WO2023100633A1

WO2023100633A1 - Squeeze container

Info

Publication number: WO2023100633A1
Application number: PCT/JP2022/042250
Authority: WO
Inventors: 宗明鍋田; 義弘松下; 信保首藤; 健司大西
Original assignee: 大成化工株式会社
Priority date: 2021-12-03
Filing date: 2022-11-14
Publication date: 2023-06-08
Also published as: JP2023082922A; DE112022005761T5; CA3240835A1

Abstract

This squeeze container has an oxygen barrier layer formed from an active energy ray-curable composition containing a cycloaliphatic epoxy compound represented by formula (1). (R is a C1-C4 alkylene group, R1-R18 are each independently a hydrogen atom or a C1-C4 alkyl group.)

Description

squeeze container

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

Conventionally, by pressing a flexible container from the outside, a liquid-like or cream-like content contained in the container (e.g., pharmaceuticals, quasi-drugs, cosmetics) can be pushed out. are known as squeeze containers and are widely used.

When the contents contained in the squeeze container come into contact with oxygen in the air, the desired characteristics of the contents may be impaired due to deterioration or the like. In order to suppress such as, a barrier layer such as an oxygen barrier layer is sometimes formed in the squeeze container.

As a container having such a barrier layer formed thereon, for example, the barrier tube container described in Patent Document 1 is known.

JP-A-11-321895

However, the conventional squeeze container formed with a barrier layer has room for improvement in terms of oxygen barrier properties, and also in terms of adhesion between the squeeze container main body, which is the base material, and the barrier layer. rice field.

An embodiment of the present invention provides a squeeze container with excellent oxygen barrier properties, which has an oxygen barrier layer with excellent adhesion to the squeeze container body.

As a result of earnest research, the inventors of the present invention have completed the present invention according to the following configuration example.
A configuration example of the present invention is as follows.

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

[2] The squeeze container according to [1], wherein the active energy ray-curable composition contains a softening agent.

[3] The squeeze container according to [2], wherein the softening agent is polycaprolactone triol.

[4] The squeeze container according to [2] or [3], wherein the softening agent has a molecular weight of 1000 or less.

[5] According to any one of [2] to [4], the content of the softening agent is 7 to 20% by mass with respect to 100% by mass of the nonvolatile matter of the active energy ray-curable composition. squeeze container.

[6] The squeeze container according to any one of [1] to [5], wherein the oxygen barrier layer has a thickness of 5 to 10 μm.

According to one embodiment of the present invention, it is possible to provide a squeeze container having an oxygen barrier layer with excellent adhesion to the squeeze container body and having excellent oxygen barrier properties.

FIG. 1 is a schematic diagram showing an example of a side view of a squeeze container (or squeeze container main body) according to one embodiment of the present invention.

≪Squeeze container≫
A squeeze container according to one embodiment of the present invention (hereinafter also referred to as "this container") is formed from an active energy ray-curable composition containing an alicyclic epoxy compound represented by the following formula (1). It has a barrier layer, and more specifically, it has a squeeze container main body (the squeeze container before the oxygen barrier layer is formed) and the oxygen barrier layer formed on the outside thereof.

The container may have a squeeze container body and an oxygen barrier layer, and may have conventionally known layers as necessary.
Examples of the conventionally known layer include a printed layer (eg, digital ink layer) for displaying contents and for designing. The printed layer is usually formed on at least part of the oxygen barrier layer (the side of the oxygen barrier layer opposite to the squeeze container body).
A conventionally known layer such as an adhesive layer may exist between the squeeze container main body and the oxygen barrier layer. Even so, it is possible to obtain a container in which the squeeze container body and the oxygen barrier layer are sufficiently in close contact with each other. Therefore, considering the production cost and ease of production of the container, it is preferable that such a layer does not exist.

The use of this container is not particularly limited, but it can be used for the use, storage, transportation, etc. of liquid or cream-like pharmaceuticals, quasi-drugs, cosmetics, foods, materials for construction, civil engineering, agriculture, etc. More preferably, it is used for the use, storage, transportation, etc. of liquid foundations, creams, facial cleansing foams, and the like.

<Oxygen barrier layer>
The oxygen barrier layer is not particularly 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).
Two or more layers of the oxygen barrier layer may be formed on the squeeze container main body. The oxygen barrier layer formed on the squeeze container body is preferably one layer.

