JP4983403B2 - Barrier paper laminate - Google Patents

Description

  The present invention relates to a barrier paper laminate excellent in gas barrier properties and mechanical properties without delamination.

  Conventionally, paper has been widely used as a packaging material because of its good air permeability and excellent various packaging functions when used as a simple substance. On the other hand, when packaging contents that require various types of gas barrier properties, paper wrapping materials in which the base paper is coated with a gas barrier resin, especially vinylidene chloride resin, have been used. When promoting recycling for the construction of a recycling-oriented society, the use of chlorinated compounds as the gas barrier layer has the problem of causing the generation of hazardous substances when the contents are discarded after packaging and incinerated. It was.

  In addition, a material in which an aluminum foil is bonded to paper or a material in which various plastic films are bonded has been widely used. For example, conventionally, as a laminated material for paper containers for filling and packaging liquid beverages, etc., a thermoplastic resin layer, an adhesive layer, a base material layer made of paperboard, an adhesive layer, a gas barrier layer, an adhesive layer, and a sealant are sequentially arranged from the outside. A multi-layer structure in which layers are laminated is often used, and as the gas barrier layer in the above-mentioned structure, aluminum foil is often used, but the one that is laminated with aluminum foil and various plastic films is used for paper recycling. At that time, there are problems such as various adverse effects in the separation process from paper.

  In order to improve these problems, as a gas barrier layer that has functions such as gas barrier properties and recyclability, as the gas barrier layer, a gas barrier layer in which a vapor-deposited thin film layer of inorganic oxide and a gas barrier coating layer are laminated on one side of a biaxially stretched polyester film A container laminate material using a film has been proposed (see, for example, Patent Document 1). However, the proposed laminate material for containers is used for liquid paper containers, and when the box is manufactured, the vapor deposition thin film layer cracks, and a very small pinhole is formed, resulting in a decrease in gas barrier properties. Therefore, it has been difficult to use the container for storing contents with a long shelf life.

  A laminated material for containers using a gas barrier film in which a vapor-deposited thin film layer of inorganic oxide and a gas barrier coating layer are laminated on one side of a biaxially stretched polyester film has been proposed (for example, see Patent Document 2).

However, recently, as consumer preferences diversify and the contents of paper containers spread to natural fruit juices and alcoholic beverages, a heat seal material superior to polyethylene resin has been demanded. On the other hand, polyethylene resin has the above-mentioned characteristics, but it absorbs the fragrance of the beverage, changes the taste and aroma of the beverage, or generates an odor peculiar to polyethylene resin, so the original flavor of the beverage is lost. It is pointed out that the so-called flavor properties are poor compared to containers such as glass bottles and PET bottles, and there is a strong demand for improvement.
Furthermore, in order to use as a packaging material, it is necessary to prevent the influence of oxygen, water vapor, and other gases that alter the contents of the packaging material in order to suppress the alteration of the contents and maintain their functions and properties. In addition, it is required to have a gas barrier property that blocks these gases.

  As a polymer resin having a barrier property, a vinylidene chloride resin film having a relatively excellent gas barrier property or a film coated with them has been often used. However, they are greatly affected by gas barrier properties due to temperature and humidity. In addition, those using metal foils made of metal such as aluminum have high gas barrier properties without the influence of temperature and humidity, but the contents cannot be confirmed through the packaging material. There are many disadvantages such as disposal of non-combustible materials when disposing, and inability to use metal detectors during inspection.

JP-A-8-216325 JP-A-2005-239230

  In view of the above circumstances, an object of the present invention is to provide a barrier paper laminate excellent in gas barrier properties and mechanical properties without delamination.

  In order to solve the above-mentioned problems, the present invention has been completed as a result of intensive studies. That is, the barrier paper laminate of the present invention is a barrier paper laminate comprising at least a paper layer and a barrier layer, and the barrier layer includes a base resin component containing the thermoplastic polyester resin A, and a thermoplastic resin. Barrier properties mainly comprising layers of a multilayer structure obtained by melting the sub-resin component including the resin B with separate extruders and molding the base resin component and the sub-resin component via the static mixer in a molten state. A barrier paper laminate characterized by being a polyester layer.

