JP2003093150A - Vessel for hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vessel for a hair cosmetic which has an EVOH layer as a barrier layer and is sufficiently prevented from lowering oxygen barrier performance of the EVOH layer due to water penetration by a means not specially causing cost up, etc. SOLUTION: This vessel for a hair cosmetic is equipped with two or more oxygen barrier layers using EVOH at an intermediate layer on a multilayer structure vessel wall. EVOH with a composition of the ethylene content not higher than 34 mol% is used for the most inner layer side oxygen barrier layer and EVOH with a monomer composition containing not lower than 36 mol% of ethylene is used for the most outer layer side oxygen barrier layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a container for hair cosmetics. More specifically, the present invention relates to a container for hair cosmetics in which the storage stability of hair cosmetics is improved by sufficiently securing the oxygen barrier property of the container wall.

[0002]

2. Description of the Related Art Hair cosmetics may contain an oxidative dye or a reducing agent. When these oxidative dyes and reducing agents react with oxygen during the distribution and storage of hair cosmetics, they cause discoloration or deterioration, so a container for hair cosmetics is required to have an oxygen barrier property that does not allow permeation of oxygen in the air. . On the other hand, hair cosmetics may contain an oxidizing agent such as hydrogen peroxide. When such an oxidizing agent permeates and volatilizes outside the container during distribution and storage of the hair cosmetic composition, the oxidizing effect of the hair cosmetic composition is reduced and the original purpose cannot be achieved.

[0003]

Therefore, it is necessary to impart a barrier property to oxygen in the air or oxygen derived from hydrogen peroxide to a container for a specific hair cosmetic which requires an oxygen barrier property as described above. Is very important.

However, conventionally, no invention has been found that proposes such a technical problem and means for solving it, focusing on a container for hair cosmetics. Further, generally, for example, the use of a fluororesin can be expected to have a high oxygen barrier property, but it is not practical because it is very expensive and has poor adhesiveness with other resins.

Therefore, the present invention shows a sufficient barrier property against oxygen in the air and oxygen derived from hydrogen peroxide in a container for storing a hair cosmetic which requires an oxygen barrier property, and oxygen based on water penetration. It is an object to be solved to provide a container for hair cosmetics which is excellent in storage stability of hair cosmetics without causing deterioration of barrier properties.

[0006]

【Viewpoints】First point In the present invention, the present inventor will
EVOH (ethylene vinyl
Attention was paid to the rucor copolymer). What is the above fluororesin?
In contrast, EVOH balances cost and performance requirements.
It is a material that satisfies well.

[0007] In a general sense, there are some known documents disclosing cosmetic containers having a multi-layered container wall containing an EVOH layer. However, in the disclosure of these documents, EVOH
It is unclear whether or not the layer has an oxygen barrier property that can meet the requirements peculiar to the container for hair cosmetics, such as the oxidation prevention of the oxidation dye and the reducing agent, and the EVOH layer is derived from an aqueous solution in which hydrogen peroxide is dissolved. It is also completely unclear whether or not it exhibits an effective oxygen barrier property against oxygen, and it is also unclear what characteristics of the material the EVOH layer can meet such requirements.

The present inventor has experimentally clarified these points, and EVOH, particularly EVOH having a specific material constitution characteristic, effectively functions as an oxygen barrier layer of a hair cosmetic container. Was revealed for the first time.

[0009]Second focus By the way, EVOH easily allows water to penetrate,
Therefore, consider the problem that the oxygen barrier property is greatly reduced.
There is a need to. Conventionally, oxygen barrier layer using EVOH
When installing a water barrier layer, add a water barrier layer
A layer is shielded from water, which itself has a certain effect
Even if it has the property, other technical factors such as EV
The optimum selection of the monomer composition of OH itself is not considered.
Absent.

However, it has been experimentally found that EVOH exhibits complicated behavior in oxygen permeability at each level of relative humidity due to the difference in ethylene content in its monomer composition. Then, the inventors of the present application have found that when two or more oxygen barrier layers using EVOH having different ethylene contents in the monomer composition are provided, a very excellent oxygen barrier property is obtained.

