JP4754383B2 - Laminated tube container - Google Patents

Description

  The present invention relates to a laminated tube container suitable for filling and packaging contents such as cosmetics, medicines, pharmaceuticals, foods, and toothpastes. The laminate tube container of the present invention relates to a laminate tube container that is excellent in oxygen barrier properties and that can protect the contents from oxidative degradation over a long period of time because the oxygen barrier properties do not decrease even after the laminate tube container is squeezed.

  Conventionally, laminated tube containers used for packaging cosmetics, medicines, pharmaceuticals, toiletries such as toothpaste, kneading, wasabi and other foods must have excellent gas barrier properties and aroma retention. In many cases, a laminated material using a resin film having an aluminum foil or an aluminum deposition layer is used. However, since the laminated material cannot be made transparent, there has been a limitation on the design of the packaging material. In addition, since it is difficult to see through the contents, it is not easy to check the contents of the contents, such as alteration and remaining amount, and it is inconvenient to squeeze the contents to the end. Furthermore, when the tube container is used as a packaging device and then discarded as garbage, aluminum remains, so that the disposal property is insufficient, and the remaining aluminum damages the incinerator.

  As a gas barrier film having transparency and excellent disposal property, a transparent vapor-deposited film having an inorganic oxide vapor-deposited layer by a vacuum vapor deposition method, a film using a polyvinylidene chloride resin, ethylene-vinyl alcohol A film in which a copolymer is used can be listed. These are also used as laminated tube containers (see, for example, Patent Documents 1 and 2).

  However, the transparent vapor deposition film is prone to cracks and other defects in the vapor deposition layer, which is a gas barrier layer, in the printing process and laminating process until the laminated tube container is manufactured, and when the laminated tube container is squeezed. Also, defects such as cracks are likely to occur, resulting in poor gas barrier properties.

  In addition, films using polyvinylidene chloride resin may cause harmful gases such as dioxins when incinerated as garbage after using a laminated tube container as a packaging device. It is.

  The ethylene-vinyl alcohol copolymer is an excellent barrier film from the viewpoints of gas barrier properties, transparency, and the environment, but the gas barrier properties decrease when the ethylene-vinyl alcohol copolymer absorbs moisture. have.

JP 11-129380 A JP 7-308994 A

  The problems to be solved by the present invention are excellent from the viewpoints of environment and disposal, the container design is diverse, has retort sterilization resistance, and has superior oxygen barrier properties compared to conventional laminated tube containers. Another object of the present invention is to provide a laminate tube container in which the oxygen barrier property does not deteriorate even when the laminate tube container is squeezed. In many cases, the contents packed in the laminate tube container are consumed little by little and the consumption period is long. An object of the present invention is to provide a laminated tube container particularly suitable for pharmaceuticals, cosmetics, foods and the like whose contents are susceptible to oxygen degradation.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have determined that the gas barrier laminate is specific to the base material and at least one surface of the base material in the laminate tube container having at least the gas barrier laminate. When the gas barrier layered body is formed by laminating gas barrier layers, the inventors have found that the above object can be achieved and have completed the present invention. That is, the present invention relates to a laminated tube container having at least a gas barrier laminate, wherein the gas barrier laminate is a gas barrier laminate including a base material and a gas barrier layer laminated on at least one surface of the base material. And the gas barrier layer comprises a composition comprising a hydrolysis condensate of compound (L) and a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group,
The compound (L) comprises at least one compound (A) represented by the following chemical formula (I) and at least one compound (B) represented by the following chemical formula (II):
The molar ratio of the compound (A) / the compound (B) is in the range of 0.5 / 99.5 to 40/60,
The laminate tube container is characterized in that at least a part of —COO— group contained in the at least one functional group is neutralized with a divalent or higher valent metal ion.
M ¹ (OR ¹ ) _n X ¹ _k Z _m−n−k (I)
[In the chemical formula (I), M ¹ is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Represents Nd. R ¹ represents an alkyl group. X ¹ represents a halogen atom. Z represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. m is equal to the valence of M ¹ . n represents an integer of 0 to (m-1). k represents an integer of 0 to (m−1). 1 ≦ n + k ≦ (m−1). ]
_{^{M 2 (OR 2) q R}} 3 p-q-r X 2 r ··· (II)
[In the chemical formula (II), M ² is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Represents Nd. R ² represents an alkyl group. R ³ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p is equal to the valence of M ² . q represents an integer of 0 to p. r represents an integer of 0 to p. 1 ≦ q + r ≦ p. ]

  The tube container of the present invention is excellent from the viewpoints of environment and disposal, has a variety of container designs, has resistance to retort sterilization, has superior oxygen barrier properties compared to conventional tube containers, and is a tube container It is possible to provide a tube container that does not deteriorate the oxygen barrier property even if squeezed.

  Embodiments of the present invention will be described below. In the following description, a specific compound may be exemplified as a substance that exhibits a specific function, but the present invention is not limited to this. In addition, the materials exemplified may be used alone or in combination unless otherwise specified.

  The laminated tube container of the present invention has a gas barrier laminate (hereinafter referred to as gas barrier property) having a base material and a specific gas barrier layer (hereinafter referred to as a gas barrier layer used in the present invention) laminated on at least one surface of the base material. A body part formed in a cylindrical shape from a laminate having a laminate (which may be referred to as a laminate (I)), and a shoulder part and a cap part having a threaded mouth part formed from a thermoplastic resin by an injection molding method or the like Consists of For example, a laminate having a gas barrier laminate is bent into a cylindrical shape, and both end edges in the longitudinal direction are overlapped, and the overlapped portions are heat-welded by high frequency and bonded to produce a cylindrical body. Hereinafter, the gas barrier layer used in the present invention will be described in detail.

(Gas barrier layer)
The gas barrier layer used in the present invention comprises a composition containing a neutralized product of a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group, and is contained in the at least one functional group. That at least a part of the —COO— group is neutralized with a divalent or higher metal ion, in other words, at least a part of the at least one functional group forms a salt with the divalent or higher metal ion. It is characterized by.

(Carboxylic acid-containing polymer)
The composition constituting the gas barrier layer includes a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The content of the neutralized product of the polymer in the composition is not particularly limited and can be, for example, in the range of 25% by weight to 95% by weight. The neutralized product of this polymer is a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group (hereinafter sometimes referred to as “carboxylic acid-containing polymer”). It is a polymer obtained by neutralizing at least part of one functional group with a divalent or higher metal ion.

  The carboxylic acid-containing polymer has two or more carboxyl groups or one or more carboxylic anhydride groups in one polymer molecule. Specifically, a polymer containing two or more structural units having one or more carboxyl groups such as an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, and an itaconic acid unit in one molecule of the polymer is used. it can. Moreover, the polymer containing the structural unit which has the structure of carboxylic anhydrides, such as a maleic anhydride unit and a phthalic anhydride unit, can also be used. There may be one type of structural unit having at least one carboxyl group and / or structural unit having a structure of carboxylic anhydride (hereinafter, both may be abbreviated as carboxylic acid-containing unit (C)). Two or more types may be included.

  Further, by setting the content of the carboxylic acid-containing unit (C) in the total structural unit of the carboxylic acid-containing polymer to 10 mol% or more, a gas barrier laminate having a good gas barrier property under high humidity can be obtained. . The content is more preferably 20 mol% or more, further preferably 40 mol% or more, and particularly preferably 70 mol% or more. In addition, when a carboxylic acid containing polymer contains both the structural unit containing 1 or more of carboxyl groups, and the structural unit which has a structure of carboxylic anhydride, both should just be the said range.

  The structural unit other than the carboxylic acid-containing unit (C) that may be contained in the carboxylic acid-containing polymer is not particularly limited, but is a methyl acrylate unit, a methyl methacrylate unit, an ethyl acrylate unit, methacrylic acid. Structural units derived from (meth) acrylates such as ethyl units, butyl acrylate units and butyl methacrylate units; structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; styrene units, One or more structural units selected from p-styrene sulfonic acid units; structural units derived from olefins such as ethylene units, propylene units, and isobutylene units. When the carboxylic acid-containing polymer contains two or more structural units, the carboxylic acid-containing polymer is in the form of an alternating copolymer, a random copolymer, a block copolymer, or a taper. It may be in the form of a type copolymer.

  Preferable examples of the carboxylic acid-containing polymer include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymer. The carboxylic acid-containing polymer may be one kind or a mixture of two or more kinds of polymers. For example, at least one polymer selected from polyacrylic acid and polymethacrylic acid may be used. Specific examples in the case of containing other structural units described above include ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid. And a saponified product of an ethylene-ethyl acrylate copolymer.

  The molecular weight of the carboxylic acid-containing polymer is not particularly limited, but the number average molecular weight is 5,000 or more because the gas barrier property of the obtained gas-barrier laminate is excellent and the mechanical properties such as drop impact strength are excellent. Preferably, it is preferably 10,000 or more, and more preferably 20,000 or more. The upper limit of the molecular weight of the carboxylic acid-containing polymer is not particularly limited, but is generally 1,500,000 or less.