The thickness of the oxygen barrier layer is preferably 5 to 10 μm from the viewpoint of sufficiently preventing permeation of oxygen, etc., and furthermore, it is possible to easily obtain the present container which is excellent in well-balanced oxygen barrier properties and squeezing properties. It is more preferably 5 to 7 μm from the point that it is possible to
The thickness of the oxygen barrier layer formed on the squeeze container body is generally uniform, but if necessary, the thickness of the oxygen barrier layer may be varied according to the location where it is formed.

The oxygen barrier layer may be formed on at least a portion of the squeeze container main body, and may be formed only on the portion of the squeeze container main body where oxygen permeation is required to be suppressed. , is usually formed on the entire surface of the squeeze container main body (the entire surface of the body portion of the squeeze container main body described below or the entire surface of the squeeze container main body other than the mouth portion described below).

<Active energy ray-curable composition>
The active energy ray-curable composition (hereinafter also referred to as "this composition") is not particularly limited as long as it contains an alicyclic epoxy compound represented by the following formula (1).
Since the composition is active energy ray-curable, the oxygen barrier layer can be easily formed even when a squeeze container body having poor heat resistance is used as the squeeze container body.

The present composition is a cationically polymerizable active energy ray-curable composition from the viewpoint that the effect of the present invention is more exhibited and an oxygen barrier layer having desired physical properties can be easily formed on the squeeze container main body. It is preferably a non-solvent type active energy ray-curable composition. In addition, by using a cationic polymerizable active energy ray-curable composition, even if the printed layer (especially the digital ink layer) is formed on the formed oxygen barrier layer, the components forming the printed layer are squeezed. It is possible to prevent the component from migrating to the container main body, and further, from passing through the squeeze container main body and migrating to the inner surface of the squeeze container main body.

[Alicyclic epoxy compound]
The composition contains an alicyclic epoxy compound represented by the following formula (1).
The alicyclic epoxy compound contained in the present composition may be of one type or two or more types.

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

Examples of R ¹ to R ¹⁸ each independently include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an i-propyl group and a t-butyl group. A group is preferred, and a hydrogen atom is more preferred.

For the alicyclic epoxy compound represented by the formula (1), a compound synthesized by a conventionally known method may be used, or a commercially available product may be used.

When the present composition does not contain the following softening agent, the content of the alicyclic epoxy compound represented by the formula (1) in the present composition is In view of the fact that an oxygen barrier layer which is excellent in resistance to cracks and can be easily obtained, the content is preferably 98 to 99.5% by mass with respect to 100% by mass of the non-volatile content of the composition.
When the present composition contains the following other components, particularly the following softening agent, the content of the alicyclic epoxy compound represented by the formula (1) in the present composition is From the point of view of easily obtaining the present container which is excellent in well-balanced adhesion to the main body and squeezability, it is preferably 79.5 to 92.5% by mass with respect to 100% by mass of the non-volatile content of the present composition. be.
The non-volatile content of the present composition refers to components other than the solvent and dispersion medium in the present composition.

[Other ingredients]
The composition may optionally contain other components than the alicyclic epoxy compound represented by the formula (1) as long as the effects of the present invention are not impaired.
Examples of other components include active energy ray-curable compounds other than the alicyclic epoxy compound represented by the formula (1), flexibility-imparting agents (plasticizers), polymerization initiators, antioxidants, and ultraviolet rays. Absorbents, surfactants, antistatic agents, flame retardants, lubricants, pigments (including extenders, coloring pigments, etc.), dyes, silane coupling agents, sensitizers, antifoaming agents, thickeners, leveling agents, Polymerization inhibitors, preservatives/antifungal agents, pH adjusters, solvents/dispersion media can be used.
One of these other components may be used independently, or two or more of them may be used.
The total content of these other components is preferably 50% by mass or less with respect to 100% by mass of nonvolatile matter in the present composition.

