JP4711065B2 - Laminates and multilayer containers - Google Patents

Description

  The present invention relates to a multilayer container for housing a first agent of an oxidative hair dye containing a dye, and a method for storing a hair dye using the container.

  As a hair cosmetic, a two-component hair dye that obtains a hair dyeing effect by mixing a first agent and a second agent is known. In the two-component hair dye, there is an oxidative hair dye in which the first agent is alkaline containing an oxidation dye and an alkaline agent (such as ammonia), and the second agent is acidic containing hydrogen peroxide. Conventionally, a tube container, an aerosol can, or the like is used as a storage container for storing the first agent of oxidative hair dye (see, for example, Patent Document 1). In this tube container, an inner surface coating with an epoxy phenol-based resin is applied to a container made of an aluminum metal, and the first agent is accommodated therein. The aerosol can is configured such that an outer container made of aluminum metal is provided with an inner container made of synthetic resin such as polyethylene, and the first agent is housed inside the inner container. ing.

  However, since it is difficult to separate the inner container and the outer container, this conventional storage container is disposed of as waste after use, and there is a problem in terms of environmental protection.

  In addition, since the inner container is a complicated configuration installed in the outer container, the manufacturing cost increases, and in addition, in the case of an aerosol can, there is a problem that the cost is further increased because of the complicated discharge mechanism. .

  Furthermore, since the tube container requires a little force to squeeze out the contents, there is a problem that it is difficult to use for the elderly. Similarly, aerosol cans are also difficult to operate for elderly people.

  Therefore, as a method for solving the above problem, an attempt has been made to store an oxidative hair dye in a packaging bag. This packaging bag is formed into a flat bag shape by a sheet material, and has been conventionally used as a portable container such as a shampoo or a rinse.

However, when the first agent of oxidative hair dye is stored in this packaging bag, ammonia or the like mixed in the first agent penetrates into the sheet material and leaks out of the packaging bag. There was a problem that the contents could not be stored stably.
JP-A-11-147548

  An object of the present invention is to provide a method for storing a hair dye that can solve the above-described problems and can improve the storage stability of the first agent of the oxidative hair dye.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a laminated material laminated with a gas barrier adhesive mainly composed of a specific epoxy resin composition, and the first oxidation hair dye. It has been found that stable storage can be achieved by filling the agent and hermetically storing it, leading to the present invention.

That is, the present invention is a laminate in which at least a base material layer containing aluminum, a layer made of a cured epoxy resin, and a thermoplastic resin layer are laminated in this order, and the cured epoxy resin is derived from bisphenol A. A laminate obtained by reacting an epoxy resin having a glycidyl ether moiety and an epoxy resin curing agent containing a skeleton structure represented by formula (1), and the use of the laminate It is related with the multilayer container formed.
The present invention also relates to a method for storing a hair dye, wherein the hair dye is sealed and stored in the multilayer container.

  According to the present invention, the first agent of the oxidative hair dye can be stably stored.

  Embodiments of the present invention will be described below.

The laminate of the present invention is a laminate in which at least a base material layer containing aluminum, a layer made of a cured epoxy resin, and a thermoplastic resin layer are laminated in this order. Examples of the layer structure (excluding the layer made of epoxy resin cured product) include base material layer / thermoplastic resin layer, thermoplastic resin layer / base material layer / thermoplastic resin layer, thermoplastic resin layer / base material layer / heat. Examples include, but are not limited to, a plastic resin layer / thermoplastic resin layer. The plurality of thermoplastic resin layers may be the same or different.
There is no restriction | limiting in particular in the manufacturing method of a laminated body, As a form of a laminated body, the laminated film, sheet | seat, preform, etc. which have such a layer structure are mentioned, for example. Moreover, a multilayer container is obtained by using this laminated body.
Examples of the shape of the multilayer container include a standing pouch, a pouch, a bottle, and a tube. In the case of a bag-like container such as a standing pouch, it is preferable to make a bag by using a laminate film having a heat-sealable thermoplastic resin layer (sealant layer). When making a bag, the base material is used on the outer surface of the bag and the sealant layer is used on the inner surface of the bag.