In this case, the oxygen permeability of the thermoplastic resin B in terms of a film thickness of 20 μm is 10 ml / m ² · day. It can be atm or less.
In this case, the thermoplastic resin B may be at least one selected from a partially aromatic polyamide resin, an ethylene vinyl alcohol copolymer resin, a polyglycolic acid resin, and a resin containing a conjugated double bond.
In this case, the auxiliary resin component can contain a transition metal compound.
In this case, the thermoplastic polyester resin A can be a thermoplastic polyester mainly containing ethylene terephthalate units as repeating units.
In this case, the content of aldehydes in the thermoplastic polyester resin A can be 10 ppm or less.
In this case, the increase amount of the cyclic ester oligomer when the thermoplastic polyester resin A is melted at a temperature of 290 ° C. for 60 minutes may be 0.40% by weight or less.
In this case, a layer containing the thermoplastic polyester resin A can be further provided as a sealant layer in the innermost layer.

  The barrier paper laminate of the present invention has no gas barrier property and delamination, and is excellent in mechanical properties, and is particularly suitable as a food container.

Hereinafter, embodiments of the barrier paper laminate of the present invention will be specifically described.
(Paper substrate)
The paper used for the paper layer is not particularly limited, and paper having formability, bending resistance, rigidity, waist, strength, and the like can be used. For example, strong-size bleached or unbleached paper Various types of paper base materials such as a base material or pure white roll paper, kraft paper, paperboard, processed paper, etc. can be used. In the present invention, as the paper substrate, those having a basis weight of about 80 to 600 g / m 2, preferably those having a basis weight of about 100 to 450 g / m 2 can be used. In the present invention, a desired printed picture such as a character, a figure, a picture, a symbol, or the like can be arbitrarily formed on the paper base by a normal printing method.

(Thermoplastic polyester resin A)
The thermoplastic polyester resin A according to the present invention is a thermoplastic polyester mainly obtained from an aromatic dicarboxylic acid component and a glycol component, preferably a polyester containing 70 mol% or more of the aromatic dicarboxylic acid unit of the acid component, Preferably, it is a polyester in which the aromatic dicarboxylic acid unit is 80 mol% or more of the acid component, more preferably, the aromatic dicarboxylic acid unit is 90 mol% or more of the acid component, and more preferably the aromatic dicarboxylic acid unit is 95% of the acid component. Polyester containing at least mol%.

  In particular, a thermoplastic polyester resin in which 70 mol% or more of the dicarboxylic acid component is an aromatic dicarboxylic acid, ethylene glycol in the glycol component is 50 to 97 mol%, and diethylene glycol is 1 to 30 mol% is preferable, If the acid component of the aromatic dicarboxylic acid unit is less than 70 mol%, the glass transition temperature of the resin tends to decrease, and the flavor properties tend to decrease accordingly, and the film moldability tends to deteriorate.

  As the aromatic dicarboxylic acid constituting the thermoplastic polyester resin A according to the present invention, in addition to terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sulfoisophthalic acid, diphenyl-4,4′- Aromatic dicarboxylic acids such as dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid and functional derivatives thereof, p-oxybenzoic acid, oxycaproic acid, etc. Oxyacids and functional derivatives thereof, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid and dimer acid and functional derivatives thereof, and fats such as hexahydroterephthalic acid, hexahydroisophthalic acid and cyclohexanedicarboxylic acid Cyclic dicarboxylic acids and their functional derivatives It includes, in particular isophthalic acid.

  In the thermoplastic polyester resin A according to the present invention, when the proportion of the aromatic dicarboxylic acid is less than 80 mol% of the total acid component, the glass transition temperature and specific gravity of the resin are lowered, and accordingly, the flavor property is lowered, Since film moldability also deteriorates, it is not preferable. When the proportion of terephthalic acid in the aromatic dicarboxylic acid is less than 75 mol%, the mechanical properties of the film, particularly the impact resistance, tends to be reduced.

  The other glycol component which comprises the thermoplastic polyester resin A which concerns on this invention can be copolymerized in the ratio of 50 mol% or less. For example, propylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, nonanediol, dimer diol, Aliphatic glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, 2,5-norbornane dimethylol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, aromatic glycol such as bisphenol A alkylene oxide adduct, polyethylene And polyalkylene glycols such as glycol and polybutylene glycol.

  The thermoplastic polyester resin A according to the present invention is preferably copolymerized with a tri- or higher functional polycarboxylic acid and a polyol in an amount of 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%. Copolymerization, most preferably 0.1 mol% to 10 mol% copolymerization tends to improve moldability (extrusion processability), and copolymerization is reduced (gelation) when 30 mol% or more is copolymerized. There is a tendency.