[0011]

(Structure of First Invention) The structure of the first invention of the present application (the invention according to claim 1) for solving the above-mentioned problems is an arbitrary intermediate in a container wall having a multilayer structure. Two or more oxygen barrier layers using EVOH (ethylene / vinyl alcohol copolymer) are provided in the layer portion, and EVOH having a monomer composition in which the ethylene content is 34 mol% or less is provided in the oxygen barrier layer on the innermost layer side. A container for hair cosmetics, which is used and uses EVOH having a monomer composition having an ethylene content of 36 mol% or more in the outermost oxygen barrier layer.

(Operation and effect of the first invention) In the first invention, the oxygen barrier layer on the innermost layer side, that is, on the side close to the inside of the container filled with the hair cosmetic containing water as a basic solvent is
EVO with relatively low ethylene content of 34 mol% or less
H is used. Such EVOH has a relatively high oxygen barrier property when used on the inner layer side located closer to the hair cosmetic solution (not in contact with the hair cosmetic solution).

The oxygen barrier layer on the outermost layer side, that is, on the side close to the outside of the container where the relative humidity is relatively low, has an ethylene content of 3%.
A relatively large amount of EVOH of 6 mol% or more is used. Such EVOH has a relatively high oxygen barrier property when used on the outer layer side located near the outside of the container.

Therefore, the oxygen barrier layers on the innermost layer side and the outermost layer side exhibit the oxygen barrier property most effectively. As a result, discoloration or deterioration due to the reaction of the oxidizing dye or reducing agent contained in the hair cosmetics with oxygen, and the permeation and volatilization of the oxidizing agents such as hydrogen peroxide contained in the hair cosmetics out of the container are effective. Will be suppressed. As a result, the storage stability of the hair cosmetic composition is improved. It should be noted that the proper use of EVOH as in the first aspect of the invention does not cause any particular cost increase or technical difficulty.

(Structure of the Second Invention) The structure of the second invention of the present application (the invention according to claim 2) for solving the above problems is as follows.
The hair cosmetic container according to the first aspect of the present invention has the following (1) to
A container for hair cosmetics, comprising a water barrier layer using COC (cyclic olefin-based copolymer) at any one or more layer sites of (3). (1) An inner layer of the two or more oxygen barrier layers. (2) An intermediate layer of the two or more oxygen barrier layers. (3) An outer layer of the two or more oxygen barrier layers.

(Operation and effect of the second invention) Since the water barrier layer using COC has a high barrier property against water,
By providing inside or outside or in the middle of two or more oxygen barrier layers using VOH, it is possible to prevent water from penetrating into the oxygen barrier layers, and as a result, decrease the oxygen barrier properties of the hair cosmetic container. Can be effectively prevented.

(Structure of the Third Invention) The structure of the third invention of the present application (the invention according to claim 3) for solving the above problems is as follows.
The multi-layered container wall according to the first invention or the second invention,
A hair cosmetic container comprising an innermost layer made of a polyolefin resin, a polyacrylonitrile resin, or a polyester resin. In the third invention, the term "polyolefin resin" means COC (cyclic olefin copolymer).
It is a concept that does not include.

(Operation and Effect of Third Invention) The polyolefin resin, polyacrylonitrile resin or polyester resin exhibits a certain water barrier property and also has chemical resistance required as the innermost layer material. Therefore, the container for hair cosmetics according to the third aspect of the present invention can exhibit a better oxygen barrier property and can also secure the chemical resistance generally required as a container for hair cosmetics.

(Structure of Fourth Invention) The structure of a fourth invention of the present application (an invention according to claim 4) for solving the above-mentioned problems is as follows.
A container for hair cosmetics, wherein the container wall having a multilayer structure according to the first invention to the third invention comprises an outermost layer using a polyolefin resin, a polyacrylonitrile resin or a polyester resin.

