative Examples. $$\begin{array}{l}\text{Oxygen concentration}\left[\%\right]={\text{<figure-callout id="2" label="O" filenames="DE112022005761T5\_0010.png" state="{{state}}">O</figure-callout>}}_{\text{2}}-\text{Peakfl}\ddot{\text{a}}\text{che}\times \\ \text{k}/\left({\text{<figure-callout id="2" label="N" filenames="DE112022005761T5\_0010.png" state="{{state}}">N</figure-callout>}}_{\text{2}}-\text{Peakfl}\ddot{\text{a}}\text{che}+{\text{<figure-callout id="2" label="O" filenames="DE112022005761T5\_0010.png" state="{{state}}">O</figure-callout>}}_{\text{2}}-\text{Peakfl}\ddot{\text{a}}\text{che}\times \text{k}\right)\times 100\end{array}$$

$$\begin{array}{l}\text{k}=\left(21.0\times {\text{Peakfl}\ddot{\text{a}}\text{che of <figure-callout id="2" label="N" filenames="DE112022005761T5\_0010.png" state="{{state}}">N</figure-callout>}}_2\text{in air}\right)/(78.1\times \text{Peakfl}\ddot{\text{a}}\text{che of}\\ {\text{<figure-callout id="2" label="O" filenames="DE112022005761T5\_0010.png" state="{{state}}">O</figure-callout>}}_2\text{in air})\end{array}$$

$$\begin{array}{l}\text{Oxygen volume}\left[{\text{cm}}^{\text{3}}\right]\text{in the squeeze bin}\ddot{\text{a}}\text{lter}=\\ \text{Oxygen concentration}\left[\%\right]\times {10}^{-2}\times \text{volume}\left[{\text{cm}}^{\text{3}}\right]\text{of}\\ \text{Squeeze}\ddot{\text{a}}\text{lters}\end{array}$$

$$\begin{array}{l}\text{Oxygen permeability}\ddot{\text{a}}\text{ssigkeit}\left[{\text{cm}}^3/\text{day}/\text{Packaging}\right]=\text{Slope of the}\\ \text{N}\ddot{\text{a}}\text{curve of the}\ddot{\text{U}}\text{transition curve of the oxygen volume in}\\ \text{squeeze}\ddot{\text{a}}\text{lter}\end{array}$$

$$\begin{array}{l}\text{Oxygen-cut ratio}\ddot{\text{a}}\text{ltnis}\left[\%\right]=\{1-(\text{Oxygen permeability}\ddot{\text{a}}\text{ssigkeit}\\ \text{of the squeeze}\ddot{\text{a}}\text{lters with}\\ \text{Oxygen barrier layer}/\text{Oxygen permeability}\ddot{\text{a}}\text{liquid of the}\\ \text{Squeeze}\ddot{\text{a}}\text{lters from comparative example 1})\}\times 100\end{array}$$

Adhesion (cross-cut test)

The cross-cut test was conducted as follows based on the adhesion strength (cross-cut method) of JIS K 5600-5-6: 1999.

Using the squeeze container having the oxygen barrier layer prepared in each of the examples and comparative examples, foreign matters such as dust, dust and oil on the oxygen barrier layer of the squeeze container were removed, and 11 longitudinal and transverse cuts each having a depth reaching to the squeeze container main bodies were made at intervals of 1 mm in the thus-treated part. A 15 mm wide cellophane tape (manufactured by Nichiban Co., Ltd.) was pressure-adhered to the cut surface, and then the cellophane tape was quickly peeled off at an angle of about 60° with respect to the oxygen barrier layer surface by holding the end of the cellophane tape. The remaining area ratio (%) representing the area of the oxygen barrier layer remaining on the squeeze container in the formed 100 squares was calculated. The squeeze container with the oxygen barrier layer prepared in each of the examples and comparative examples was tested using 10 samples, the average value of the residual area ratio was calculated, and the adhesiveness was evaluated according to the following criteria. The results are shown in Table 1.