  Examples of the tri- or higher functional polycarboxylic acid and polyol include trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, pentaerythritol, benzophenone tetracarboxylic acid, and polyglycerin.

Moreover, it is preferable to copolymerize the thermoplastic polyester resin A according to the present invention with a dicarboxylic acid or glycol containing a sulfonic acid metal base in a range of 10 mol% or less. Examples of the dicarboxylic acid containing a sulfonic acid metal base include metal salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. it can. Examples of the glycol containing a sulfonic acid metal base include metal salts such as 2-sulfo-1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol. Examples of the metal salt include salts of Li, Na, K, Mg, Ca, Cu, Fe and the like.
There is a tendency that moldability (extrusion processability) is improved by copolymerizing dicarboxylic acid or glycol containing sulfonic acid metal base.

  Furthermore, a known extender can be used, for example, an epoxy compound, an isocyanate compound, a carbodiimide compound, a carboxylic anhydride compound and the like. By using a known extender, moldability (extrusion processability) is improved. There is a tendency.

  The thermoplastic polyester resin A according to the present invention can basically be produced by a conventionally known melt polycondensation method or a solid phase polymerization method in which a prepolymer produced by this method is subjected to solid phase polymerization. The melt polycondensation reaction may be performed in one stage or may be performed in multiple stages. These may be comprised from a batch-type reaction apparatus, and may be comprised from the continuous-type reaction apparatus. The melt polycondensation step and the solid phase polymerization step may be operated continuously or may be operated separately.

  The polycondensation reaction is performed using a polycondensation catalyst. As the polycondensation catalyst, at least one compound selected from Ge, Sb, Ti, or Al compounds is preferably used. These compounds are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, ethylene glycol slurries and the like.

  Examples of the Ge compound include amorphous germanium dioxide, crystalline germanium dioxide powder or ethylene glycol slurry, a solution obtained by heating and dissolving crystalline germanium dioxide in water, or a solution obtained by adding ethylene glycol to this and heat treatment. In particular, in order to obtain the polyester used in the present invention, it is preferable to use a solution in which germanium dioxide is dissolved by heating in water, or a solution in which ethylene glycol is added and heated. In addition, compounds such as germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and germanium phosphite can also be used. These polycondensation catalysts can be added during the esterification step. When a Ge compound is used, the amount used is preferably 10 to 150 ppm, more preferably 13 to 100 ppm, and still more preferably 15 to 70 ppm as the residual amount of Ge in the polyester.

  Examples of Ti compounds include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate, and partial hydrolysates thereof, titanium acetate, titanyl oxalate, titanyl oxalate, titanyl oxalate Sodium, titanyl oxalate, titanyl calcium oxalate, titanyl oxalate compounds such as titanium strontium oxalate, titanium trimellitate, titanium sulfate, titanium chloride, titanium halide hydrolyzate, titanium oxalate, titanium fluoride, titanium hexafluoride Titanium with potassium acid, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, titanium acetylacetonate, hydroxy polyvalent carboxylic acid or nitrogen-containing polyvalent carboxylic acid A phosphorus compound is reacted with a complex compound, a composite oxide composed of titanium and silicon or zirconium, a reaction product of titanium alkoxide and a phosphorus compound, or a reaction product of titanium alkoxide and an aromatic polycarboxylic acid or its anhydride. The reaction product obtained by the above. The Ti compound is added so that the amount of Ti remaining in the produced polymer is 0.1 to 50 ppm, preferably 0.5 to 10 ppm.

  Examples of the Sb compound include antimony trioxide, antimony acetate, antimony tartrate, antimony potassium tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony. The Sb compound is added so that the residual amount of Sb in the produced polymer is in the range of 50 to 300 ppm, preferably 50 to 250 ppm, preferably 50 to 200 ppm, and more preferably 50 to 180 ppm.

  Al compounds include aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate and other inorganic acid salts, aluminum n-propoxide, aluminum iso-propoxide Aluminum alkoxides such as aluminum n-butoxide and aluminum t-butoxide, aluminum chelate compounds such as aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, trimethylaluminum, triethylaluminum, etc. Organic aluminum compounds and partial hydrolysates thereof, aluminum oxide, etc. It is. Of these, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred. The Al compound is added so that the remaining amount of Al in the produced polymer is in the range of 5 to 200 ppm.