(Operation and effect of the fourth invention) The polyolefin resin, polyacrylonitrile resin or polyester resin exhibits a certain water barrier property and also has the printability, water resistance and surface treatment required as the outermost layer material. And surface gloss. Therefore, the container for hair cosmetics of the fourth invention exhibits further good oxygen barrier properties, and at the same time has printability, water resistance, easiness of surface treatment, and surface property which are generally required as a container for hair cosmetics. It can also secure the luster.

(Structure of the Fifth Invention) The structure of the fifth invention of the present application (the invention according to claim 5) for solving the above-mentioned problems is as follows.
A container for hair cosmetics, wherein the container for hair cosmetics according to the first invention to the fourth invention is used as a container for hair cosmetics requiring oxygen barrier properties.

(Operation / Effect of Fifth Invention) The container for hair cosmetics is particularly preferably used as a container for hair cosmetics requiring oxygen barrier properties.

(Structure of Sixth Invention) The structure of a sixth invention of the present application (an invention according to claim 6) for solving the above-mentioned problems is as follows.
The hair cosmetics requiring oxygen barrier properties according to the fifth aspect of the invention are the first or second agent of an oxidative hair dye, the first or second agent of a hair bleaching agent, or the permanent wave agent. A container for hair cosmetics, which is a first agent or a second agent.

(Operation / Effect of Sixth Invention) As hair cosmetics requiring oxygen barrier properties, those listed in the sixth invention are particularly preferable.

(Structure of Seventh Invention) The structure of a seventh invention of the present application (an invention according to claim 7) for solving the above-mentioned problems is as follows.
A container for hair cosmetics according to any one of the first to sixth inventions, which is an inner bag of an aerosol container.

(Operation and Effect of Seventh Invention) First to Sixth Inventions
The use or use form of the container for hair cosmetics according to the invention is not limited, but it can be preferably used as an inner bag of an aerosol container as in the seventh invention.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the first invention to the seventh invention will be described. In the following, simply "the present invention"
When referring to, the first to seventh inventions are collectively referred to.

[Oxygen Barrier Layer] The container for hair cosmetics according to the present invention comprises a container wall having a multi-layer structure, and two or more oxygen barrier layers using EVOH are provided at any intermediate layer site on the container wall. Prepare That is, two or more oxygen barrier layers can be provided in any intermediate layer other than the innermost layer or the outermost layer. Basically, it is preferable to provide a water barrier layer described later inside the two or more oxygen barrier layers. In the present invention, EVOH used for the oxygen barrier layer has the following specific restrictions.

That is, EVOH is obtained by copolymerizing an ethylene component and a vinyl alcohol component as monomers, but in the present invention, the oxygen barrier layer on the innermost layer side among the oxygen barrier layers of two or more layers is used. Ethylene content is 34
EVOH having a monomer composition of not more than mol% is used, and more preferably EVOH having a monomer composition having an ethylene content of not more than 29 mol% is used. Further, among the two or more oxygen barrier layers, EVOH having a monomer composition having an ethylene content of 36 mol% or more is used for the oxygen barrier layer on the outermost layer side, and more preferably, the ethylene content is 39 mol% or more. EVOH having a monomer composition of

When three or more oxygen barrier layers are provided, the ethylene content of EVOH used for the oxygen barrier layer provided in the layer portion other than the innermost layer side and the outermost layer side can be arbitrarily set, but usually, Its ethylene content is 3
An appropriate value between 4 mol% and 36 mol%, for example 35
It is preferably about mol%.

The layer thickness of the oxygen barrier layer formed by using EVOH as described above is not limited, but in order to eliminate the possibility of pinholes, it is preferable that each oxygen barrier layer has a thickness of 25 μm or more. It is particularly preferable that the film thickness is 40 μm or more. EVOH is a resin that is hard to some extent, so if the container for hair cosmetics is a bottle type, the upper limit of the layer thickness of the oxygen barrier layer does not need to be so important, but the container for hair cosmetics requires flexibility. In the case of the tube type, the total thickness of each oxygen barrier layer is more preferably about 150 μm or less.