Among other components, the composition preferably contains a softening agent.
When the present composition contains such a softening agent, the present container having excellent squeezability can be easily obtained.
As the softening agent, a compound having an ester bond (-COO-) is preferable, and examples thereof include acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and glycerol triacetate. Classes; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethylphthalyl ethyl glycolate, isodecyl phthalate, diundecyl phthalate, diisoundecyl phthalates such as phthalates; aliphatic monobasic acid esters such as butyl oleate; -butoxyethoxy)ethyl)adipate, bis(2-ethylhexyl)azelate, dimethyl sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, diethylsuccinate, dioctyl adipate, aliphatic dibasic acids such as isodecyl succinate Esters; 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; polyesters obtained by reacting an acid with a dihydric alcohol; 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 laurate; epoxies such as epoxidized soybean oil, epoxidized linseed oil, and benzyl epoxystearate;

Among these, polyester polyols are preferable, and polycaprolactone triol is more preferable, in terms of easily obtaining a container having an excellent balance of oxygen barrier properties, adhesion to the main body of the squeeze container, and squeezing properties.

The molecular weight of the flexibility-imparting agent makes it possible to easily obtain a solvent-free composition with excellent paintability on the main body of the squeeze container. It is preferably 1000 or less, more preferably 850 or less, and still more preferably 550 or less from the point of view that the present container can be easily obtained.

When the present composition contains a softening agent, the content of the softening agent makes it possible to easily obtain a container having an excellent balance of oxygen barrier property, adhesion to the squeeze container body, and squeezing property. From the point of view, it is preferably 7 to 20% by mass, more preferably 9 to 15% by mass, based on 100% by mass of the non-volatile content of the composition.

<Squeeze container body>
The squeeze container main body is not particularly limited as long as it is a container having flexibility and capable of pushing out the contents in the container by pressing from the outside.
The shape of the squeeze container body is not particularly limited, and may be the shape of a conventionally known squeeze container. For example, as shown in FIG. A squeeze container having a shoulder portion 3 and a body portion 2 (a portion to be squeezed when squeezing the container) is mentioned.
A preferred example of the shape of the squeeze container body is a tube container.

The squeeze container main body is preferably a squeeze container main body made of a thermoplastic resin containing 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 made of polyethylene, and more preferably made of low-density polyethylene.
The polyethylene may be a biomass-derived resin or a fossil fuel-derived resin, but is preferably an injection-moldable resin.
The thermoplastic resin contained in the squeeze container main body may be of one type alone, or may be of two or more types.

The squeeze container main body may contain stabilizers such as antioxidants, heat stabilizers, light stabilizers, and weather stabilizers, UV scattering agents, anti-slip agents, anti-fogging agents, colorants, dispersants, and fillers, if necessary. Additives such as agents, antistatic agents, lubricants, softeners, plasticizers, and processing aids may be contained within the range that does not impair the effects of the present invention.
The squeeze container main body may contain each of these additives singly or in combination of two or more.

Although the squeeze container main body is not particularly limited, it is preferably an injection-molded squeeze container main body formed by injection molding because the container main body can be easily formed into a desired shape.
When the squeeze container main body is the squeeze container main body shown in FIG. 1, it is preferably an injection-molded squeeze container main body in which the head portion and the trunk portion are integrally molded. In this case, the tube container main body can be formed by welding or the like the end of the body portion opposite to the head portion side.

The thickness of the trunk portion of the squeeze container main body may be appropriately selected according to the desired application. It is preferably 1.0 mm or less, more preferably 0.5 to 1.0 mm, still more preferably 0.5 to 0.9 mm from the viewpoint that the present container having excellent flexibility can be easily obtained.
A squeeze container body containing polyethylene can be easily made into an injection-molded squeeze container body having such a thickness of the body, and even if the body has such a thickness, injection moldability and flexibility can be easily obtained. This is preferable because the injection-molded squeeze container main body is excellent in durability and stress cracking resistance.

The length of the body of the squeeze container body may also be appropriately selected according to the desired application, preferably 10 cm or more, more preferably 10 to 20 cm.
Squeeze container bodies comprising polyethylene are easily made into injection molded squeeze container bodies of such lengths, and even with such lengths of barrels, injection moldability, flexibility and durability are maintained. This is preferable because the injection-molded squeeze container main body is excellent in stress cracking resistance.

<Manufacturing method of this container>
For example, the present container can be produced by providing the present composition on a squeeze container body and curing the present composition by irradiating it with active energy rays.

Examples of the method of providing the present composition on the squeeze container main body include a method of coating the present composition on the squeeze container main body by a known coating method such as a roll coater, a curtain coater, and various types of printing, and a method of coating the squeeze container main body with the composition. is immersed in the composition to provide the composition on the main body of the squeeze container.
Alternatively, once the present composition is coated on a support to form a film, the film may be transferred onto the main body of the squeeze container.