  Moreover, in manufacture of the thermoplastic polyester resin A which concerns on this invention, you may use together an alkali metal compound or an alkaline-earth metal compound as needed. The alkali metal or alkaline earth metal is preferably at least one selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and the use of an alkali metal or a compound thereof is preferable. More preferred. When using an alkali metal or a compound thereof, use of Li, Na, K is particularly preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.

  The alkali metal compound or alkaline earth metal compound is added to the reaction system as a powder, an aqueous solution, an ethylene glycol solution, or the like. The alkali metal compound or alkaline earth metal compound is added so that the residual amount of these elements in the produced polymer is in the range of 1 to 50 ppm.

  Furthermore, the thermoplastic polyester resin A according to the present invention was selected from the group consisting of silicon, manganese, iron, cobalt, zinc, gallium, strontium, zirconium, niobium, molybdenum, indium, tin, hafnium, thallium, tungsten. A metal compound containing at least one element may be contained. These metal compounds include saturated aliphatic carboxylates such as acetates of these elements, unsaturated aliphatic carboxylates such as acrylates, aromatic carboxylates such as benzoic acid, and halogens such as trichloroacetic acid. Hydroxycarboxylates such as carboxylates and lactates, inorganic acid salts such as carbonates, organic sulfonates such as 1-propanesulfonate, organic sulfates such as lauryl sulfate, oxides, hydroxides, chlorides Products, alkoxides, acetylacetonates, and the like, and are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, ethylene glycol slurries, and the like. These metal compounds are added so that the residual amount of elements of these metal compounds per ton of the produced polymer is in the range of 0.05 to 3.0 mol. These metal compounds can be added at any stage of the polyester formation reaction step.

  Also, as stabilizers, phosphoric acid, phosphoric acid esters such as polyphosphoric acid and trimethyl phosphate, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, phosphine compounds It is preferable to use at least one phosphorus compound selected from the group consisting of: Specific examples include phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, Phosphoric acid, phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid Diphenyl ester and the like. These stabilizers can be added during the esterification reaction step from a slurry preparation tank of terephthalic acid and ethylene glycol. The P compound is added so that the residual amount of P in the produced polymer is preferably in the range of 2 to 100 ppm.

  When an Al compound is used as the polycondensation catalyst, it is preferably used in combination with a phosphorus compound, and is preferably used as a solution or slurry in which an aluminum compound and a phosphorus compound are previously mixed in a solvent. In the case of an Al compound, a more preferable phosphorus compound is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is a phosphorus compound. By using these phosphorus compounds, an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as thermal stability of the polyester is seen. Among these, use of a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity. Among the above-described phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.

  The intrinsic viscosity of the thermoplastic polyester resin A used in the present invention is 0.45 to 1.30 deciliter / gram, preferably 0.50 to 1.20 deciliter / gram, more preferably 0.60 to 0.90 deciliter. / G range. A thermoplastic polyester resin having such properties is excellent in heat sealability, fragrance retention, mechanical properties, and the like.

The thermoplastic polyester resin A used in the present invention may include other thermoplastic resins, thermoplastic elastomers, heat stabilizers, heat stabilizers, antistatic agents, slip agents, organic peroxides, interfaces as necessary. Activating agent, antifogging agent, dropping agent, nucleating agent, pigment, dye, silica, talc, mica, carbon, calcium carbonate, magnesium carbonate, metal stearate, cellulose powder and other inorganic or organic additives, fillers May be added as long as the object of the present invention is not impaired.
These organic or inorganic additives and fillers can be added by various known methods such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, etc. A melt-kneading method using a screw extruder, a kneader, a Banbury mixer, etc., granulating or pulverizing, or a dry blend product or a blending method using an auto feeder without prior melt-kneading can be used.

(Thermoplastic resin B)
The thermoplastic resin B of the barrier paper laminate has an oxygen transmission rate of 10 ml / m ² · day. A thermoplastic resin that is atm or less is preferably used, and can be selected from a partially aromatic polyamide resin, an ethylene vinyl alcohol copolymer resin, and a polyglycolic acid resin. Thus, the oxygen transmission rate is 10 ml / m ² · day. The barrier paper laminate obtained by using a thermoplastic resin B of atm or less is useful as a barrier paper laminate filled with a content that is easily oxidized by oxygen.