  Further, the molecular weight distribution of the carboxylic acid-containing polymer is not particularly limited, but from the viewpoint of improving the surface appearance such as haze of the gas barrier laminate, and the storage stability of the solution (S) described later, The molecular weight distribution represented by the weight average molecular weight / number average molecular weight ratio of the carboxylic acid-containing polymer is preferably in the range of 1-6, more preferably in the range of 1-5, and in the range of 1-4. More preferably.

  The polymer constituting the gas barrier layer used in the present invention contains at least one functional group selected from the carboxyl group and carboxylic anhydride group of the carboxylic acid-containing polymer (hereinafter sometimes referred to as functional group (F)). For example, 10 mol% or more (for example, 15 mol% or more) of the —COO— group is neutralized with a bivalent or higher metal ion. Note that the carboxylic anhydride group is considered to contain two —COO— groups. That is, when there are a moles of carboxyl groups and b moles of carboxylic anhydride groups, the total number of —COO— groups contained is (a + 2b) moles. The proportion of the -COO- group contained in the functional group (F) that is neutralized with a divalent or higher metal ion is preferably 20 mol% or more, more preferably 30 mol% or more, and Preferably it is 40 mol% or more, More preferably, it is 50 mol% or more, Most preferably, it is 60 mol% or more. Although there is no restriction | limiting in particular in the upper limit of the ratio neutralized with the metal ion more than bivalence among -COO- groups contained in a functional group (F), For example, it can be 95 mol% or less. When the carboxyl group and / or carboxylic anhydride group in the carboxylic acid-containing polymer is neutralized with a metal ion having a valence of 2 or more, the gas barrier layer used in the present invention is subjected to a dry condition and a high humidity condition. Both show good gas barrier properties.

The degree of neutralization (ionization degree) of the functional group (F) is determined by measuring the infrared absorption spectrum of the gas barrier laminate by the ATR (total reflection measurement) method, or by scraping the gas barrier layer from the gas barrier laminate. It can be determined by measuring the infrared absorption spectrum by the KBr method. Before neutralization peak attributed to C = O stretching vibration of the carboxyl group or carboxylic anhydride group (ionization front) was observed in the range of 1600cm ^-1 ~1850cm ^-1, after being neutralized (ionized) C = O stretching vibration of the carboxyl group is to be observed in a range of 1500cm ^-1 ~1600cm ^-1, it can be evaluated by separating the two in the infrared absorption spectrum. Specifically, the ratio is obtained from the maximum absorbance in each range, and the ionization degree of the polymer constituting the gas barrier layer in the gas barrier laminate can be calculated using a calibration curve prepared in advance. A calibration curve can be created by measuring infrared absorption spectra for a plurality of standard samples having different degrees of neutralization.

  It is important that the metal ion neutralizing the functional group (F) is divalent or higher. When the functional group (F) is not neutralized or is neutralized only by monovalent ions described later, a laminate having good gas barrier properties cannot be obtained. However, when the functional group (F) is neutralized with a small amount of monovalent ions (cations) in addition to divalent or higher metal ions, the haze of the gas barrier laminate is reduced and the surface appearance is reduced. Becomes better. Thus, the present invention includes the case where the functional group (F) of the carboxylic acid-containing polymer is neutralized with both a divalent or higher-valent metal ion and a monovalent ion. Examples of the divalent or higher metal ion include calcium ion, magnesium ion, divalent iron ion, trivalent iron ion, zinc ion, divalent copper ion, lead ion, divalent mercury ion, barium ion, A nickel ion, a zirconium ion, an aluminum ion, a titanium ion, etc. can be mentioned. For example, at least one ion selected from calcium ions, magnesium ions, and zinc ions may be used as the divalent or higher metal ion.

  In the present invention, 0.1 to 10 mol% of the —COO— group contained in the functional group (F) (carboxyl group and / or carboxylic acid anhydride) of the carboxylic acid-containing polymer is a monovalent ion. It is preferable that they are summed. However, when the degree of neutralization with monovalent ions is high, the gas barrier properties of the gas barrier laminate are deteriorated. The degree of neutralization of the functional group (F) with monovalent ions is more preferably in the range of 0.5 to 5 mol%, and still more preferably in the range of 0.7 to 3 mol%. Examples of monovalent ions include ammonium ions, pyridinium ions, sodium ions, potassium ions, and lithium ions, with ammonium ions being preferred.

  The composition constituting the gas barrier layer used in the present invention is a metal atom in which at least one characteristic group (atomic group) selected from a halogen atom and an alkoxy group is bonded in addition to the carboxylic acid-containing polymer and the neutralized product thereof. It is preferable that the hydrolysis condensate of at least 1 type of compound (L) containing is included. By including the hydrolysis condensate of compound (L), extremely good gas barrier properties are achieved.

(Hydrolysis condensate)
As the compound (L), at least one of the compound (A) and / or the compound (B) described below can be applied. Hereinafter, the compound (A) and the compound (B) will be described.

Compound (A) is at least one compound represented by the following chemical formula (I).
M ¹ (OR ¹ ) _n X ¹ _k Z ¹ _mnk (I)
In chemical formula (I), M ¹ is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and Represents an atom selected from Nd. M ¹ is preferably Si, Al, Ti or Zr, and particularly preferably Si. In the chemical formula (I), R ¹ is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or a t-butyl group, preferably a methyl group or an ethyl group. It is a group. In the chemical formula (I), X ¹ represents a halogen atom. Examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. In the chemical formula (I), Z ¹ represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. Here, examples of the functional group having reactivity with a carboxyl group include an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, or a carbodiimide group. An amino group, mercapto group, isocyanate group, ureido group, or halogen atom is preferred. Examples of the alkyl group substituted with such a functional group include those described above. In the chemical formula (I), m is equal to the valence of the metal element M ¹ . In chemical formula (I), n represents an integer of 0 to (m-1). Moreover, in chemical formula (I), k represents an integer of 0 to (m−1), and 1 ≦ n + k ≦ (m−1).

  Specific examples of the compound (A) include γ-glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ -Bromopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and the like. The methoxy group portion of these compounds is substituted with ethoxy group, n A compound having an alkoxy group or a chlorine group such as a -propoxy group, an iso-propoxy group, an n-butoxy group, or a t-butoxy group may be used. Also, chloromethylmethyldimethoxysilane, chloromethyldimethylmethoxysilane, 2-chloroethylmethyldimethoxysilane, 2-chloroethyldimethylmethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, mercaptomethylmethyldimethoxy Silane, mercaptomethyldimethylmethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyldimethylmethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, isocyanatemethylmethyldimethoxysilane, isocyanatemethyldimethylmethoxy Silane, 2-isocyanatoethylmethyldimethoxysilane, 2-isocyanatoethyldimethyl Rumethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, ureidomethylmethyldimethoxysilane, ureidomethyldimethylmethoxysilane, 2-ureidoethylmethyldimethoxysilane, 2-ureidoethyldimethylmethoxysilane, 3- Examples include ureidopropylmethyldimethoxysilane, 3-ureidopropyldimethylmethoxysilane, and bis (chloromethyl) methylchlorosilane. The methoxy group portion of these compounds is substituted with ethoxy group, n-propoxy group, iso-propoxy group, n- A compound having an alkoxy group or a chlorine group such as a butoxy group or a t-butoxy group may be used. Further, chloromethyltrimethoxysilane, 2-chloroethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2-chloropropyltrimethoxysilane, 4-chlorobutyltrimethoxysilane, 5-chloropentyltrimethoxysilane, 6- Chlorohexyltrimethoxysilane, (dichloromethyl) dimethoxysilane, (dichloroethyl) dimethoxysilane, (dichloropropyl) dimethoxysilane, (trichloromethyl) methoxysilane, (trichloroethyl) methoxysilane, (trichloropropyl) methoxysilane, mercaptomethyl Trimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltrimethoxysilane, 4-mercaptobutylto Methoxysilane, 5-mercaptopentyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, (dimercaptomethyl) dimethoxysilane, (dimercaptoethyl) dimethoxysilane, (dimercaptopropyl) dimethoxysilane, (trimercaptomethyl) methoxysilane , (Trimercaptoethyl) methoxysilane, (trimercaptopropyl) methoxysilane, fluoromethyltrimethoxysilane, 2-fluoroethyltrimethoxysilane, 3-fluoropropyltrimethoxysilane, bromomethyltrimethoxysilane, 2-bromoethyltri Methoxysilane, 3-bromopropyltrimethoxysilane, iodomethyltrimethoxysilane, 2-iodoethyltrimethoxysilane, 3-iodopropyltrimethoxysilane , (Chloromethyl) phenyltrimethoxysilane, (chloromethyl) phenylethyltrimethoxysilane, 1-chloroethyltrimethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, (3-chlorocyclohexyl) trimethoxysilane, ( 4-chlorocyclohexyl) trimethoxysilane, (mercaptomethyl) phenyltrimethoxysilane, (mercaptomethyl) phenylethyltrimethoxysilane, 1-mercaptoethyltrimethoxysilane, 2- (mercaptomethyl) allyltrimethoxysilane, (3- Mercaptocyclohexyl) trimethoxysilane, (4-mercaptocyclohexyl) trimethoxysilane, N- (3-triethoxysilylpropyl) gluconamide, N- (3-triethoxysilylpropyl) -4 -Hydroxybutyramide, isocyanate methyltrimethoxysilane, 2-isocyanatoethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatopropyltrimethoxysilane, 4-isocyanatobutyltrimethoxysilane, 5-isocyanatepentyltrimethoxysilane 6-isocyanatohexyltrimethoxysilane, (diisocyanatemethyl) dimethoxysilane, (diisocyanateethyl) dimethoxysilane, (diisocyanatepropyl) dimethoxysilane, (triisocyanatemethyl) methoxysilane, (triisocyanateethyl) methoxysilane, (triisocyanatepropyl) ) Methoxysilane, ureidomethyltrimethoxysilane, 2-ureidoethyltrimeth Sisilane, 3-ureidopropyltrimethoxysilane, 2-ureidopropyltrimethoxysilane, 4-ureidobutyltrimethoxysilane, 5-ureidopentyltrimethoxysilane, 6-ureidohexyltrimethoxysilane, (diureidomethyl) dimethoxysilane, (Diureidoethyl) dimethoxysilane, (diureidopropyl) dimethoxysilane, (triureidomethyl) methoxysilane, (triureidoethyl) methoxysilane, (triureidopropyl) methoxysilane, and the methoxy group of these compounds Alternatively, a compound having an alkoxy group such as an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a t-butoxy group or a chlorine group may be used.