The base material layer in the present invention is a layer containing aluminum, and generally a metal foil made of aluminum or an aluminum vapor deposition film (hereinafter collectively referred to as “aluminum film”) is used. By using an aluminum film, the contents can be prevented from drying and solidifying.
Moreover, the said base material layer may laminate | stack the following film materials on the aluminum film, and may use multiple aluminum films. Examples of the film material include polyolefin films such as low density polyethylene, high density polyethylene, linear low density polyethylene, and polypropylene, polyester films such as polyethylene terephthalate and polybutylene terephthalate, polyacrylonitrile films, and poly (meth) acrylic. Plastic films such as polyethylene films, polystyrene films, polycarbonate films, ethylene-vinyl alcohol copolymer (EVOH) films, polyvinyl alcohol films, and papers such as cartons.
In addition, the film material is coated with various polymers such as polyvinylidene chloride (PVDC) resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, acrylic resin, and various inorganic compounds such as silica and alumina. A vapor-deposited film, a film in which an inorganic filler or the like is dispersed, a film having an oxygen scavenging function, or the like can be used.
Here, an inorganic filler can also be disperse | distributed also about the various polymers to coat. Examples of inorganic fillers include layered silicates, silica, alumina, mica, talc, aluminum flakes, glass flakes, etc., but layered silicates such as montmorillonite are preferred, and examples of the dispersion method include extrusion kneading and resin. A conventionally known method such as a mixed dispersion method in a solution can be used. Examples of methods for imparting oxygen scavenging functions include hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol and other low molecular organic compounds that react with oxygen, cobalt, manganese, nickel, iron And a method of using a composition containing a transition metal compound such as copper at least in part.
The thickness of these film materials is about 10 to 300 μm, preferably about 10 to 100 μm, and in the case of a plastic film, it may be stretched in a uniaxial or biaxial direction. These film materials can also be used when manufacturing an aluminum vapor deposition film. When laminating these film materials, a known laminating method such as dry lamination, non-solvent lamination, extrusion lamination, or the like may be used. Moreover, the adhesive agent in this invention may be used, and another adhesive agent may be used.

  Various surfaces such as flame treatment and corona discharge treatment are formed on the surface of the base material layer as necessary so that an adhesive layer (a layer made of a cured epoxy resin) free from defects such as film breakage and repellency is formed. It is desirable that processing be performed. Such a treatment promotes good adhesion of the adhesive layer to the substrate layer. Moreover, after an appropriate surface treatment is performed on the surface of the base material layer, a printing layer can be provided as necessary. In providing the printing layer, general printing equipment that has been used for printing on a conventional polymer film such as a gravure printing machine, a flexographic printing machine, and an offset printing machine can be similarly applied. In addition, the ink for forming the printing layer is also applied to conventional polymer films formed from pigments such as azo and phthalocyanine, resins such as rosin, polyamide resin and polyurethane, solvents such as methanol, ethyl acetate and methyl ethyl ketone. The inks that have been used for the printing layer can be applied as well.

  Examples of the material constituting the thermoplastic resin layer in the present invention include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, polyolefin-based film or sheet material such as ethylene-vinyl acetate copolymer, and polyester such as polyethylene terephthalate. Film or sheet material, polyacrylonitrile film or sheet material, nylon 6, nylon 6,6, polyamide film or sheet material such as metaxylene adipamide (N-MXD6), poly (meth) acrylic film or sheet Materials, polystyrene film or sheet material, polycarbonate film or sheet material, ethylene-vinyl alcohol copolymer (EVOH) film or sheet material, polyvinyl alcohol film Etc. flexible polymer film such as a sheet material. In the case of producing a bag-like container, it is preferable to select a polyolefin film such as a polyethylene film, a polypropylene film, or an ethylene-vinyl acetate copolymer film in consideration of the expression of good heat sealability. The thickness of these films is practically about 10 to 300 μm, preferably about 10 to 100 μm, and various surface treatments such as flame treatment and corona discharge treatment may be performed on the surface of the film.

In the laminate of the present invention, the cured epoxy resin is a cured product obtained by reacting an epoxy resin having a glycidyl ether moiety derived from bisphenol A and an epoxy resin curing agent containing a skeleton structure of the formula (1). It has a high gas barrier property and also has a function of adhering the base material layer and the thermoplastic resin layer. When the skeleton structure of the formula (1) is contained at a high level in the cured epoxy resin, a high gas barrier property is exhibited. According to the present invention, it is also possible to obtain an epoxy resin cured product having an oxygen barrier property with an oxygen permeability coefficient of 20 ml · mm / (m ² · day · MPa) or less at 23 ° C. and 60% RH. Below, an epoxy resin and an epoxy resin hardening | curing agent are demonstrated.

  The epoxy resin in the present invention has a glycidyl ether moiety derived from bisphenol A. Specifically, Epicoat 828, which is a bisphenol A basic liquid resin manufactured by Japan Epoxy Resin Co., Ltd., is preferably used.

  Moreover, in order to improve various performances such as flexibility, impact resistance, heat and humidity resistance, and gas barrier properties, various epoxy resins can be mixed and used at an appropriate ratio. Specifically, an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidylamine derived from diaminodiphenylmethane Epoxy resin having glycidylamine moiety and / or glycidyl ether moiety derived from paraaminophenol, epoxy resin having glycidyl ether moiety derived from bisphenol F, glycidyl ether moiety derived from phenol novolac An epoxy resin having a glycidyl ether moiety derived from resorcinol can be used.