  The partially aromatic polyamide according to the present invention is mainly composed of a polyamide having a unit derived from an aliphatic dicarboxylic acid and an aromatic diamine as a main structural unit, or a unit derived from an aromatic dicarboxylic acid and an aliphatic diamine. Polyamide as a unit.

Examples of the aromatic dicarboxylic acid component constituting the partially aromatic polyamide according to the present invention include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and diphenoxy. Examples include ethanedicarboxylic acid and functional derivatives thereof.
As the aliphatic dicarboxylic acid component constituting the partially aromatic polyamide according to the present invention, a linear aliphatic dicarboxylic acid is preferable, and a linear aliphatic dicarboxylic acid having an alkylene group having 4 to 12 carbon atoms is particularly preferable. preferable. Examples of such linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecanoic acid, dodecanedioic acid, dimer Examples thereof include acids and functional derivatives thereof.

Examples of the aromatic diamine component constituting the partially aromatic polyamide according to the present invention include metaxylylenediamine, paraxylylenediamine, and para-bis- (2-aminoethyl) benzene.
The aliphatic diamine component constituting the partially aromatic polyamide according to the present invention is an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof. The aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine. Specific examples of such linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples include aliphatic diamines such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine.

Moreover, as a dicarboxylic acid component which comprises the partial aromatic polyamide which concerns on this invention, alicyclic dicarboxylic acid can also be used other than the above aromatic dicarboxylic acid and aliphatic dicarboxylic acid. Examples of the alicyclic dicarboxylic acid include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.
Moreover, as a diamine component which comprises the partial aromatic polyamide which concerns on this invention, an alicyclic diamine other than the above aromatic diamine and an aliphatic diamine can also be used. Examples of the alicyclic diamine include alicyclic diamines such as cyclohexanediamine and bis- (4,4′-aminohexyl) methane.

  In addition to the diamine and dicarboxylic acid, lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid, etc. It can be used as a copolymerization component. In particular, the use of ε-caprolactam is desirable.

Preferred examples of the partially aromatic polyamide according to the present invention are derived from metaxylylenediamine or mixed xylylenediamine containing metaxylylenediamine and 30% or less of the total amount of paraxylylenediamine and an aliphatic dicarboxylic acid. A metaxylylene group-containing polyamide containing at least 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more in the molecular chain. Such a polyamide resin may be referred to as a metaxylylene group-containing polyamide resin.
The partially aromatic polyamide according to the present invention may contain a structural unit derived from a polybasic carboxylic acid having 3 or more bases such as trimellitic acid and pyromellitic acid within a substantially linear range. Good.

  Examples of these polyamides include homopolymers such as polymetaxylylene adipamide, polymetaxylylene sebacamide, polymetaxylylene speramide, and metaxylylenediamine / adipic acid / isophthalic acid copolymers, metaxylylene. / Paraxylylene adipamide copolymer, metaxylylene / paraxylylene piperamide copolymer, metaxylylene / paraxylylene azelamide copolymer, metaxylylenediamine / adipic acid / isophthalic acid / ε-caprolactam copolymer And metaxylylenediamine / adipic acid / isophthalic acid / ω-aminocaproic acid copolymer.

In addition, other preferable examples of the partially aromatic polyamide according to the present invention include at least 20 mol% of a structural unit derived from an aliphatic diamine and at least one acid selected from terephthalic acid or isophthalic acid in the molecular chain. More preferably, it is a polyamide containing 30 mol% or more, particularly preferably 40 mol% or more.
Examples of these polyamides include polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, hexamethylene diamine / terephthalic acid / isophthalic acid copolymer, polynonamethylene terephthalamide, polynonamethylene isophthalamide, nonamethylene diamine / terephthalic acid. / Isophthalic acid copolymer, nonamethylenediamine / terephthalic acid / adipic acid copolymer, and the like.