Before the present composition is provided on the squeeze container main body, the squeeze container main body should be subjected to corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, or the like. You can

Examples of the active energy rays include rays such as far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays and infrared rays; electromagnetic waves such as X-rays and γ-rays; Ultraviolet rays and/or electron beams are preferred because they cause less damage to the beam.

The irradiation time depends on the intensity of the light, the thickness of the oxygen barrier layer to be formed, and the present composition used, but is usually about 0.1 to 10 seconds.
When curing the present composition, it may be heated, if necessary, in order to promote polymerization.

Hereinafter, one embodiment of the present invention will be described in more detail with examples, but the present invention is not limited by these.

[Example 1]
The surface ( The outer surface) was subjected to corona discharge treatment (inter-electrode distance: 5 mm, number of revolutions: 60 rpm, treatment time: 1 second), and a mixed solution for wet tension test (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used. A squeeze container body having a wetting tension of 72 dyn was obtained.
3′,4′-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate was applied to the corona discharge-treated surface of the obtained squeeze container main body using a roll coater so that the resulting oxygen barrier layer had a thickness of 7 μm. Using a UV exposure machine (metal halide lamp), the integrated amount of light is 531 mJ/cm ² (intensity: 1710 mW/cm ² , irradiation distance: 65 mm, rotation speed: 50 rpm, irradiation output: 120 W, irradiation time: 3 seconds), a squeeze container having an oxygen barrier layer was produced.

[Example 2]
In Example 1, instead of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 100 parts by mass of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 1, except that a composition previously mixed with 14 parts by mass of polycaprolactone triol (molecular weight: 300) was used.

[Example 3]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2, except that polycaprolactone triol (molecular weight: 550) was used instead of polycaprolactone triol (molecular weight: 300).

[Example 4]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2, except that polycaprolactone triol (molecular weight: 850) was used instead of polycaprolactone triol (molecular weight: 300).

[Example 5]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2, except that the oxygen barrier layer was formed to have a thickness of 5 μm.

[Example 6]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2, except that the oxygen barrier layer was formed to have a thickness of 10 μm.

[Example 7]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2, except that the amount of polycaprolactone triol (molecular weight: 300) used was changed to 11 parts by mass.

[Example 8]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2, except that the amount of polycaprolactone triol (molecular weight: 300) was changed to 17 parts by mass.

[Example 9]
A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 2 except that dibutyl phthalate (molecular weight: 278) was used instead of polycaprolactone triol (molecular weight: 300).

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

[Comparative Example 2]
In Example 1, instead of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, urethane acrylate (Folcido No. 300M [manufactured by Chugoku Toryo Co., Ltd.]) was used. A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 1.

[Comparative Example 3]
In Example 1, EVOH containing an inorganic layered filler (Ecostage GB [manufactured by Sakata Inx Co., Ltd.]) was used instead of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. A squeeze container having an oxygen barrier layer was produced in the same manner as in Example 1.

<Oxygen barrier property (oxygen cut rate)>
The oxygen barrier property (oxygen cut rate) of the squeeze container having the oxygen barrier layer produced in each example and comparative example was measured as follows.
In a glove box filled with nitrogen, the mouth and hem of the squeeze container (the end opposite to the mouth 1 in the barrel 2 in FIG. 1) were sealed with aluminum, and the inside of the squeeze container was filled with nitrogen. Sealed.
This squeeze container was stored in a thermo-hygrostat at 23° C. and 50% RH. For the squeeze containers having an oxygen barrier layer produced in Examples and Comparative Examples other than Example 1, the squeeze containers were taken out from the constant temperature and humidity chamber four times every other week, and the oxygen concentration inside each squeeze container was measured by gas chromatography ( Measured with a Clarus 680 manufactured by Perkin Elmer), and the oxygen cut rate was calculated from the following formula. Table 1 shows the results. The oxygen cut rate shown in Table 1 is the average value of the oxygen cut rate measured using six squeeze containers each having an oxygen barrier layer produced in each example and comparative example.