  Preferred compounds (A) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-aminopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane.

The compound (B) is at least one compound represented by the following chemical formula (II).
M ² (OR ² ) _q R ³ _pqr X ² _r (II)
In chemical formula (II), M ² is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and It represents an atom selected from Nd, preferably Si, Al, Ti or Zr, and particularly preferably Si, Al or Ti. In the chemical formula (II), R ² represents an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or a t-butyl group, preferably a methyl group. Or it is an ethyl group. In the chemical formula (II), X ² represents a halogen atom. Examples of the halogen atom represented by X ² include a chlorine atom, a bromine atom and an iodine atom, but a chlorine atom is preferred. In the chemical formula (II), R ³ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. Examples of the alkyl group represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and an n-octyl group. Moreover, examples of the aralkyl group represented by R ³ include a benzyl group, a phenethyl group, and a trityl group. Examples of the aryl group represented by R ³ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. In addition, examples of the alkenyl group represented by R ³ include a vinyl group and an allyl group. Furthermore, in the chemical formula (II), p is equal to the valence of the metal element M ² . In chemical formula (II), q represents an integer of 0 to p. Moreover, in chemical formula (II), r represents the integer of 0-p and is 1 <= q + r <= p.

In the chemical formulas (I) and (II), M ¹ and M ² may be the same or different. R ¹ and R ² may be the same or different.

  Specific examples of the compound (B) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, chlorotri Silicon alkoxides such as methoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; halogenated silanes such as vinyltrichlorosilane, tetrachlorosilane, and tetrabromosilane; tetramethoxytitanium, tetra Alkoxytitanium compounds such as ethoxytitanium, tetraisopropoxytitanium, methyltriisopropoxytitanium; titanium halides such as tetrachlorotitanium Alkoxyaluminum compounds such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, tributoxyaluminum, diethoxyaluminum chloride; alkoxy such as tetraethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium A zirconium compound etc. are mentioned.

  It is preferable that the composition which comprises the gas barrier layer used for this invention contains the hydrolysis-condensation product of a compound (L). By hydrolyzing the compound (L), at least a part of the halogen and alkoxy groups of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which metal elements are bonded through oxygen. When this condensation is repeated, it becomes a compound that can be regarded as a metal oxide substantially.

  The hydrolysis condensate of compound (L) contained in the gas barrier layer of the gas barrier laminate preferably has a condensation degree P defined below of 65 to 99%, more preferably 70 to 99%. Preferably, it is 75 to 99%. The degree of condensation P (%) in the hydrolysis condensate of compound (L) is calculated as follows.

  A compound in which the total number of alkoxy groups and halogen atoms in one molecule of compound (L) is a, and the total of condensed alkoxy groups and halogen atoms is i (pieces) in the hydrolyzed condensate of compound (L) When the ratio of (L) is yi (%) in all the compounds (L), i is an integer of 1 to a (including 1 and a) for each value {(i / a) × yi} And add them. That is, the degree of condensation P (%) is defined by the following mathematical formula.

上記したｙｉの値は、ガスバリア層中の化合物（Ｌ）の加水分解縮合物については固体のＮＭＲ（ＤＤ／ＭＡＳ法）等によって測定することができる。

The value of yi described above can be measured by solid NMR (DD / MAS method) or the like for the hydrolysis condensate of compound (L) in the gas barrier layer.

  The hydrolysis-condensation product is a compound (L), a compound (L) partially hydrolyzed, a compound (L) completely hydrolyzed, or a compound (L) partially hydrolyzed and condensed. For example, a compound obtained by completely hydrolyzing the compound (L) and partially condensing it, or a combination thereof can be produced by a method used in a known sol-gel method, for example. These raw materials may be produced by a known method, or commercially available ones may be used. Although there is no particular limitation, for example, a condensate obtained by hydrolysis and condensation of about 2 to 10 molecules can be used as a raw material. Specifically, for example, a material obtained by hydrolyzing and condensing tetramethoxysilane to obtain a dimer to 10-mer linear condensate can be used as a raw material.

  The number of molecules condensed in the hydrolytic condensate of the compound (L) in the composition constituting the gas barrier layer of the gas barrier laminate is the amount of water, the type and concentration of the catalyst used in the hydrolysis and condensation, It can be controlled by the temperature at which decomposition condensation is performed.

  The method for producing the hydrolyzed condensate of compound (L) is not particularly limited, but in a typical example of the sol-gel method, hydrolysis and condensation are performed by adding water, an acid and an alcohol to the above-described raw material.

  Hereinafter, the compound (L) may be described as a metal alkoxide (a compound including a metal to which an alkoxy group is bonded), but a compound including a metal to which a halogen is bonded may be used instead of the metal alkoxide.

  As described above, the compound (L) can be at least one of the compound (A) and / or the compound (B). When the compound (L) contains only the compound (A) or contains both the compound (A) and the compound (B), it is preferable because the gas barrier property of the gas barrier laminate is improved. The compound (L) substantially consists of both the compound (A) and the compound (B), and the molar ratio of the compound (A) / the compound (B) is 0.5 / 99.5 to 40 /. More preferably, it is in the range of 60. When the compound (A) and the compound (B) are used together in this ratio, the gas barrier properties of the gas barrier laminate, such as mechanical properties such as tensile strength and elongation, appearance, and handling properties are excellent. The molar ratio of compound (A) / compound (B) is more preferably in the range of 3/97 to 40/60, and still more preferably in the range of 4/96 to 30/70.

(Inorganic components, etc.)
When an inorganic component is contained in the composition constituting the gas barrier layer, the content of the inorganic component is preferably in the range of 5 to 50% by weight from the viewpoint of good gas barrier properties of the gas barrier laminate. This content is more preferably in the range of 10 to 45% by weight, still more preferably in the range of 15 to 40% by weight. The content of the inorganic component in the composition can be calculated from the weight of the raw material used when preparing the composition. That is, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed, compound (L) The weight of the metal oxide is calculated on the assumption that the product is completely hydrolyzed and partly condensed, or a combination of these is completely hydrolyzed and condensed into a metal oxide. Then, the content of the inorganic component is calculated by regarding the calculated weight of the metal oxide as the weight of the inorganic component in the composition. In addition, when adding inorganic additives, such as a metal salt, a metal complex, and a metal oxide which are mentioned later, the weight of the added inorganic additive is added to the weight of an inorganic component as it is. The calculation of the weight of the metal oxide will be described more specifically. When the compound (A) represented by the chemical formula (I) is completely hydrolyzed and condensed, the composition formula is M ¹ O _{(n + k) / 2} Z ^1. It becomes a compound represented by _mnk . Of this compound, the MO _{(n + k) / 2} portion is a metal oxide. Z ¹ is regarded as an organic component without being included in the inorganic component. Further, when the compound (B) represented by the chemical formula (II) is completely hydrolyzed and condensed, the composition formula becomes a compound represented by M ¹ O _{(q + r) / 2} R ³ _pqr . Among these, the part of M ¹ O _{(q + r) / 2} is a metal oxide.