[Water Barrier Layer] In the container for hair cosmetics according to the present invention, one or more layers of COC (cyclic olefin-based copolymer) are preferably used in the container wall of the multilayer structure. With a water barrier layer.

Any known cyclic olefin copolymer can be used, and the kind thereof is not limited, but an alicyclic hydrocarbon compound, more preferably an alicyclic compound having an ethylenically unsaturated bond and a bicyclo ring. Selected from group hydrocarbon compounds, particularly preferably bicyclo [2,2,1]
It is appropriately selected from hept-2-ene derivatives. For example,
"COC" in Japanese Patent Laid-Open No. 2001-157705
Any of the compounds disclosed as can be selected.

The water barrier layer can be provided (1) inside two or more oxygen barrier layers, that is, inside the innermost oxygen barrier layer in the two or more oxygen barrier layers. or,
The water barrier layer may be provided in (2) any intermediate layer portion of the two or more oxygen barrier layers. Furthermore, the water barrier layer
(3) It can also be provided outside the two or more oxygen barrier layers, that is, outside the oxygen barrier layer on the outermost layer side of the two or more oxygen barrier layers. Above regarding water barrier layer (1)
Two or more of the embodiments (3) to (3) can be performed simultaneously.

[Innermost layer and outermost layer of container for hair cosmetics]
The container wall of the multilayer structure in the container for hair cosmetics according to the present invention preferably comprises an innermost layer using a polyolefin resin, a polyacrylonitrile resin or a polyester resin. Moreover, the container wall of the multilayer structure in the container for hair cosmetics according to the present invention preferably comprises an outermost layer using a polyolefin resin, a polyacrylonitrile resin or a polyester resin. The polyolefin resin layer constituting the outermost layer may be composed of two layers from the viewpoint of ease of surface treatment, suitability for printing, maintenance of surface gloss and the like.

The type of polyolefin resin is not limited, but high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDP)
E), linear low-density polyethylene (LLDPE), polypropylene (PP), ethylene-propylene copolymer,
It is possible to arbitrarily select ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer, ionomer resin and the like. it can. In particular, HDPE, MDPE, LDPE,
LLDPE and PP are preferred.

The type of polyacrylonitrile-based resin is not limited, but for example, the trade name "Barex" manufactured by Mitsui Toatsu Chemicals, Inc. can be appropriately selected. The type of polyester resin is not limited, but for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT)
Etc. can be appropriately selected.

[Structure of Hair Cosmetic Container] From the above various embodiments, some preferred examples of the layer structure of the container wall in the hair cosmetic container according to the present invention will be listed below.
In the following layer configuration example, the left end is the innermost layer and the right end is the outermost layer. Further, “EVOH” is the specific EVO according to the present invention.
H is shown, and "PO" shows a polyolefin resin. In each of the following examples, a PO layer or C provided in two or more layers
The OC layers may be made of the same material as each other,
In some cases, the materials are the same, but have different specific contents such as monomer composition and average molecular weight.

A) PO / EVOH / PO / EVOH / P
O b) PO / COC / EVOH / PO / EVOH / COC
/ PO c) PO / COC / EVOH / PO / EVOH / COC
/ PO / PO d) PO / COC / EVOH / PO / EVOH / PO e) PO / COC / EVOH / PO / EVOH / PO /
PO f) PO / EVOH / PO / EVOH / COC / PO.

In the container for hair cosmetics having a multi-layer structure as described above, the layers may be adhered to each other or may be adhered using an adhesive. When an adhesive is used, there are a method of providing an adhesive layer between the layers and a method of previously blending the adhesive with the constituent material of each layer. At least for the oxygen barrier layer, a method of providing an adhesive layer between the layers is preferable to the adhesive blending method in order to avoid the concern that the oxygen barrier property of EVOH is slightly lowered.

Although the kind of the adhesive is not limited, for example, modified polyolefin can be preferably used. Examples of the modified polyolefin include PP and HDP modified with unsaturated carboxylic acid, acid anhydride, ester or amide.
E, LDPE, LLDPE, EVA and the like can be preferably used.