Evaluation criteria

10 points: The cut edge is completely smooth and there is no peeling in any grid.
8 points: The oxygen barrier layer detaches slightly at the intersection points of the cuts and the remaining surface area is at least 95%.
6 points: The oxygen barrier layer has peeled off along the cut edge and/or at the intersection point, and the remaining area proportion is 85% or more and less than 95%.
4 points: The oxygen barrier layer was partially or completely detached along the cut edge, and the residual area proportion was 65% or more and less than 85%.
2 points: The oxygen barrier layer was partially or completely detached along the cut edge, and the residual area proportion was 35% or more and less than 65%.
0 points: The oxygen barrier layer was partially or completely detached along the cut edge and the remaining area fraction was less than 35%.

Stickiness

Using the squeeze container having the oxygen barrier layer prepared in each of the Examples and Comparative Examples, when the finger was rotated by 45° while pressing the oxygen barrier layer with the finger for 2 to 3 seconds immediately after irradiation with ultraviolet rays, the case where the oxygen barrier layer did not stick to the finger was evaluated as ○, and the case where the oxygen barrier layer stuck to the finger was evaluated as ×. The results are shown in Table 1.

Crushing property

A printed layer was printed on the oxygen barrier layer by inkjet printing using the squeeze container having the oxygen barrier layer prepared in each of the examples and comparative examples. The squeeze container on which the printed layer was printed was wrung out and kept for 10 seconds, and then the surface of the printed layer was after the force was released at the time of wringing was observed using a microscope, and the crushing property was evaluated according to the following evaluation criteria. The results are shown in Table 1.

Evaluation criteria

10 points: The printed layer does not peel off.
8 points: There are fine point-like detachments of a few millimeters and/or linear detachments, and the area of the detached part of the printed layer is less than 15% of the photographed area when photographed with a microscope (10x magnification).
6 points: The area of the detached part of the printed layer when photographed with a microscope (10x magnification) is 15% or more and less than 35% of the photographed area.
4 points: The area of the detached part of the printed layer when photographed with a microscope (10x magnification) is 35% or more and less than 65% of the photographed area.
2 points: The area of the detached part of the printed layer when photographed with a microscope (10x magnification) is 65% or more of the photographed area. [Table 1] Oxygen barrier property Adhesive strength Stickiness Crushing property Example 1 77.0% 10 points ◯ 6 points Example 2 74.3% 10 points ◯ 10 points Example 3 - 10 points ◯ 10 points Example 4 61.4% 10 points ◯ 10 points Example 5 66.9% 10 points ◯ 10 points Example 6 79.1% 10 points ◯ 10 points Example 7 73.6% 10 points ◯ 10 points Example 8 67.6% 10 points ◯ 10 points Example 9 54.0% 10 points ◯ 10 points Comparison example 1 - - - - Comparison example 2 38.2% 2 points ◯ 2 points Comparison example 3 73.0% 4 points ◯ 6 points

REFERENCE SIGN LIST

1

Mouthpiece

2

Body part

3

Shoulder part

QUOTES INCLUDED IN THE DESCRIPTION

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Cited patent literature

• JP H11321895 A [0005]

Claims (6)

A squeeze container comprising an oxygen barrier layer formed of an active energy ray curable composition comprising an alicyclic epoxy compound represented by the following formula (1):

wherein R is an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Squeeze container according to Claim 1 wherein the active energy radiation curable composition comprises a softening agent. Squeeze container according to Claim 2 , where the softening agent is polycaprolactone triol. Squeeze container according to Claim 2 or 3 wherein a molecular weight of the softening agent is 1000 or less. Squeeze container according to any of the Claims 2 until 4 wherein a content of the softening agent is 7 to 20 mass% based on 100 mass% of a non-volatile content of the active energy ray-curable composition. Squeeze container according to any of the Claims 1 until 5 , wherein the thickness of the oxygen barrier layer is 5 to 10 µm.

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