  Further, the composition constituting the gas barrier layer may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, boric acid within the range not impairing the effects of the present invention. Salts, inorganic acid metal salts such as aluminate; organic acid metal salts such as oxalate, acetate, tartrate, stearate; acetylacetonate metal complexes such as aluminum acetylacetonate, titanocene, etc. Contains metal complexes such as cyclopentadienyl metal complexes and cyano metal complexes; layered clay compounds, crosslinking agents, polyalcohols or other polymer compounds, plasticizers, antioxidants, UV absorbers, flame retardants, etc. It may be. The composition constituting the gas barrier layer is a fine powder of a metal oxide produced by hydrolyzing and condensing the above metal alkoxide; a metal oxide prepared by hydrolyzing, condensing or burning the metal alkoxide dry. A fine powder of silica; a fine silica powder prepared from water glass may be contained.

  By adding polyalcohols to the composition constituting the gas barrier layer used in the present invention, the surface appearance of the gas barrier laminate is improved. More specifically, the inclusion of polyalcohols makes it difficult for cracks to occur in the gas barrier layer during production of the gas barrier laminate, and a gas barrier laminate having a good surface appearance can be obtained.

  Such polyalcohols used in the present invention are compounds having at least two or more hydroxyl groups in the molecule, and include from low molecular weight compounds to high molecular weight compounds. Preferably, polyvinyl alcohol, polyvinyl acetate partial saponification product, ethylene-vinyl alcohol copolymer, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, polysaccharides derived from polysaccharides such as starch High molecular weight compounds such as derivatives.

  As for the usage-amount of the above-mentioned polyalcohol, it is preferable that the weight ratio of carboxylic acid containing polymer / polyalcohol is in the range of 10/90 to 99.5 / 0.5. The weight ratio is more preferably in the range of 30/70 to 99/1, still more preferably 50/50 to 99/1, and most preferably 70/30 to 98/2.

  The gas barrier layer used in the present invention is composed of a composition containing a neutralized product of a carboxyl group-containing polymer and preferably a hydrolysis condensate of the above-described compound (L) on at least one surface of a base film. A gas barrier layer is formed. This gas barrier layer may be formed on only one surface of the substrate, or may be formed on both surfaces. A laminate in which a gas barrier layer is formed on both surfaces of a substrate has an advantage that post-processing such as bonding another film is easy.

  The thickness of the gas barrier layer is not particularly limited, but is preferably in the range of 0.1 μm to 100 μm. When it is thinner than 0.1 μm, the gas barrier property of the gas barrier laminate may be insufficient. On the other hand, when the thickness is greater than 100 μm, the gas barrier layer may be easily cracked during processing, transportation, and use of the gas barrier laminate. The thickness of the gas barrier layer is more preferably in the range of 0.1 μm to 50 μm, and still more preferably in the range of 0.1 μm to 20 μm.

  As a base material on which the gas barrier layer of the present invention is formed, a transparent thermoplastic resin film or thermosetting resin film can be used. Among them, the thermoplastic resin film is particularly useful as a base material for gas barrier laminates used for food packaging materials. The base material may have a multilayer structure composed of a plurality of materials.

Examples of the thermoplastic resin film include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof; polyamide 6, polyamide 66, Polyamide resins such as polyamide 12; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, polyarylate, regenerated cellulose, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone And a film obtained by molding an ionomer resin or the like. The base material of the laminate used for the food packaging material is preferably a film made of polyethylene, polypropylene, polyethylene terephthalate, polyamide 6 or polyamide 66, more preferably polyethylene terephthalate, polyamide 6 or polyamide 66. The thermoplastic resin film may be either an unstretched film or a stretched film, but a stretched film is preferred from the viewpoint of moldability.

The gas barrier laminate used in the present invention may further include an adhesive layer (T) disposed between the base material and the gas barrier layer. According to this structure, the adhesiveness of a base material and a gas barrier layer can be improved. The adhesive layer (T) made of an adhesive resin can be formed by treating the surface of the substrate with a known anchor coating agent or applying a known adhesive to the surface of the substrate.

  In addition, the gas barrier laminate used in the present invention may include a layer made of an inorganic substance (hereinafter sometimes referred to as “inorganic layer”) between the base material and the gas barrier layer. The inorganic layer can be formed of an inorganic material such as an inorganic oxide. The inorganic layer can be formed by a vapor deposition method such as a vapor deposition method.

  The inorganic substance which comprises an inorganic layer should just have gas barrier property with respect to oxygen, water vapor | steam, etc., Preferably it has transparency. For example, the inorganic layer can be formed using an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof. Among these, aluminum oxide, silicon oxide, and magnesium oxide can be preferably used from the viewpoint of excellent barrier properties against gases such as oxygen and water vapor.

  Although the preferable thickness of an inorganic layer changes with kinds of inorganic oxide which comprises an inorganic layer, it is the range of 2 nm-500 nm normally. Within this range, a thickness that provides good gas barrier properties and mechanical properties of the gas barrier laminate may be selected. When the thickness of the inorganic layer is less than 2 nm, there is a case where the barrier property against the gas such as oxygen and water vapor is not reproducible and sufficient gas barrier property may not be exhibited. When the thickness of the inorganic layer exceeds 500 nm, the gas barrier property tends to be lowered when the gas barrier laminate is pulled or bent. The thickness of the inorganic layer is preferably in the range of 5 to 200 nm, more preferably in the range of 10 to 100 nm.

  The inorganic layer can be formed by depositing an inorganic oxide on the substrate. Examples of the forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), and the like. Among these, the vacuum evaporation method can be preferably used from the viewpoint of productivity. As a heating method in performing vacuum deposition, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Moreover, in order to improve the adhesiveness of an inorganic layer and a base material, and the denseness of an inorganic layer, you may vapor-deposit using a plasma assist method or an ion beam assist method. Moreover, in order to raise the transparency of an inorganic layer, you may employ | adopt the reactive vapor deposition method which blows in oxygen gas etc. and produces a reaction in the case of vapor deposition.

  The laminate tube container of the present invention includes a body formed in a cylindrical shape from a laminate having a gas barrier laminate (hereinafter sometimes referred to as gas barrier laminate (I)) used in the present invention, and a thermoplastic. It is composed of a shoulder portion having a screwed mouth portion and a cap portion that are molded from resin by an injection molding method or the like. For example, a laminate having a gas barrier laminate is bent into a cylindrical shape, and both end edges in the longitudinal direction are overlapped, and the overlapped portions are heat-welded by high frequency and bonded to produce a cylindrical body. One end of the cylindrical body portion is a mouth portion, and the other end is a bottom portion, and a shoulder portion having a threaded mouth portion formed from a thermoplastic resin by an injection molding method or the like is bonded to the mouth portion of the cylindrical body portion. The method of bonding the mouth part of the cylindrical body part and the shoulder part is a method in which shoulder parts are set on the mouth part of the cylindrical body part and thermally welded by high frequency welding or a gas burner. It is possible to employ a method in which a thermoplastic resin is melt-injected and compression-molded at the mouth of the fixed cylindrical body portion. It is possible to manufacture a laminated tube container by attaching a cap part molded by injection molding to the threaded mouth part, subsequently filling the contents from the butt part, and then joining the butt part by heating welding with high frequency etc. it can.

  The configuration of the laminate used in the present invention is not particularly limited as long as it includes the gas barrier laminate (I) including the gas barrier layer used in the present invention. From the viewpoint of sealing properties, a polyolefin layer (hereinafter sometimes referred to as PO layer) is preferred. The structure of the laminate used in the present invention includes, for example, a PO layer / gas barrier laminate (I) / PO layer, PO layer from the outer layer to the inner layer when used as a laminate container. / Pigment-containing PO layer / PO layer / gas barrier laminate (I) / PO layer, PO layer / polyamide layer / gas barrier laminate (I) / PO layer, PO layer / pigment-containing PO layer / PO layer / polyamide layer / Gas barrier laminate (I) / PO layer, PO layer / Gas barrier laminate (I) / ethylene-vinyl alcohol copolymer layer (hereinafter EVOH layer) / PO layer, PO layer / pigment-containing PO layer / PO layer / Gas barrier laminate (I) / EVOH layer / PO layer, PO layer / polyamide layer / gas barrier laminate (I) / EVOH layer / PO layer, PO layer / pigment-containing PO layer / PO layer / polyamide layer / gas barrier Sex laminate (I) / EVOH layer / PO layer, it may include those which can be taken a configuration of. Particularly preferred laminate structures include PO layer / gas barrier laminate (I) / PO layer, PO layer / pigment-containing PO layer / PO layer / gas barrier laminate (I) / PO layer. An adhesive layer can be appropriately provided between the layers. Hereinafter, the polyolefin layer, the pigment-containing polyolefin layer, the polyamide layer, and the EVOH layer will be described in detail.

  Examples of the polyolefin (PO) layer include low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-α olefin copolymer, ionomer, A resin composed of one or more resins such as an ethylene-acrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, an ethylene-propylene copolymer, or a sheet obtained by filming them. Can be used. These polyolefin layers may be either stretched or unstretched. The preferred polyolefin layer is a resin composed of low density polyethylene, linear (linear) low density polyethylene, or polypropylene, or a sheet formed from these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. From the viewpoint of easiness of molding process, heat resistance, etc., any PO layer constituting the laminate is unstretched low density polyethylene, unstretched linear (linear) low density polyethylene, or unstretched polypropylene. Preferably, non-stretched linear (linear) low density polyethylene and unstretched polypropylene are more preferable.