The epoxy resin curing agent in the present invention contains a skeleton structure represented by the formula (1). The epoxy resin curing agent is a compound containing a skeleton structure of the formula (1), specifically metaxylylenediamine or paraxylylenediamine, and a reaction product with an epoxy resin or a monoglycidyl compound using these as raw materials, Reaction product with alkylene oxide having 2 to 4 carbon atoms, reaction product with epichlorohydrin, polyfunctional having at least one acyl group capable of forming an amide group site and reacting with these to form an oligomer A reaction product with a functional compound, a polyfunctional compound having at least one acyl group capable of forming an amide group site to form an oligomer by reaction with these, a monovalent carboxylic acid and / or a derivative thereof Contains reaction products and the like.
The epoxy resin curing agent containing the skeleton structure of the formula (1) preferably contains 60% by weight or more, more preferably 70% by weight or more of the skeleton structure of the formula (1). When the skeleton structure of the formula (1) is contained at a high level in the cured epoxy resin, a high gas barrier property is exhibited. According to the present invention, it is also possible to obtain an epoxy resin cured product having an oxygen barrier property with an oxygen permeability coefficient of 20 ml · mm / m ² · day · MPa (23 ° C., 60% RH) or less.

In addition, the epoxy resin curing agent in the present invention includes aliphatic, alicyclic, aromatic or heterocyclic polyamines, phenols, acid anhydrides, carboxyls, in addition to the compound containing the skeleton structure of formula (1). It can be used by mixing with an epoxy resin curing agent that can be generally used such as acids in an appropriate ratio. These epoxy resin curing agents can be selected according to the use application of the laminate film and the required performance in the application.
Specifically, polyamines include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, alicyclic amines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, Examples include aromatic amines such as diaminodiphenylmethane and metaphenylenediamine.
Also, reaction products with epoxy resins or monoglycidyl compounds made from these polyamines, reaction products with alkylene oxides having 2 to 4 carbon atoms, reaction products with epichlorohydrin, these polyamines A reaction product with a polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with, an oligomer with an amide group site formed by reaction with these polyamines A reaction product of a polyfunctional compound having at least one acyl group and a monovalent carboxylic acid and / or a derivative thereof can be used.

Examples of phenols include multi-substituent monomers such as catechol, resorcinol and hydroquinone, and resole type phenol resins.
Acid anhydrides or carboxylic acids include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride, and alicyclic acid anhydrides such as (methyl) tetrahydrophthalic anhydride and (methyl) hexahydrophthalic anhydride. Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and carboxylic acids thereof can be used.

In consideration of high gas barrier properties and good adhesion to the base material layer or the thermoplastic resin layer, as the epoxy resin curing agent, the following reaction products (A) and (B), or (A), It is particularly preferable to use the reaction products (B) and (C).
(A) Metaxylylenediamine or paraxylylenediamine
(B) A polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with a polyamine to form an oligomer
(C) C1-C8 monovalent carboxylic acid and / or derivative thereof

  Examples of the polyfunctional compound having at least one acyl group that can form an amide group site by reaction with the (B) polyamine to form an oligomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, Carboxylic acids such as malic acid, tartaric acid, adipic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid and their derivatives such as esters, amides, acid anhydrides, acid chlorides, etc., especially acrylic acid Methacrylic acid and derivatives thereof are preferred.

  In addition, monovalent carboxylic acids having 1 to 8 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid, and derivatives thereof such as esters, amides, acid anhydrides, acid chlorides, etc. The polyfunctional compound may be used in combination with the starting polyamine. The amide group site introduced by the reaction has a high cohesive force, and the presence of the amide group site in a high proportion in the epoxy resin curing agent results in higher oxygen barrier properties and a base material layer or thermoplastic resin layer. Good adhesion strength to can be obtained.

  The reaction molar ratio of (A) and (B) or (A), (B), and (C) is the reactive functionality contained in (B) with respect to the number of amino groups contained in (A). The ratio of the number of groups, or the ratio of the total number of reactive functional groups contained in (B) and (C) to the number of amino groups contained in (A) is in the range of 0.3 to 0.97 Is preferred. When the ratio is less than 0.3, a sufficient amount of amide groups are not formed in the epoxy resin curing agent, and a high level of gas barrier properties and adhesion to the base material layer or the thermoplastic resin layer are not exhibited. Moreover, the ratio of the volatile molecule which remains in the epoxy resin curing agent is increased, which causes odor generation from the obtained cured product. Moreover, since the ratio of the hydroxyl group produced | generated by reaction of an epoxy group and an amino group in the hardening reaction material becomes high, it becomes a factor by which oxygen barrier property in a high humidity environment falls remarkably. On the other hand, in the range higher than 0.97, the amount of amino groups reacting with the epoxy resin is reduced, and excellent impact resistance and heat resistance are not exhibited, and the solubility in various organic solvents or water is lowered. When particularly considering the high gas barrier property, high adhesion, suppression of odor generation, and high oxygen barrier property in a high humidity environment of the obtained cured product, the molar ratio of the polyfunctional compound to the polyamine component is 0.6. A range of ˜0.97 is more preferable. In consideration of the expression of adhesiveness to a higher level of the base material layer and the thermoplastic resin layer, at least 6% by weight of amide in the epoxy resin curing agent in the present invention is based on the total weight of the curing agent. It is preferred that a group is contained.