Oxygen concentration [%] = _O2 peak area x k/( _N2 peak area + _O2 peak area x k) x 100
k = (21.0 x peak area of _N2 in air)/(78.1 x peak area of _O2 in air)
Oxygen volume in the squeeze container [cm ³ ]=Oxygen concentration [%]×10 ⁻² ×Volume of the squeeze container [cm ³ ]
Oxygen permeability [cm ³ /day/package] = Slope of approximate curve of transition plot of oxygen volume in squeeze container Oxygen cut rate [%] = {1-(Oxygen permeability of squeeze container having oxygen barrier layer/comparison Oxygen permeability of the squeeze container used in Example 1)}×100

<Adhesion (cross-cut test)>
The cross-cut test was performed as follows based on the adhesion (cross-cut method) of JIS K5600-5-6:1999.
Using a squeeze container having an oxygen barrier layer prepared in each of the examples and comparative examples, foreign substances such as dirt, dust and oil on the oxygen barrier layer on the squeeze container were removed. Eleven cuts having a depth reaching the body of the squeeze container on the side were made at intervals of 1 mm. After a 15 mm wide cellophane tape (manufactured by Nichiban Co., Ltd.) was crimped to the cut surface, the cellophane tape was rapidly peeled off at an angle of about 60° to the oxygen barrier layer surface while holding the edge of the cellophane tape. The remaining area ratio (%), which is the area of the oxygen barrier layer remaining on the squeeze container among the 100 squares formed, was calculated. The squeeze container having the oxygen barrier layer prepared in each of the examples and comparative examples was tested using 10 specimens, the average value of the residual area ratio was calculated, and the adhesion was evaluated according to the following criteria. Table 1 shows the results.

(Evaluation criteria)
10 points: The edge of the cut is completely smooth, and no peeling occurs in any grid mesh. 8 points: There is small peeling of the oxygen barrier layer at the intersection of the cuts, and the remaining area ratio is 95% or more. 6 points: The oxygen barrier layer. is peeled off along the edge of the cut and/or at the intersection, and the remaining area ratio is 85% or more and less than 95%. 4 points: The oxygen barrier layer is partially or completely peeled off along the edge of the cut. , residual area ratio of 65% or more and less than 85% 2 points: the oxygen barrier layer is partially or entirely peeled off along the edge of the cut, and the residual area ratio is 35% or more and less than 65% 0 points: oxygen barrier layer is partially or completely removed along the edge of the cut with less than 35% remaining area

<Tackiness>
Using a squeeze container having an oxygen barrier layer prepared in each example and comparative example, the oxygen barrier layer was pressed with a finger for 2 to 3 seconds immediately after being irradiated with ultraviolet rays, and when the finger was rotated 45°, the pressure was applied to the finger. The case where the oxygen barrier layer did not stick was evaluated as ◯, and the case where the oxygen barrier layer adhered to the finger was evaluated as x. Table 1 shows the results.

<Squeezability>
Using the squeeze container having the oxygen barrier layer produced in each example and comparative example, a printed layer was printed on the oxygen barrier layer by inkjet printing. The squeeze container printed with the printed layer is squeezed with a dust cloth and kept for 10 seconds, and then the surface of the printed layer after releasing the force of squeezing with the dust cloth is observed using a microscope and squeezed according to the following evaluation criteria. evaluated the sex. Table 1 shows the results.

(Evaluation criteria)
10 points: No peeling of the printed layer 8 points: There is fine point peeling and / or line peeling of several millimeters, and the area of the peeled part of the printed layer when photographed with a microscope (magnification: 10 times) is the photographed area Less than 15% 6 points: The area of the peeled part of the printed layer when photographed with a microscope (magnification: 10 times) is 15% or more and less than 35% of the photographed area 4 points: Photographed with a microscope (magnification: 10 times) The area of the peeled part of the printed layer when photographed is 35% or more and less than 65% of the photographed area 2 points: The area of the peeled part of the printed layer when photographed with a microscope (magnification: 10 times) is 65% or more of the photographed area

1: Mouth 2: Body 3: Shoulder

Claims

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 each of R 1 to R 18 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The squeeze container according to claim 1, wherein the active energy ray-curable composition contains a softening agent.
The squeeze container according to claim 2, wherein the softening agent is polycaprolactone triol.
The squeeze container according to claim 2 or 3, wherein the softening agent has a molecular weight of 1000 or less.
The squeeze container according to any one of claims 2 to 4, wherein the content of the softening agent is 7 to 20% by mass with respect to 100% by mass of nonvolatile matter in the active energy ray-curable composition.
The squeeze container according to any one of claims 1 to 5, wherein the oxygen barrier layer has a thickness of 5 to 10 µm.