  In particular, the PO layer disposed in the innermost layer of the laminate is preferably composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.

  The thickness of the PO layer is not particularly limited, but from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc., it is preferably in the range of 10 to 300 μm, and in the range of 50 to 200 μm. More preferably.

As the polyamide layer, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, a resin composed of one or more resins of polyamide MXD6, or a sheet obtained by filming them can be used. These polyamide layers may be stretched or unstretched. A preferred polyamide layer is a sheet obtained by forming polyamide 6 and polyamide 66 into a film and stretching.
The thickness of the polyamide layer is not particularly limited, but from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc., it is preferably in the range of 5 to 200 μm, and in the range of 5 to 100 μm. More preferably.

As the ethylene-vinyl alcohol copolymer (EVOH) layer, one kind of ethylene-vinyl alcohol copolymer, two kinds or more of resins having different ethylene contents, or a sheet made of these can be used. These EVOH layers may be stretched or unstretched. A preferable EVOH layer is a sheet obtained by forming a film of an ethylene-vinyl alcohol copolymer resin and stretching it.
The thickness of the EVOH layer is not particularly limited, but from the viewpoint of gas barrier properties, mechanical toughness, impact resistance, puncture resistance, etc., it is preferably in the range of 5 to 200 μm, and 5 to 100 μm. More preferably, it is in the range.

  As a method for forming a polyolefin (PO) layer, a polyamide layer, and an EVOH layer, a non-stretched polyolefin film, a stretched polyolefin film, a non-stretched polyamide film, a stretched polyamide film, a non-stretched EVOH, a stretched EVOH film, etc. PO layer and polyamide on the film constituting the other layer by a method of pasting the film constituting the layer with a known dry lamination method, wet lamination method, hot melt lamination method, etc., or a known T-die extrusion method, etc. A method of forming a layer, an EVOH layer, or the like can be employed. Moreover, an adhesive layer can be arrange | positioned between a polyolefin layer and another layer as needed. The adhesive layer is formed using an anchor coat agent, an adhesive, an adhesive resin, or the like.

  The threaded shoulder and the cap of the laminated tube container of the present invention can be manufactured by a known structure and a known method. For example, it can be manufactured by molding a thermoplastic resin by an injection molding method or the like. Examples of the thermoplastic resin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, polyolefins such as olefin elastomers, ethylene-α-olefin copolymers, ionomers, ethylene- Gas barrier properties such as acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, and these resins and ethylene-vinyl acetate copolymer, MXD6 polyamide, etc. Blends with resins can be used.

(Method for producing gas barrier laminate)
Hereinafter, a method for producing the gas barrier laminate used in the present invention will be described. According to this method, the gas barrier laminate used in the present invention can be easily produced. Since the materials used in the manufacturing method of the present invention and the configuration of the laminate are the same as those described above, description of overlapping portions may be omitted.

  In the method for producing a gas barrier laminate used in the present invention, first, a hydrolysis condensate of at least one compound (L) containing a metal atom bonded to at least one characteristic group selected from a halogen atom and an alkoxy group; And a layer comprising a composition comprising a polymer (carboxylic acid-containing polymer) containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group (first step). . In the first step, for example, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed and condensed And a solution (S) containing at least one metal element-containing compound selected from a product obtained by completely hydrolyzing the compound (L) and condensing a part thereof, and a carboxylic acid-containing polymer; The step of applying the solution (S) to a substrate and drying it to form a layer containing the above-described components can be carried out. The solution (S) can be dried by removing the solvent contained in the solution (S).

  In the carboxylic acid-containing polymer contained in the solution (S), as described above, a part of the —COO— group (for example, 0.1 to 10 mol%) contained in the functional group (F) is monovalent. It may be neutralized by the ions.

  Next, the layer formed on the substrate is brought into contact with a solution containing a metal ion having a valence of 2 or more (second step; hereinafter, this step may be referred to as an ionization step). In the second step, at least a part of the functional group (F) (carboxylic acid and / or carboxylic anhydride) contained in the carboxylic acid-containing polymer in the layer is neutralized with a divalent metal ion. At this time, the rate of neutralization with divalent metal ions (degree of ionization) is adjusted by changing conditions such as the temperature of the solution containing metal ions, the concentration of metal ions, and the immersion time in the solution containing metal ions. it can.

  In the second step, for example, a solution containing divalent or higher metal ions is sprayed on the formed layer, or both the base material and the layer on the base material are immersed in a solution containing divalent or higher metal ions. Can be done.

  In the following description, the laminate before the ionization step may be referred to as a laminate (A), and the laminate after the ionization step may be referred to as a laminate (B).

  Hereinafter, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed and condensed, and compound (L At least one metal element-containing compound selected from those in which L) is completely hydrolyzed and partially condensed is sometimes referred to as “compound (L) -based component”. The solution (S) can be prepared using a compound (L) component, a carboxylic acid-containing polymer, and a solvent. For example, it is possible to employ a method in which (1) the compound (L) component is added and mixed in a solvent in which the carboxylic acid-containing polymer is dissolved. Moreover, the method of adding the compound (A) which is a compound (L) type component to (2) the solvent in which the carboxylic acid-containing polymer is dissolved, and then adding and mixing the compound (L) type component can also be adopted. . (3) An oligomer (a kind of hydrolysis condensate) is prepared from the compound (L) component in the presence or absence of a solvent, and a solution in which a carboxylic acid-containing polymer is dissolved is mixed with the oligomer. It is also possible to adopt a method of In addition, a compound (L) type | system | group component and its oligomer may be added to a solvent independently, and may be added to a solvent with the form of the solution which dissolved them.

  By using the above preparation method (3) as a method for preparing the solution (S), a gas barrier laminate having a particularly high gas barrier property can be obtained. Hereinafter, the preparation method (3) will be described more specifically.

  In the preparation method (3), an oligomer is prepared by dissolving a carboxylic acid-containing polymer in a solvent to prepare a solution (St1) and hydrolyzing and condensing the compound (L) component under specific conditions. A step (St2) and a step (St3) of mixing the solution obtained in the step (St1) and the oligomer obtained in the step (St2).

  In the step (St1), the solvent used for dissolving the carboxylic acid-containing polymer may be selected according to the type of the carboxylic acid-containing polymer. For example, in the case of a water-soluble polymer such as polyacrylic acid or polymethacrylic acid, water is suitable. In the case of a polymer such as an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer, water containing an alkaline substance such as ammonia, sodium hydroxide, or potassium hydroxide is preferred. Further, in the step (St1), alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and trioxane; ketones such as acetone and methyl ethyl ketone; ethylene glycol, as long as the dissolution of the carboxylic acid-containing polymer is not hindered Glycols such as propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane, and the like can be used in combination.

  In the step (St2), an oligomer can be obtained by hydrolyzing and condensing the compound (L) component in a reaction system containing the compound (L) component, an acid catalyst, water and, if necessary, an organic solvent. preferable. Specifically, a technique used in a known sol-gel method can be applied. When the compound (L) is used as the compound (L) component, a gas barrier laminate having higher gas barrier properties can be obtained.

As the acid catalyst used in the step (St2), a known acid catalyst can be used. For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, Maleic acid or the like can be used. Of these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred. Although the preferable usage-amount of an acid catalyst changes with kinds of catalyst to be used, it is preferable that it is the range of 1 * 10 < ^-5 > -10 mol with respect to 1 mol of metal atoms of a compound (L) type | system | group component, 1 *. The range of 10 ^{−4 to} 5 mol is more preferable, and the range of 5 × 10 ⁻⁴ to 1 mol is more preferable. When the amount of the acid catalyst used is within this range, a gas barrier laminate having a high gas barrier property can be obtained.

  Moreover, although the preferable usage-amount of water in a process (St2) changes with kinds of compound (L) type | system | group component, the alkoxy group of a compound (L) type | system | group component or a halogen atom (when both are mixed together) 1 mol Is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.1 to 4 mol, and still more preferably in the range of 0.2 to 3 mol. When the amount of water used is in this range, the gas barrier property of the resulting gas barrier laminate is particularly excellent. In the step (St2), when a component containing water such as hydrochloric acid is used, the amount of water used is preferably determined in consideration of the amount of water introduced by the component.

  Furthermore, in the reaction system of the step (St2), an organic solvent may be used as necessary. The organic solvent used will not be specifically limited if it is a solvent in which a compound (L) type component dissolves. For example, alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used as the organic solvent, and alcohols having the same molecular structure (alkoxy component) as the alkoxy group contained in the compound (L) component are more preferable. Used for. Specifically, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. Although the usage-amount of an organic solvent is not specifically limited, It is the quantity from which the density | concentration of a compound (L) type-component becomes 1 to 90 weight%, More preferably, it is 10 to 80 weight%, More preferably, it is 10 to 60 weight%. Is preferred.