  A laminate such as a laminate film produced using the cured epoxy resin in the present invention has a laminate strength (initial adhesive strength) of 30 g / 15 mm or more immediately after lamination (before aging) at a peeling speed of 300 mm / min. It is preferably 40 g / 15 mm or more, particularly preferably 50 g / 15 mm or more. When the initial adhesive force is not sufficient, problems such as tunneling of the laminate film and winding deviation when winding the sheet occur.

When considering the expression of high initial adhesive strength, for example, metaxylylenediamine or paraxylylenediamine, which is an epoxy resin curing agent, and the polyamine can form an amide group site to form an oligomer. The reaction ratio of the reaction product with the polyfunctional compound having one acyl group is 0.6 to 0.97, preferably 0.8 to 0.97, particularly in terms of the molar ratio of the polyfunctional compound to the polyamine component. It is preferable to use an epoxy resin curing agent in which the average molecular weight of the oligomer as the reaction product is increased, preferably in the range of 0.85 to 0.97.
A more preferred epoxy resin curing agent is a reaction product of metaxylylenediamine and acrylic acid, methacrylic acid and / or derivatives thereof. Here, the reaction molar ratio of acrylic acid, methacrylic acid and / or derivatives thereof to metaxylylenediamine is preferably in the range of 0.8 to 0.97.

  About the mixture ratio of the epoxy resin and epoxy resin hardening | curing agent in this invention, you may be a standard compounding range in the case of producing an epoxy resin hardened material by reaction of an epoxy resin and an epoxy resin hardening | curing agent generally. Specifically, the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is in the range of 0.5 to 5.0. If the range is less than 0.5, the remaining unreacted epoxy group causes the gas barrier property of the resulting cured product to decrease, and if it is greater than 5.0, the remaining unreacted amino group results in the resulting cured product. It becomes a cause of lowering the heat and heat resistance. When the gas barrier property and heat-and-moisture resistance of the obtained cured product are particularly considered, the range of 0.8 to 3.0 is more preferable, and the range of 0.8 to 1.4 is particularly preferable.

  In the mixture of the epoxy resin and the epoxy resin curing agent in the present invention (hereinafter referred to as an epoxy resin composition), a polyurethane-based resin composition and a polyacrylic resin are used as long as they do not impair the effects of the present invention. A thermosetting resin composition such as a composition or a polyurea resin composition may be mixed.

  If necessary, a moistening agent such as silicon or an acrylic compound may be added to the epoxy resin composition to help wet the surface of the base material layer or the thermoplastic resin layer. Suitable wetting agents include BYK331, BYK333, BYK348, BYK381 available from Big Chemie. When adding these, the range of 0.01 weight%-2.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  In the epoxy resin composition, a xylene resin, a terpene resin, a phenol resin, if necessary, in order to improve the adhesion to the base material layer and the thermoplastic resin layer immediately after application to the base material layer and the thermoplastic resin layer, A tackifier such as rosin resin may be added. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

In addition, in order to improve various properties such as gas barrier properties, impact resistance, heat resistance, etc. of the layer formed of the epoxy resin composition formed of the epoxy resin composition, silica, alumina, mica are included in the epoxy resin composition. Inorganic fillers such as talc, aluminum flakes and glass flakes may be added.
In consideration of the transparency of the laminate, such an inorganic filler is preferably flat. When adding these, the range of 0.01 weight%-10.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  Moreover, you may add the compound etc. which have an oxygen capture | acquisition function to the said epoxy resin composition as needed. Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.

  Furthermore, in order to improve the adhesiveness of the epoxy resin cured layer formed from the epoxy resin composition to the base material layer and the thermoplastic resin layer, the epoxy resin composition contains a silane coupling agent and a titanium cup. A coupling agent such as a ring agent may be added. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  Furthermore, since the cured epoxy resin in the present invention is excellent in toughness and heat-and-moisture resistance, a gas barrier laminate or multilayer container excellent in impact resistance, boiling resistance, retort resistance and the like can be obtained.

  When using the epoxy resin composition of the present invention as an adhesive and laminating a base material layer or a thermoplastic resin layer to produce a laminate, a known laminating method such as dry lamination, non-solvent lamination, extrusion lamination, etc. Can be used.