The shape of the container for hair cosmetics is freely known, such as a standing pouch container, a pouch container, a bottle container, a tube container, and an inner bag of an aerosol container, which are known in this kind of cosmetic container. You can choose. Above all, an inner bag of a bottle container, a tube container or an aerosol container is preferable.

[Use of Hair Cosmetic Container] The use of the hair cosmetic container according to the present invention is not limited, but it is preferably used as a container for hair cosmetics requiring oxygen barrier properties. Hair cosmetics requiring oxygen barrier properties include the first or second agent of oxidative hair dye, and the first agent of hair bleaching agent.
The agent or the second agent, or the first agent or the second agent of the permanent wave agent is representatively exemplified. In addition, the container for hair cosmetics can also be used as a container for shampoo, conditioner, conditioner, hair dressing, hair liquid, hairnic, acidic hair dye, hair treatment, remover for acidic hair dye, hair restorer, etc. it can.

When the hair cosmetic is the first oxidative hair dye containing at least an oxidative dye and an alkaline agent, the hair cosmetic container of the present invention prevents the permeation / invasion of oxygen from the outside of the container. Therefore, the reaction between the oxidation dye and oxygen can be prevented. Therefore, the storage stability of the oxidative hair dye first agent can be improved. Hair cosmetics
Even in the case of the first agent for permanent wave containing at least a reducing agent and an alkaline agent, similarly, deterioration of the reducing agent due to a reaction between the reducing agent and oxygen permeated / invaded from the outside of the container can be prevented. The storage stability of the first agent for wave can be improved.

When the hair cosmetic composition is the second agent for an oxidation hair dye containing at least an oxidizing agent, the container for hair cosmetics according to the present invention prevents permeation and volatilization of the oxidizing agent to the outside of the container. The storage stability of the second agent for the oxidative hair dye can be improved. Even when the hair cosmetic is the second agent for permanent wave containing at least an oxidizing agent,
Similarly, prevent permeation and volatilization of the oxidizer to the outside of the container,
The storage stability of the second agent for permanent wave can be improved.

The dosage form of the hair cosmetic composition contained in the container for hair cosmetic composition according to the present invention is not limited. For example, it may be a viscous dosage form such as gel, gel, cream or paste, or a liquid dosage form.

[0047]

[Examples] Non-colored containers for hair cosmetics according to Examples 1 and 2 and Comparative Examples 1 and 2 shown in Table 1 at the end were prepared. Each of these containers is a tube container manufactured by the same blow molding method, has a capacity of 50 mL, and has a container wall thickness of about 450 μm.

Each of these containers has a single-layer or multi-layer structure as shown in the column "Material composition" in Table 1. That is, Comparative Example 2 is composed of a single layer of LDPE. For example, in Example 2, the innermost layer is the LDPE layer, the EVOH layer is provided via AD (adhesive), the LDPE layer is further provided via AD, and the EVOH layer is further provided via AD (adhesive), Further, the outermost layer is the LDPE layer through AD. EVO used for the inner and outer layer EVOH layers according to each applicable example
The ethylene content of H is shown in Table 1.

The thickness (unit: μm) of each layer of the container wall according to each example is as follows from the innermost layer side (the layer side shown at the left end of Table 1) in order. Example 1: LDPE = 80 / AD = 20 / COC = 40
/ AD = 20 / EVOH = 25 / AD = 20 / LDPE
= 40 / AD = 20 / EVOH = 25 / AD = 20 / C
OC = 40 / AD = 20 / LDPE = 80. Example 2: LDPE = 140 / AD = 20 / EVOH =
25 / AD = 20 / LDPE = 40 / AD = 20 / EV
OH = 25 / AD = 20 / LDPE = 140. Comparative Example 1: The thickness of each layer is the same as in Example 2. Comparative Example 2: LDPE = 450.