  In the step (St2), when the hydrolysis and condensation of the compound (L) component is performed in the reaction system, the temperature of the reaction system is not necessarily limited, but is usually in the range of 2 to 100 ° C. Preferably it is the range of 4-60 degreeC, More preferably, it is the range of 6-50 degreeC. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.1. It is in the range of ~ 6 hours. The atmosphere of the reaction system is not necessarily limited, and an atmosphere such as an air atmosphere, a carbon dioxide atmosphere, a nitrogen stream, or an argon atmosphere can be employed.

  In the step (St2), the total amount of the compound (L) component may be added to the reaction system all at once, or may be added to the reaction system in several small portions. In any case, it is preferable that the total amount of the compound (L) component used satisfies the above preferred range. The oligomer prepared by the step (St2) preferably has a degree of condensation of about 25 to 60% when expressed by the degree of condensation P described above.

  In the step (St3), a solution (S) is prepared by mixing an oligomer derived from the compound (L) component and a solution containing a carboxylic acid-containing polymer. From the viewpoint of storage stability of the solution (S) and gas barrier properties of the resulting gas barrier laminate, the pH of the solution (S) is preferably in the range of 1.0 to 7.0, and preferably 1.0 to 6 More preferably, it is in the range of 0.0, more preferably in the range of 1.5 to 4.0.

  The pH of the solution (S) can be adjusted by a known method, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, It can adjust by adding basic compounds, such as sodium carbonate and sodium acetate. At this time, if a basic compound that provides a monovalent cation is used in the solution, a part of the carboxyl group and / or carboxylic anhydride group of the carboxylic acid-containing polymer may be neutralized with a monovalent ion. The effect that it can be obtained.

  Further, the solution (S) may be carbonate, hydrochloride, nitrate, hydrogencarbonate, sulfate, hydrogensulfate, phosphate, borate, and aluminan as long as the effect of the present invention is not impaired as desired. Inorganic acid metal salts such as acid salts; organic acid metal salts such as oxalate, acetate, tartrate and stearate; acetylacetonate metal complexes such as aluminum acetylacetonate; cyclopentadiene such as titanocene Metal complexes such as enyl metal complexes and cyano metal complexes; including layered clay compounds, crosslinking agents, polyalcohols described above, and other polymer compounds, plasticizers, antioxidants, UV absorbers, flame retardants, etc. May be. The solution (S) is a fine powder of a metal oxide produced by hydrolyzing and polycondensing the above metal alkoxide; a metal oxide prepared by hydrolyzing, polycondensing or burning the metal alkoxide in a dry process. Fine powder; silica fine powder prepared from water glass may be included.

  The amount of polyalcohol added to the solution (S) is preferably such that the weight ratio of carboxylic acid-containing polymer / polyalcohol is in the range of 10/90 to 99.5 / 0.5. The range of the weight ratio is more preferably 30/70 to 99/1, still more preferably 50/50 to 99/1, and most preferably 70/30 to 98/2.

  The solution (S) prepared in the step (St3) is applied to at least one surface of the substrate. Before applying the solution (S), the surface of the substrate may be treated with a known anchor coating agent, or a known adhesive may be applied to the surface of the substrate. The method for applying the solution (S) to the substrate is not particularly limited, and a known method can be used. Preferable methods include, for example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method, metering bar coating method, chamber doctor combined coating Method, curtain coating method and the like.

  After the solution (S) is applied on the substrate, the solvent contained in the solution (S) is removed to obtain a laminate (laminate (A)) before the ionization step. The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination. A drying temperature will not be restrict | limited especially if it is 15-20 degreeC or more lower than the flow start temperature of a base material, and 15-20 degreeC or more lower than the thermal decomposition start temperature of a carboxylic acid containing polymer. The drying temperature is preferably in the range of 80 ° C to 200 ° C, more preferably in the range of 100 to 180 ° C, and still more preferably in the range of 110 to 180 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  Gas barrier properties used in the present invention by bringing the laminate (A) obtained by the above process into contact with a solution containing metal ions having a valence of 2 or more (hereinafter sometimes referred to as solution (MI)) (ionization process). A laminate is obtained. The ionization process may be performed at any stage as long as the effects of the present invention are not impaired. For example, the ionization step may be performed before or after being processed into the form of the packaging material, or may be performed after the packaging material is filled with the contents and sealed.

  The solution (MI) can be prepared by dissolving a compound (a polyvalent metal compound) that releases metal ions having a valence of 2 or more by dissolution in a solvent. As a solvent used in preparing the solution (MI), it is desirable to use water, but it may be a mixture of an organic solvent miscible with water and water. Examples of such a solvent include lower alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, and trioxane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone; ethylene glycol, Examples include glycols such as propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; organic solvents such as acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and dimethoxyethane.

As the polyvalent metal compound, compounds capable of releasing the metal ions exemplified for the gas barrier layer used in the present invention (that is, divalent or higher metal ions) can be used. For example, calcium acetate, calcium hydroxide, calcium chloride, calcium nitrate, calcium carbonate, magnesium acetate, magnesium hydroxide, magnesium chloride, magnesium carbonate, iron acetate (II), iron chloride (II), iron acetate (III), chloride Iron (III), zinc acetate, zinc chloride, copper acetate (II), copper acetate (III), lead acetate, mercury acetate (II), barium chloride, barium sulfate, nickel sulfate, lead sulfate, zirconium chloride, zirconium nitrate, Aluminum sulfate, potassium alum (KAl (SO ₄ ) ₂ ), titanium (IV) sulfate, or the like can be used. Only one type of polyvalent metal compound may be used, or two or more types may be used in combination. Preferred polyvalent metal compounds include calcium acetate, calcium hydroxide, magnesium acetate, and zinc acetate.

The concentration of the polyvalent metal compound in the solution (MI) is not particularly limited, but is preferably in the range of 5 × 10 ⁻⁴ wt% to 50 wt%, more preferably 1 × 10 ⁻² wt% to 30 wt%. More preferably, it is in the range of 1 to 20% by weight.

  When the laminate (A) is brought into contact with the solution (MI), the temperature of the solution (MI) is not particularly limited, but the higher the temperature, the faster the ionization rate of the carboxyl group-containing polymer. A preferable temperature is, for example, in the range of 30 to 140 ° C, preferably in the range of 40 ° C to 120 ° C, and more preferably in the range of 50 ° C to 100 ° C.

  It is desirable to remove the solvent remaining in the laminate after bringing the laminate (A) into contact with the solution (MI). The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied singly or in combination of two or more. The temperature at which the solvent is removed is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the substrate and 15 to 20 ° C. or lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. A drying temperature becomes like this. Preferably it is the range of 40-200 degreeC, More preferably, it is the range of 40-150 degreeC, More preferably, it is the range of 40-100 degreeC. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  In order not to impair the appearance of the surface of the gas barrier laminate, it is preferable to remove excess polyvalent metal compound adhering to the surface of the laminate before or after removing the solvent. As a method for removing the polyvalent metal compound, washing using a solvent in which the polyvalent metal compound dissolves is preferable. As the solvent in which the polyvalent metal compound dissolves, a solvent that can be used for the solution (MI) can be used, and the same solvent as the solvent for the solution (MI) is preferably used.

  In the method for producing a gas barrier laminate used in the present invention, the layer formed in the first step is heated to 120 to 240 ° C. after the first step and before and / or after the second step. It may further include a step of heat-treating. That is, you may heat-process with respect to a laminated body (A) or (B). The heat treatment may be performed at any stage as long as the removal of the solvent of the applied solution (S) is almost completed. However, the laminate (ie, the laminate (A)) before the ionization step is performed. By performing the heat treatment, a gas barrier laminate having a good surface appearance can be obtained. The temperature of the heat treatment is preferably in the range of 120 ° C to 240 ° C, more preferably in the range of 130 to 230 ° C, and still more preferably in the range of 150 ° C to 210 ° C. The heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.

  Moreover, in the manufacturing method of this invention, you may irradiate a laminated body (A) or (B) with an ultraviolet-ray. The ultraviolet irradiation may be performed any time after the removal of the solvent of the coated solution (S) is almost completed. The method is not particularly limited, and a known method can be applied. The wavelength of the ultraviolet rays to be irradiated is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and / or in the range of 230 to 250 nm. Further, instead of ultraviolet irradiation, radiation such as an electron beam or γ-ray may be irradiated.

  Only one of heat treatment and ultraviolet irradiation may be performed, or both may be used in combination. By performing heat treatment and / or ultraviolet irradiation, the gas barrier performance of the laminate may be expressed to a higher degree.

  In order to dispose the adhesive layer (T) between the base material and the gas barrier layer, the surface of the base material is treated (treatment with an anchor coating agent or application of an adhesive) before the application of the solution (S). In this case, after the first step (application of the solution (S)) and before the heat treatment and the second step (ionization step), the substrate coated with the solution (S) is relatively It is preferable to perform an aging treatment that is allowed to stand for a long time at a low temperature. The temperature of the aging treatment is preferably 30 to 200 ° C, more preferably 30 to 150 ° C, still more preferably 30 to 120 ° C. The time for aging treatment is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and further preferably in the range of 1 to 5 days. By performing such an aging treatment, the adhesive force between the base material and the gas barrier layer becomes stronger. After the aging treatment, it is preferable to perform the above heat treatment (heat treatment at 120 ° C. to 240 ° C.).