  When the adhesive is applied to a base material layer or a thermoplastic resin layer and laminated, it is carried out at a concentration and temperature of an epoxy resin composition sufficient to obtain a layer made of a cured epoxy resin. Can vary depending on the choice of starting materials and lamination method. That is, the concentration of the epoxy resin composition is about 5% by weight using a certain kind of appropriate organic solvent and / or water from the case where no solvent is used depending on the type and molar ratio of the selected material, the laminating method, and the like. Various states can be taken up to the case where the coating liquid is prepared by diluting to the composition concentration. As the organic solvent to be used, any solvent having solubility with an adhesive can be used. For example, water-insoluble solvents such as toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, Glycol ethers such as 1-ethoxy-2-propanol and 1-propoxy-2-propanol, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol, N, N-dimethyl Examples include aprotic polar solvents such as formamide, N, N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

  The adhesive (coating solution) diluted with a solvent can be diluted at a concentration such that the Zahn cup (No. 3) viscosity is in the range of 5 to 30 seconds (25 ° C.). When the Zahn cup (No. 3) viscosity is 5 seconds or less, the adhesive is not sufficiently applied to the object to be coated, which causes contamination of the roll. If the Zahn cup (No. 3) viscosity is 30 seconds or more, the adhesive does not sufficiently transfer to the roll, and it becomes difficult to form a uniform adhesive layer. For example, in dry lamination, the Zahn cup (No. 3) viscosity is preferably 10 to 20 seconds (25 ° C.) during use.

  In order to suppress foaming of the coating liquid when preparing the coating liquid in the present invention, an antifoaming agent such as silicon or an acrylic compound may be added to the coating liquid. Suitable antifoaming agents include BYK019, BYK052, BYK067N, BYK070, BYK080, etc. available from Big Chemie. When adding these, the range of 0.01 weight%-2.0 weight% is preferable on the basis of the total weight of the epoxy resin composition in a coating liquid.

  When a solvent is used, the solvent drying temperature after application of the adhesive may vary from 20 ° C. to 140 ° C., but it is close to the boiling point of the solvent and affects the object to be coated. No temperature is desirable. When the drying temperature is 20 ° C. or lower, the solvent remains in the laminate, causing poor adhesion and odor. If the drying temperature is 140 ° C. or higher, it becomes difficult to obtain a laminate having a good appearance due to softening of the thermoplastic resin layer. For example, when apply | coating an adhesive agent to a stretched polypropylene film, 40 to 120 degreeC is desirable.

  Any of the commonly used coating types such as roll coating, spray coating, air knife coating, dipping, and brush coating can be used as the coating method when applying adhesive to the base material layer or thermoplastic resin layer. obtain. Roll coating or spray coating is preferred. For example, the same roll coat or spray technique and equipment as those used when applying and laminating a polyurethane adhesive component to a base material layer or a thermoplastic resin layer can be applied.

Next, specific operations in each laminating method will be described. In the case of the dry laminating method, the coating liquid is applied to a material to be a base material by a roll such as a gravure roll, and then the solvent is dried and a thermoplastic resin layer is immediately bonded to the surface by a nip roll to obtain a laminate. be able to. The solvent for preparing the adhesive is preferably a solvent having good solubility and a relatively low boiling point and containing an alcohol having 3 or less carbon atoms. The group consisting of methanol, ethanol, isopropanol, and n-propanol The solvent which has as a main component 1 or more types chosen from is illustrated. In addition, it is a mixed solution in which a solvent having an ester group, ketone group, or aldehyde group functional group that has the effect of delaying the reaction between the epoxy resin and the polyamine and suppressing the increase in the viscosity of the adhesive to prolong the working time. Preferably there is. As a mixed liquid in which a solvent having any functional group of an ester group, a ketone group or an aldehyde group is mixed, one kind selected from the group consisting of ethyl acetate, acetone, methyl ethyl ketone, acetaldehyde and propionaldehyde having a relatively low boiling point The liquid mixture which mixed the above is illustrated. In order to obtain a film with a small amount of solvent remaining in the resulting laminate, the content of the solvent having any functional group of ester group, ketone group and aldehyde group is preferably 20% by weight or less in the total solvent. Here, since a bad odor is caused when a large amount of solvent remains in the laminated body, the amount of the remaining solvent is practically 7 mg / m ² or less, and when it is larger than 7 mg / m ² , a strange odor is felt from the film. Cause. Preferably 5 mg / ^{m 2} or less in the case of strictly control the odor of the film, 3 mg / ^{m 2} or less is particularly preferred.

  In the dry laminating method, the adhesive can be applied not only to the base material layer but also to the thermoplastic resin layer, and is applied to polyolefin films such as polyethylene film, polypropylene film, and ethylene-vinyl acetate copolymer film. After drying, a laminate can be produced by laminating a stretched polypropylene film, a polyamide-based film, a polyethylene terephthalate film, or the like.

  In the case of bonding by nip roll, the nip roll can be heated and bonded to 20 ° C. to 120 ° C., but 40 to 100 ° C. is desirable.

  In this case, it is desirable to complete the curing reaction by performing aging at 20 ° C. to 60 ° C. for a certain time as necessary after lamination. By aging for a certain period of time, a cured epoxy resin is formed with a sufficient reaction rate, and high gas barrier properties are exhibited. When the aging is 20 ° C. or less or without aging, the reaction rate of the epoxy resin composition is low, and sufficient gas barrier properties and adhesive strength cannot be obtained. Also, aging at 60 ° C. or higher can cause problems such as polymer film blocking and additive elution.