Other preferred examples of the partially aromatic polyamide according to the present invention include, in addition to at least one acid selected from aliphatic diamine and terephthalic acid or isophthalic acid, lactams such as ε-caprolactam and laurolactam, and aminocaproic acid. An aminocarboxylic acid such as aminoundecanoic acid, an aromatic aminocarboxylic acid such as para-aminomethylbenzoic acid or the like as a copolymerization component, and at least selected from an aliphatic diamine and terephthalic acid or isophthalic acid Polyamide containing at least 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more of a structural unit derived from one kind of acid in the molecular chain.
Examples of these polyamides include hexamethylenediamine / terephthalic acid / ε-caprolactam copolymer, hexamethylenediamine / isophthalic acid / ε-caprolactam copolymer, hexamethylenediamine / terephthalic acid / adipic acid / ε-caprolactam copolymer Examples include coalescence.

  The ethylene vinyl alcohol copolymer resin according to the present invention is obtained by saponifying a copolymer composed of ethylene and vinyl ester using an alkali catalyst or the like. A typical vinyl ester is vinyl acetate, but fatty acid vinyl esters such as vinyl propionate and vinyl pivalate can also be used. In addition, other comonomer such as propylene, butylene, or unsaturated carboxylic acid such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, etc., as long as the object of the present invention is not hindered. It is also possible to copolymerize an acid or an ester thereof, vinylpyrrolidone such as N-vinylpyrrolidone, and a vinylsilane compound.

The ethylene vinyl alcohol copolymer resin according to the present invention has an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%, more preferably 25 to 50 mol%. When the ethylene content is less than 20 mol%, the gas barrier property under high humidity is lowered and the melt moldability is also deteriorated. If it exceeds 60 mol%, sufficient gas barrier properties cannot be obtained.
Moreover, the saponification degree of the vinyl ester component of the ethylene vinyl alcohol copolymer resin according to the present invention is 90% or more, preferably 95% or more, and more preferably 98% or more. If the degree of saponification is less than 90%, not only the gas barrier property at high humidity is lowered, but also the thermal stability of the ethylene vinyl alcohol copolymer resin is deteriorated, and gel is easily generated in the molded product.

  The polyglycolic acid resin according to the present invention has the following formula (1):

It is a thermoplastic resin containing the repeating unit represented by these.

  The content of the repeating unit represented by the formula (1) in the polyglycolic acid resin is 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and the upper limit is 100% by weight. is there. When the content ratio of the repeating unit represented by the formula (1) is too small, gas barrier properties, heat resistance and the like are impaired.

  In addition, other comonomers such as ethylene oxalate (that is, 1,4-dioxane-2,3-dione), lactide, and lactones (for example, β-protein) may be used as long as the object of the present invention is not inhibited. Piolactone, β-butyrolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, etc.), trimethylene carbonate, and cyclic monomers such as 1,3-dioxane, lactic acid, 3 -Hydroxy carboxylic acids such as hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid and 6-hydroxycaproic acid or alkyl esters thereof, aliphatic diols such as ethylene glycol and 1,4-butanediol, and succinic acid , Aliphatic dicarboxylic acids such as adipic acid or alkyl esters thereof Substantially equimolar mixtures of, or may be copolymerized two or more thereof.

  The partially aromatic polyamide resin used in the present invention has a melt viscosity of 100 to 10,000 Pa · s measured at 250 ° C. and a shear rate of 100 / sec. The barrier paper laminate of the present invention maintains a multilayer structure. This is a necessary condition. If it is less than 100 Pa · s, the partially aromatic polyamide resin does not form a layer, so that the barrier property of the barrier paper laminate is not improved. On the other hand, if it exceeds 10,000 Pa · s, the melt viscosity becomes so high that sufficient fluidity cannot be obtained at the time of molding, and the high-speed moldability is inferior, and the color tone and appearance of the barrier paper laminate deteriorate.

  In addition, the melt viscosity of the ethylene vinyl alcohol copolymer resin used in the present invention measured at 210 ° C. and a shear rate of 100 / sec is 100 to 10,000 Pa · s. The barrier paper laminate of the present invention has a multilayer structure. It is a necessary condition for maintaining If the viscosity is less than 100 Pa · s, the barrier property of the barrier paper laminate is not improved because the ethylene vinyl alcohol copolymer resin is not layered. On the other hand, if it exceeds 10,000 Pa · s, the melt viscosity becomes so high that sufficient fluidity cannot be obtained at the time of molding, and the high-speed moldability is inferior, and the color tone and appearance of the barrier paper laminate deteriorate.