  The laminated tube container of the present invention has a high oxygen barrier property, and the oxygen barrier property does not decrease even after squeezing. Therefore, it is possible to protect contents that are susceptible to oxygen degradation from oxygen for a long period of time. Furthermore, the contents can be seen through, and there is no problem in disposal. The laminate tube container of the present invention can be used as a laminate tube container containing toiletries such as cosmetics, medicines, pharmaceuticals, and toothpastes, foods such as kneaded and wasabi.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Measurement and evaluation in the following examples were performed by the following methods (1) to (3). In the following examples, when describing the layer structure of the laminate, only the substance name may be described, and the “layer” may be omitted.

(1) Measurement of oxygen barrier property A sample for measuring oxygen permeability was cut out from the laminate tube container obtained in the examples. The oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). Specifically, the laminate is set so that the inner layer of the laminate faces the carrier gas side so that the outer layer of the laminate constituting the lid material faces the oxygen supply side, the temperature is 20 ° C., and the humidity on the oxygen supply side Oxygen permeability (unit: cm ³ / m ² · day · atm) was measured under the conditions of 90% RH, humidity 90% RH on the carrier gas side, oxygen pressure 1 atm, and carrier gas pressure 1 atm.

(2) Oxygen barrier property after squeezing A laminate tube container filled with kneaded wasabi was sandwiched between fingers and reciprocated along the laminate tube so as to be pressed with a certain force with the fingers. After 2000 reciprocations, the kneaded wasabi of the contents was taken out, and a sample for measuring oxygen permeability was cut out from the laminate tube container. The contents were wiped off with a paper towel. The measurement of oxygen permeability was carried out under the same conditions as the measurement in (1) above.

(3) Degree of neutralization of carboxyl groups by ions (degree of ionization)
About the laminated body (B-1) obtained in Examples 1 and 2, using a Fourier transform infrared spectrophotometer (manufactured by Shimadzu Corporation, 8200PC), in the mode of ATR (total reflection measurement), the gas barrier layer The peak of the C═O stretching vibration contained in was observed. Peak attributed to C = O stretching vibration of the carboxyl group of the ionization front of a carboxylic acid containing polymer was observed in a range of ^{1600cm -1 ~1850cm} -1, C = O stretching vibration of the carboxyl group after being ionized It was observed in the range of 1500cm ^-1 ~1600cm ^-1. Then, the ratio was calculated from the maximum absorbance in each range, and the degree of ionization was determined using the ratio and a calibration curve prepared in advance by the following method.

[Create calibration curve]
Polyacrylic acid having a number average molecular weight of 150,000 was dissolved in distilled water, and the carboxyl group was neutralized with a predetermined amount of sodium hydroxide. The obtained aqueous solution of neutralized polyacrylic acid was coated on a substrate so as to have the same thickness as the gas barrier layer of the laminate to be measured for ionization degree, and dried. Stretched PET whose surface is coated with a two-component anchor coating agent (Mitsui Takeda Chemical Co., Ltd., Takelac A626 (trade name) and Takenate A50 (trade name), hereinafter sometimes abbreviated as AC)) A film (manufactured by Toray Industries, Inc., Lumirror (trade name), thickness 12 μm, hereinafter may be abbreviated as “OPET”) was used. In this way, 11 types of standard samples [layered product (layer comprising a neutralized product of polyacrylic acid / AC / OPET)] in which the degree of neutralization of carboxyl groups varies by 10 mol% between 0 and 100 mol%. Was made. About these samples, the infrared absorption spectrum was measured in the mode of ATR (total reflection measurement) using the Fourier-transform infrared spectrophotometer (the Shimadzu Corporation make, 8200PC). The two peaks corresponding to the C = O stretching vibration in the layer consisting of neutralized product of polyacrylic acid, ^i.e., a peak observed in the range of 1600cm ^-1 ~1850cm -1 and ^1500cm -1 ^{~1600cm -} The ratio of the maximum absorbance was calculated for the peak observed in the range of ¹ . Then, a calibration curve was created using the calculated ratio and the ionization degree of each standard sample.

  Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl group of the polyacrylic acid, so that the solid content concentration in the aqueous solution A polyacrylic acid aqueous solution having a content of 10% by weight was obtained.

  Next, 68.4 parts by weight of tetramethoxysilane (TMOS) is dissolved in 82.0 parts by weight of methanol, and then 13.6 parts by weight of γ-glycidoxypropyltrimethoxysilane is dissolved. 13 parts by weight and 12.7 parts by weight of 0.1N (0.1 N) hydrochloric acid were added to prepare a sol, and this was stirred and hydrolyzed and condensed at 10 ° C. for 1 hour. The obtained sol was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10 wt% polyacrylic acid aqueous solution under stirring to obtain a solution (S1).

  On the other hand, a two-component anchor coating agent (AC; Takelac A626 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; Lumirror (trade name) manufactured by Toray Industries, Inc.) A substrate (AC / OPET) having an anchor coat layer was prepared by coating on the substrate and drying the solution on the anchor coat layer of this substrate by a bar coater so that the thickness after drying was 1 μm. After coating (S1), it was dried for 5 minutes at 80 ° C. Similarly, the opposite surface of the stretched PET film was coated with the anchor coating agent and the solution (S1), and then further in dry air at 200 ° C. for 5 minutes. In this way, a laminate (gas barrier layer (1 μm) / AC layer / OP having a gas barrier layer that is colorless and transparent and has a good appearance) An ET layer (12 μm) / AC layer / gas barrier layer (1 μm)) was obtained (hereinafter, this laminate may be referred to as a laminate (1)).

  Next, calcium acetate was dissolved in distilled water to a concentration of 10% by weight, and this aqueous solution was kept at 80 ° C. And the laminated body (1) obtained above was immersed in this aqueous solution (80 degreeC; MI-1) for about 300 seconds. After the immersion, the laminate is taken out, the surface of the laminate is washed with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes, so that the gas barrier laminate laminate used in the present invention is used. (B-1) was obtained. About this laminated body (B-1), the neutralization degree of the carboxyl group of the polyacrylic acid in a gas barrier layer was measured by said method. As a result, it was found that 94 mol% of the carboxyl groups were neutralized with calcium ions.

Two-component adhesive (Mitsui Takeda Chemical Co., Ltd.) on unstretched polypropylene film (Tosero Co., Ltd., RXC-18 (trade name), thickness 100 μm, hereinafter sometimes abbreviated as “PP”) , A-385 (trade name) and A-50 (trade name)) were prepared by drying and one of the laminates (B-1; gas barrier layer / AC / OPET / AC / gas barrier layer) was prepared. The surface was printed by the gravure method and laminated with the printed surface. Thus, a laminate (B-1-1) having a structure of CPP / adhesive / gas barrier layer / AC layer / OPET layer / AC layer / gas barrier layer / printing layer / adhesive / adhesive / CPP is obtained. It was. After cutting out from this laminated body into a predetermined shape, the cylindrically overlapped portion was heat-sealed to produce a cylindrical body. Next, the cylindrical barrel manufactured as described above is attached to a mandrel for forming a tube container, and then a cylindrical trapezoidal shoulder and a narrow neck continuous therewith are attached to one end of the cylindrical barrel by a conventional method. A tube container according to the present invention was manufactured by molding a head composed of the mouth and neck of the above by a compression molding method using polypropylene resin. Next, a cap made of polypropylene resin was spiraled around the mouth and neck of the cylindrical body having the head. Subsequently, the other opening part of this cylindrical trunk | drum was heat-sealed and the laminated tube container was manufactured. A squeeze test was performed by the method described above. Rake -'s previous oxygen permeability ^{0.15cm 3 / m 2 · day ·} at, oxygen permeability ^{0.17cm 3 / m 2 · day ·} atm after squeezing. Even after squeezing, the oxygen barrier property was not reduced. Furthermore, the oxygen permeability before retorting testing ^{0.15cm 3 / m 2 · day ·} at, 120 ℃, an oxygen transmission rate after the retort test 30 minutes conditions ^{0.20cm 3 / m 2 · day ·} atm, There was almost no decrease in oxygen permeability, and the retort resistance was also excellent. Excellent environment and disposal, and the contents could be seen through.

  On the other hand, a two-pack anchor coating agent (AC; Takelac A626 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are made of a stretched polyamide film (Emblem (trade name) manufactured by Unitika Ltd., thickness). A substrate (AC / OPA) having an anchor coat layer was prepared by coating the substrate and drying the bar coater on the anchor coat layer of the substrate so that the thickness after drying was 1 μm. Then, the solution (S1) obtained in Example 1 was coated and then dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched polyamide film was coated with the anchor coating agent and the solution (S1). Heat treatment was performed in dry air for 5 minutes at 200 ° C. In this way, a laminate (gas gas) having a gas barrier layer that was colorless and transparent and had a good appearance. Barrier layer (1 μm) / AC layer / OPA layer (15 μm) / AC layer / gas barrier layer (1 μm)) was obtained (hereinafter, this laminate may be referred to as a laminate (2)).