  Further, in the case of the non-solvent laminating method, by using a roll such as a gravure roll in which the adhesive in the present invention that has been heated to about 40 ° C. to 100 ° C. in advance to the material to be the base material is heated to 40 ° C. to 120 ° C. Immediately after application, a laminate can be obtained by bonding a thermoplastic resin layer to the surface. In this case as well, as in the case of the dry laminating method, it is desirable to perform aging for a predetermined time after the lamination as necessary.

In the case of the extrusion laminating method, a diluted solution of an epoxy resin and an epoxy resin curing agent, which are the main components of the adhesive in the present invention, as an adhesion auxiliary agent (anchor coating agent) for the base material, with an organic solvent and / or water Is applied by a roll such as a gravure roll, and after drying and curing reaction of the solvent at 20 ° C. to 140 ° C., a laminate can be obtained by laminating a polymer material melted by an extruder. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
These laminating methods and other generally used laminating methods can be combined as necessary, and the layer structure of the laminate can be changed depending on the application and form.

The thickness of the adhesive layer after applying, drying, bonding and heat-treating the adhesive in the present invention to various materials is 0.1 to 100 μm, preferably 0.5 to 10 μm. If the thickness is less than 0.1 μm, sufficient gas barrier properties and adhesiveness are hardly exhibited. On the other hand, if the thickness exceeds 100 μm, it is difficult to form an adhesive layer having a uniform thickness.
In this case, the laminate strength at a peeling speed of 300 mm / min is preferably 600 g / 15 mm or more, and more preferably 700 g / 15 mm or more.

  A multilayer container can be manufactured using the laminate of the present invention. There is no restriction | limiting in the method of manufacturing a multilayer container, A well-known container manufacturing method is employable. For example, a bag-like container will be described. The bag-like container is a bag-like container in which a laminate film including at least a base material layer containing aluminum, a layer made of a cured epoxy resin, and a thermoplastic resin layer having heat sealability is formed, and the heat seal thereof The surfaces of the thermoplastic resin layer having properties can be opposed to each other, and then the peripheral end portions thereof can be heat sealed to form a seal portion. As the bag making method, for example, the laminated film is folded or overlapped so that the inner layer faces each other, and the peripheral edge thereof is, for example, a side seal type, a two-side seal type, a three-side seal type, a four-sided type. Examples of the heat sealing method include a seal type, an envelope sticking seal type, a palm sticking seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a square bottom seal type, a gusset type, and the like. The bag-like container can take various forms depending on the use environment and use form. In addition, for example, a self-supporting packaging bag (standing pouch) is also possible. As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  The bag-shaped container is filled with a hair dye-containing article such as a first agent of an oxidative hair dye from the opening, and then the opening is heat-sealed to store the hair dye-containing article. I can do it. Other contents that can be filled include soap sheets such as pore sheets, body wiping sheets, wiping cloths, cleaning wet wipes, face wash, liquid soap, powder soap, hand soap, laundry soap, kitchen detergent, etc. Shampoos, conditioners, treatments, etc., toothpaste cleaners, toothpastes, bath preparations, bath oil, makeup remover, cleansing oil, lotion, light remover, beauty pack masks / sheets, poultices, paints, etc. Pharmaceuticals, cooling sheets, disinfecting cotton, contraceptives, insecticides, fragrances, insect repellents and the like.

  Next, various components blended in the first agent of the oxidative hair dye will be described. Examples of the oxidative dye intermediate compounded in the first part of the oxidative hair dye include phenylenediamines, aminophenols, toluylenediamines, aminonitrophenols, diphenylamines, diaminophenylamines, and N-phenylphenylenediamine. , Diaminopyridines and the like and salts thereof are used. Examples of the salt include hydrochloride, sulfate, acetate and the like. Among these, paraphenylenediamine, paratoluylenediamine, N, N-bis (2-hydroxyethyl) -paraphenylenediamine, N-phenyl-paraphenylenediamine, 4,4′-diaminodiphenylamine, 2-chloroparaphenylenediamine N, N-dimethylparaphenylenediamine, paraaminophenol, 2,6-dichloroparaphenylenediamine, paraaminophenylsulfamic acid and their salts are preferred from the viewpoint of hair dyeing power.

  The blending amount of the oxidation dye intermediate is preferably 0.01 to 15% by weight with respect to the first agent, and if it is less than 0.01% by weight, a sufficient hair dyeing effect cannot be obtained, and even if it exceeds 15% by weight. The effect remains the same and is not economical. Furthermore, 0.1 to 10 weight% is especially preferable, and the more excellent hair dyeing effect is acquired by mix | blending 0.1 weight% or more. On the other hand, if it exceeds 10% by weight, the increase in hair dyeing effect is reduced.