As the above-mentioned AD (adhesive) layer,
Actually, the product name “Admar” of Mitsui Petrochemical Industry Co., Ltd. is used. This "Admer" is an adhesive polyolefin obtained by graft-reacting a polyolefin by introducing a functional group, and can strongly bond a gas barrier resin and the like by a thermal reaction.

The hair cosmetic container according to each of the above examples
Each is filled with the first oxidative hair dye composition shown below.
Then, it was capped and stored in a constant temperature bath at 45 ° C. for 3 months.First agent composition Paraphenylenediamine 2.0% by weight Resorcin 1.0% by weight Polyoxyethylene (10) oleyl ether 3.0% by weight Cetostearyl alcohol 8.0% by weight Liquid paraffin 2.0% by weight Ammonia water pH 9 amount The rest of purified water.

The above-mentioned container for hair cosmetics after storage for 3 months was opened, the hair cosmetics as the contents were discharged, and the degree of coloring of the hair cosmetics was visually evaluated. Through this evaluation, the more remarkable the coloring of hair cosmetics,
By judging that the storage stability is poor, it is possible to evaluate the oxygen barrier property of the container for hair cosmetics, and thus the storage stability of the first agent.

The results are shown in the "Evaluation" column of Table 1, and in the same column, "⊚" means "no coloring of hair cosmetics was observed". "○" indicates that "coloring of the hair cosmetic was hardly observed". “Δ” indicates that “coloring of the hair cosmetic was slightly recognized”.
“X” indicates that “a considerable amount of coloring was found in the hair cosmetic”.

[0054]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Inoue             Aki Prefecture Aichi-gun Nagakute Town             12 of the ground Hoyu Co., Ltd. Research Institute (72) Inventor Akira Wakasugi             Aki Prefecture Aichi-gun Nagakute Town             12 of the ground Hoyu Co., Ltd. Research Institute (72) Inventor Shigeharu Itoda             Aki Prefecture Aichi-gun Nagakute Town             12 of the ground Hoyu Co., Ltd. Research Institute (72) Inventor Tomomi Kanaiwa             Aki Prefecture Aichi-gun Nagakute Town             12 of the ground Hoyu Co., Ltd. Research Institute F term (reference) 3E086 AD01 AD03 AD04 BA04 BA15                       BA24 BB05 CA35

Claims (7)

[Claims] 1. An oxygen barrier layer having two or more layers using EVOH (ethylene vinyl alcohol copolymer) is provided at an arbitrary intermediate layer portion in a container wall having a multilayer structure, and the oxygen barrier layer on the innermost layer side is provided. A hair characterized by using EVOH having a monomer composition having an ethylene content of 34 mol% or less and using EVOH having a monomer composition having an ethylene content of 36 mol% or more in the outermost oxygen barrier layer. Cosmetic container. 2. The container for hair cosmetics comprises the following (1) to
The container for hair cosmetics according to claim 1, wherein a water barrier layer using COC (cyclic olefin-based copolymer) is provided on any one or more layer portions of (3). (1) An inner layer of the two or more oxygen barrier layers. (2) An intermediate layer of the two or more oxygen barrier layers. (3) An outer layer of the two or more oxygen barrier layers. 3. The hair makeup according to claim 1 or 2, wherein the container wall having the multilayer structure is provided with an innermost layer using a polyolefin resin, a polyacrylonitrile resin or a polyester resin. Container for food. 4. The container wall of the multi-layer structure comprises an outermost layer using a polyolefin resin, a polyacrylonitrile resin or a polyester resin, according to any one of claims 1 to 3. Container for hair cosmetics. 5. The hair according to claim 1, wherein the container for hair cosmetics is used as a container for hair cosmetics requiring oxygen barrier properties. Cosmetic container. 6. The hair cosmetic requiring oxygen barrier properties is a first or second agent for an oxidative hair dye, a first or second agent for a hair bleaching agent, or a first or second agent for a permanent waving agent. The container for hair cosmetics according to claim 5, wherein the container is a first agent or a second agent. 7. The container for hair cosmetics according to claim 1, wherein the container for hair cosmetics is an inner bag of an aerosol container.