  Next, calcium acetate was dissolved in distilled water to a concentration of 10% by weight, and this aqueous solution was kept at 80 ° C. And the laminated body (2) obtained above was immersed in this aqueous solution (80 degreeC; MI-1) for about 300 seconds. After the immersion, the laminate is taken out, the surface of the laminate is washed with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain the laminate (B-2) of the present invention. Obtained. About this laminated body (B-2), the neutralization degree of the carboxyl group of the polyacrylic acid in a gas barrier layer was measured by said method. As a result, it was found that 95 mol% of the carboxyl groups were neutralized with calcium ions.

Two-component adhesive (Mitsui Takeda Chemical Co., Ltd.) on unstretched polypropylene film (Tosero Co., Ltd., RXC-18 (trade name), thickness 100 μm, hereinafter sometimes abbreviated as “PP”) , A-385 (trade name) and A-50 (trade name)) are dried and prepared, and the laminate (B-2; gas barrier layer / AC layer / OPA layer / AC layer / gas barrier layer) is prepared. ) Was printed by the gravure method and laminated with the printed surface. Thus, a laminate (B-2-1) having a structure of CPP / adhesive / gas barrier layer / AC layer / OPA layer / AC layer / gas barrier layer / printing layer / adhesive / CPP was obtained. After cutting out from this laminated body into a predetermined shape, the cylindrically overlapped portion was heat-sealed to produce a cylindrical body. Next, the cylindrical barrel manufactured as described above is attached to a mandrel for forming a tube container, and then a cylindrical trapezoidal shoulder and a narrow neck continuous therewith are attached to one end of the cylindrical barrel by a conventional method. A tube container according to the present invention was manufactured by molding a head composed of the mouth and neck of the above by a compression molding method using polypropylene resin. Next, a cap made of polypropylene resin was spiraled around the mouth and neck of the cylindrical body having the head. Subsequently, the other opening part of this cylindrical trunk | drum was heat-sealed and the laminated tube container was manufactured. A squeeze test was performed by the method described above. Rake -'s previous oxygen permeability ^{0.19cm 3 / m 2 · day ·} at, oxygen permeability ^{0.19cm 3 / m 2 · day ·} atm after squeezing. Even after squeezing, the oxygen barrier property was not reduced. Furthermore, the oxygen permeability before retorting testing ^{0.19cm 3 / m 2 · day ·} at, 120 ℃, an oxygen transmission rate after the retort test 30 minutes conditions ^{0.24cm 3 / m 2 · day ·} atm, There was almost no decrease in oxygen permeability, and the retort resistance was also excellent. Excellent environment and disposal, and the contents could be seen through.

On an unstretched linear (linear) low-density polyethylene film (manufactured by Tosello Co., Ltd., Tosero TUX (trade name), thickness 100 μm, hereinafter sometimes abbreviated as “LLDPE”), respectively A two-component adhesive (made by Mitsui Takeda Chemical Co., Ltd., A-385 (trade name) and A-50 (trade name)) was prepared by drying and the laminate obtained in Example 1 was prepared. One side of the body (B-1; gas barrier layer / AC layer / OPET layer / AC layer / gas barrier layer) was printed by the gravure method and laminated with the printed surface. In this way, a laminate (B-1-2) having a structure of LLDPE / adhesive / gas barrier layer / AC layer / OPET layer / AC layer / gas barrier layer / printing layer / adhesive / LLDPE was obtained. After cutting out from this laminated body into a predetermined shape, the cylindrically overlapped portion was heat-sealed to produce a cylindrical body. Next, the cylindrical barrel manufactured as described above is attached to a mandrel for forming a tube container, and then a cylindrical trapezoidal shoulder and a narrow neck continuous therewith are attached to one end of the cylindrical barrel by a conventional method. A tube container according to the present invention was manufactured by molding a head composed of the neck and neck of the above by a compression molding method using a linear polyethylene resin. Next, a cap made of a linear polyethylene resin was spiraled around the mouth and neck of the cylindrical body having the head. Subsequently, the other opening part of this cylindrical trunk | drum was heat-sealed and the laminated tube container was manufactured. A squeeze test was performed by the method described above. Rake -'s previous oxygen permeability ^{0.19cm 3 / m 2 · day ·} at, oxygen permeability ^{0.22cm 3 / m 2 · day ·} atm after squeezing. Even after squeezing, the oxygen barrier property was not reduced. Excellent environment and disposal, and the contents could be seen through.

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a polyacrylic acid aqueous solution (S4) having a solid content concentration of 10% by weight in the aqueous solution.
Hereinafter, the operation as in Example 1 was performed except that the solution (S4) was used instead of the solution (S1) to obtain a laminate (4) having a gas barrier layer that was colorless and transparent and had a good appearance.

  Next, calcium acetate was dissolved in distilled water to a concentration of 10% by weight, and this aqueous solution was kept at 80 ° C. And the laminated body (4) obtained above was immersed in this aqueous solution (80 degreeC; MI-1) for about 300 seconds. After the immersion, the laminate is taken out, the surface of the laminate is washed with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain the laminate (B-4) of the present invention. Obtained. About this laminated body (B-4), the neutralization degree of the carboxyl group of the polyacrylic acid in a gas barrier layer was measured by said method. As a result, it was found that 95 mol% of the carboxyl groups were neutralized with calcium ions.

  Hereafter, except having used a laminated body (B-4) instead of the laminated body (B-1) of Example 1, operation as Example 1 was performed and the laminated tube container was manufactured.

A squeeze test was performed on the above-described laminated tube container by the method described above. Rake -'s previous oxygen permeability ^{1.5cm 3 / m 2 · day ·} at, oxygen permeability ^{1.8cm 3 / m 2 · day ·} atm after squeezing. Even after squeezing, the oxygen barrier property was not reduced. Furthermore, the oxygen permeability 1.5cm before retort test ^{3 / m 2 · day · at} , 120 ℃, an oxygen transmission rate after the retort test 30 minutes condition ^{3.1cm 3 / m 2 · day ·} atm, There was almost no decrease in oxygen permeability, and the retort resistance was also excellent. Excellent environment and disposal, and the contents could be seen through.

The present invention relates to a tube container suitable for filling and packaging contents such as cosmetics, medicines, pharmaceuticals, foods, and toothpastes. The laminate tube container of the present invention relates to a laminate tube container that is excellent in oxygen barrier properties and that can protect the contents from oxidative degradation over a long period of time because the oxygen barrier properties do not decrease even after the laminate tube container is squeezed.

Claims (6)

A laminate tube container comprising a base material and a gas barrier laminate comprising a gas barrier layer laminated on at least one surface of the base material, wherein the gas barrier layer comprises a hydrolysis condensate of compound (L), A composition comprising a neutralized product of a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group;
The compound (L) comprises at least one compound (A) represented by the following chemical formula (I) and at least one compound (B) represented by the following chemical formula (II):
The molar ratio of the compound (A) / the compound (B) is in the range of 0.5 / 99.5 to 40/60,
A laminate tube container, wherein at least a part of —COO— group contained in the at least one functional group is neutralized with a divalent or higher metal ion.
M ¹ (OR ¹ ) _n X ¹ _k Z _m−n−k (I)
[In the chemical formula (I), M ¹ is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Represents Nd. R ¹ represents an alkyl group. X ¹ represents a halogen atom. Z represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. m is equal to the valence of M ¹ . n represents an integer of 0 to (m-1). k represents an integer of 0 to (m−1). 1 ≦ n + k ≦ (m−1). ]
_{^{M 2 (OR 2) q R}} 3 p-q-r X 2 r ··· (II)
[In the chemical formula (II), M ² is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Represents Nd. R ² represents an alkyl group. R ³ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p is equal to the valence of M ² . q represents an integer of 0 to p. r represents an integer of 0 to p. 1 ≦ q + r ≦ p. ] In the chemical formula (I), the functional group having reactivity with a carboxyl group is at least one functional group selected from an epoxy group, an amino group, a halogen group, a mercapto group, an isocyanate group, a ureido group, and a hydroxyl group. Item 2. The laminated tube container according to Item 1 . The laminate tube container according to claim 1 or 2 , wherein the polymer is at least one polymer selected from polyacrylic acid and polymethacrylic acid. The laminate tube container according to any one of claims 1 to 3 , wherein the metal ion is at least one ion selected from calcium ion, magnesium ion, barium ion, and zinc ion. The laminate tube container according to any one of claims 1 to 4 , wherein the innermost layer of the laminate tube container is an unstretched polypropylene layer. The laminate tube container according to any one of claims 1 to 5 , wherein the gas barrier laminate has a layer made of an inorganic material obtained by a vapor deposition method between a base material and a gas barrier layer.