  Moreover, as a coupler, resorcinol, pyrogallol, catechol, metaaminophenol, metaphenylenediamine, orthoaminophenol, 2,4-diaminophenol, 1,2,4-benzenetriol, toluene-2,4-diamine, hydroquinone, α -Naphthol, 2,6-diaminopyridine, 1,5-dihydroxynaphthalene, 5-aminoorcresol, diphenylamine, paramethylaminophenol, phloroglucin, 2,4-diaminophenoxyethanol, gallic acid, tannic acid, ethyl gallate, gallic acid At least one selected from methyl acid, propyl gallate, 5- (2-hydroxyethylamino) -2-methylphenol, and salts thereof may be added to the first agent.

  The blending amount is preferably 0.01 to 10% by weight, and if it is less than 0.01% by weight, sufficient dyeability cannot be obtained, and even if it exceeds 10% by weight, the effect is not changed and it is not economical. Furthermore, 0.1 to 5 weight% is preferable, and by mix | blending 0.1 weight% or more, the more outstanding dyeability is obtained. On the other hand, when it exceeds 5% by weight, the increase in dyeability is reduced. In addition, those listed in "Quasi-drug raw material standards" (issued in June 1991, Yakuji Nippo) may be appropriately blended.

  As direct dyes blended in the first agent, 4-nitro-o-phenylenediamine, 4-nitro-m-phenylenediamine, 2-nitro-p-phenylenediamine, picramic acid, 1-amino-4-methylanthraquinone , 1,4-diaminoanthraquinone, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picric acid and their salts, and "Ministerial ordinance for determining tar dyes that can be used for pharmaceuticals, etc." Red dye No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, red 201, red 227, red 230 (1), red 230 (2), red 231, red 232, red 401, red 502, red 503, Red 504, Red 506, Yellow 4, Yellow 5, Yellow 202 (1), Yellow 202 (2), Yellow 203, Yellow 402, Yellow 403 (1) , Yellow 406, yellow 407, orange 205, orange 207, orange 402, green 3, green 204, green 205, green 401, green 402, purple 401, blue 1 No. 2, Blue No. 2, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Black No. 401 and the like are used. Further, by blending this direct dye, a more excellent effect can be obtained in dyeing and dyeability.

  The blending amount of the direct dye is preferably 0.001 to 10% by weight, and if it is less than 0.001% by weight, sufficient dyeing and dyeability cannot be obtained, and even if it exceeds 10% by weight, the effect does not change. Not economical. Furthermore, 0.01 to 5% by weight is particularly preferable, and by blending 0.01% by weight or more, more excellent dyeing and dyeability can be obtained. On the other hand, when the amount exceeds 5% by weight, dyeing and dyeing are less likely to increase.

  Examples of the alkaline agent blended in the first agent include ammonia, alkanolamines (triethanolamine, diethanolamine, monoethanolamine, isopropanolamine, diisopropanolamine, etc.), organic amines (2-amino-2-methyl- 1-propanol, 2-amino-2-methyl-1,3-propanediol, guanidine, etc.), inorganic alkali (sodium hydroxide, potassium hydroxide, etc.), basic amino acids (arginine, lysine, etc.) and their salts, etc. At least one selected from is used. Furthermore, they may be combined to form a buffer solution. The pH of the first agent is adjusted to pH 8-11.

  In the multilayer container of the present invention, since the layer made of the cured epoxy resin has a high barrier property against ammonia or the like, the first agent of the oxidative hair dye can be stably stored by sealing in the container. it can. The layer configuration of the multilayer container (or laminate) can vary depending on the usage form. That is, the laminate in the present invention can be used as a gas barrier laminate material for preserving the hair dye-containing article as it is, and if necessary, an oxygen absorbing layer, a thermoplastic resin film layer, a paper layer, a metal foil layer, etc. Can be further laminated on the laminate in the present invention. Under the present circumstances, you may laminate using the adhesive agent consisting of the epoxy resin hardened | cured material in this invention, and you may laminate | stack using another adhesive agent and an anchor coat agent.

  Next, the operation of the hair dye storage container configured as described above will be described. The aluminum film used for the base material layer prevents the penetration of oxygen, moisture, etc. from the outside when the first agent of the oxidative hair dye is stored in the hair dye storage container of the embodiment. It has the characteristic to do. However, since aluminum film is inferior in pinhole resistance, the barrier property may be lowered depending on the use situation, but the barrier property is lowered because it has an adhesive having a barrier property on the inner layer side. Therefore, it is possible to prevent oxidation (blackening) of the dye in the container body due to oxygen from the outside. In addition, since the epoxy adhesive has a characteristic of preventing the penetration of ammonia in the hair dye, there is no possibility that the amount of the dye or ammonia in the first agent is reduced during storage.

  Moreover, since it forms by joining a resin raw material, a structure is simple and can aim at reduction of material cost and manufacturing cost compared with the conventional aerosol can and a tube container.

  Examples of the present invention are introduced below, but the present invention is not limited to these examples.

<Epoxy resin curing agent a>
A reaction vessel was charged with 1 mole of metaxylylenediamine. The temperature was raised to 60 ° C. under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 1 hour, and further heated to 160 ° C. in 3 hours while distilling off generated methanol. The mixture was cooled to 100 ° C., and a predetermined amount of methanol was added so that the solid content concentration became 70% by weight to obtain an epoxy resin curing agent a. The content of amide groups in the epoxy resin curing agent a was 21% by weight.

Moreover, the evaluation method of laminate strength is as follows.
<Lamination strength (g / 15mm)>
Using the method specified in JISK-6854, the laminate strength of the laminate film was measured by a T-type peel test at a peel rate of 300 mm / min.

<Example 1>
Methanol / ethyl acetate = 9/1 solution containing 50 parts by weight of an epoxy resin having a glycidyl ether moiety derived from bisphenol A (Japan Epoxy Resin Co., Ltd .; Epicoat 828) and 71 parts by weight of epoxy resin curing agent a ( Solid content concentration: 35% by weight) was prepared, and 0.3 part by weight of an acrylic wetting agent (BIC Chemie; BYK381) was added thereto and stirred well to obtain an adhesive.
This adhesive was applied using a bar coater No. 8 to the aluminum side of a multilayer film obtained by laminating a stretched PET film having a thickness of 12 μm and an aluminum film having a thickness of 40 μm (application amount: 4.5 g / m ² ( Solid content)), dried at 85 ° C. for 10 seconds, and then a 40 μm-thick linear low-density polyethylene film (TUX MC-S manufactured by Tosero Co., Ltd.) was applied by a nip roll heated to 40 ° C. In addition, the laminated film A was obtained by aging at 40 ° C. for 4 days.

<Comparative Example 1>
A laminated film B was obtained in the same manner as in Example 1 except that a two-component curable polyurethane adhesive (TM-329 / CAT-8B manufactured by Toyo Morton Co., Ltd.) was used as the adhesive.

<Example 2>
Two sheets of laminated film A (size: 150 mm x 100 mm) are prepared, the linear low-density polyethylene film faces are placed facing each other, and the edges around the outer periphery are heat-sealed to form a seal part. A three-side-seal type packaging bag having an opening on the upper side was produced. The produced three-side seal type packaging bag was filled with 100 g of the hair dye composition from the opening, and the opening was sealed by heat sealing to produce a package.
As the hair dye composition, Hoyu Co., Ltd. “Bigen-scented hair color early dyeing type (for white hair)” was used. The contents of the first agent were paraamino orthocresol, paraaminophenol, paraphenylenediamine, metaaminophenol, monoethanolamine, resorcin, stearyl alcohol, cetanol, paraben, and fragrance.

  After the packaging body was stored at 35 ° C. for 3 months, the appearance of the packaging body was observed, and the packaging body was cut to observe changes in the color tone of the hair dye composition therein. The appearance of the package was the same as that immediately after storage, there was no swelling and the color tone of the hair dye was well maintained without change.

<Comparative Example 2>
Instead of using the laminated film A, a package was produced in the same manner as in Example 2 except that the laminated film B was used.

  After the packaging body was stored at 40 ° C. for 3 months, the appearance of the packaging body was observed, and the packaging body was cut to observe changes in the color tone of the hair dye composition. As for the appearance, penetration of the dye into the package was observed. Moreover, discoloration of the hair dye was seen and quality deterioration was confirmed.

Claims (6)

A multilayer container for storing a hair dye, comprising a laminate in which at least a base material layer containing aluminum, a layer made of a cured epoxy resin, and a thermoplastic resin layer are laminated in this order, the cured epoxy resin, an epoxy resin having a derived glycidyl ether moiety from bisphenol a, (1) Ri cured der epoxy resin curing agent is obtained by reaction containing skeleton structure of formula, wherein multilayer containers epoxy resin curing agent is characterized in the reaction product der Rukoto of the following and (a) (B).
(A) Metaxylylenediamine
(B) Acrylic acid, methacrylic acid and / or its ester, amide, acid anhydride or acid chloride
^2. The multilayer container according to claim 1, wherein the cured epoxy resin has an oxygen permeability coefficient of 20 ml · mm / (m ² · day · MPa) or less at 23 ° C. and 60% RH. At least, the base layer containing aluminum, multilayer container according to claim 1, wherein the bag-like container having Seibukuro a laminate film comprising a thermoplastic resin layer having a layer and heat sealability comprising an epoxy resin cured product. A hair dye storage method, wherein the hair dye is sealed and stored in the multilayer container according to claim 1 . The multilayer container according to claim 1, wherein the reaction molar ratio of (B) to (A) is in the range of 0.8 to 0.97. The multilayer container according to claim 1, wherein the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is in the range of 0.8 to 1.4.