  In addition, the polyglycolic acid resin used in the present invention has a melt viscosity of 100 to 5000 Pa · s measured at 240 ° C. and a shear rate of 100 / sec. This is a necessary condition for maintaining the structure. If it is less than 100 Pa · s, the polyglycolic acid resin does not form a layer, so that the barrier property of the barrier paper laminate is not improved. On the other hand, if it exceeds 5000 Pa · s, the melt viscosity becomes so high that sufficient fluidity cannot be obtained at the time of molding, and the high-speed moldability is inferior, and the color tone and appearance of the barrier paper laminate are deteriorated.

  The resin containing a conjugated double bond according to the present invention is a polyester obtained by copolymerizing a polyolefin resin having a conjugated double bond such as polybutadiene or polyisoprene, or an oxygen-absorbing low molecular weight polyolefin oligomer such as a polybutadiene oligomer. Examples thereof include a resin and a copolymer resin from an aromatic vinyl compound and a diene compound.

  For example, polybutadiene is a polymer obtained by polymerization of butadiene, but in the polymer chain,

In addition to the above-mentioned units,

And 1,4-butadiene unit represented by

  Further, as a polyester resin obtained by copolymerizing an oxygen-absorbing low molecular weight polyolefin oligomer, a copolymer comprising a polyolefin ligomer segment such as polypropylene, poly (4-methyl) -1-pentene and polybutadiene and a polyethylene terephthalate segment. A polyester resin, which is described in, for example, Japanese Patent No. 3657275.

(Sub resin component including thermoplastic resin B)
The sub-resin component according to the present invention mainly contains the thermoplastic resin B described above, but various thermoplastic resins and additives may be contained within a range in which the effects of the present invention are not inhibited.

  As the transition metal compound used in the present invention, a compound of a group VIII transition metal (Fe, Co, Ni) in the periodic table is preferable, but a group I metal such as Cu and Ag, Sn, Ti, It may be a compound of a Group IV metal such as Zr, a Group V metal such as V, a Group VI metal such as Cr, or a Group VII metal such as Mn. Among these, a Co compound is most suitable in terms of an oxygen absorption promoting effect.

These metal compounds are organic acid salts, chlorides, phosphates, phosphites, hypophosphites, pyrophosphates, metaphosphates, sulfates, alkyl phosphates, or phthalocyanine complexes of the above metals. And may be used alone or as a mixture thereof.
Examples of organic acid salts include salts of C2-C22 aliphatic alkyl acids such as acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, or malonic acid, succinic acid, adipic acid, sebacic acid, hexahydrophthalic acid, Dibasic acid salts, butanetetracarboxylic acid salts, benzoic acid, toluic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid and other aromatic carboxylates, or polyacrylic acid, ethylene / acrylic acid Examples thereof include a polymer carboxylic acid salt such as a polymer alone or a mixture thereof.
Examples of the metal complex include complexes with β-diketone or β-keto acid ester.

  The compounding amount of these transition metal compounds is 1 to 5000 ppm, preferably 10 to 3000 ppm, particularly preferably 100 to 1000 ppm as the content of metal atoms.

In the case where the thermoplastic resin B is a resin containing a conjugated double bond, the blending of the transition metal compound is essential.
For the sub-resin component used in the present invention, for example, a heat stabilizer, a plasticizer, an ultraviolet absorber, an antioxidant, a colorant, a filler, other resins, and the like are used as long as the object of the present invention is not hindered. can do. As the addition method, the method described in the thermoplastic polyester resin A can be used.

(Barrier layer)
The barrier layer according to the present invention is a barrier layer having a multilayer structure in which at least three sub-resin components including thermoplastic polyester resin A and thermoplastic resin B, which are base resins, are laminated in the thickness direction.
The barrier paper laminate is characterized in that the number of barrier layers in the thickness direction is preferably 10 layers or more, more preferably 100 layers or more. The upper limit of the number of layers is 1,000,000, and characteristics such as oxygen permeability cannot be improved even if the number of layers exceeds this number.

  Further, the content of the thermoplastic polyester resin A in the barrier layer varies depending on the type of the thermoplastic polyester resin A to be used, but it is 99 to 53% by weight, preferably 95% in consideration of the price, barrier properties, mechanical properties and the like. It is -55 weight%, More preferably, it is 90-58 weight%, 80-60 weight%. When the content of the thermoplastic polyester resin A exceeds 99% by weight, the oxygen permeation amount of the barrier layer is not so different from the oxygen permeation amount of the base resin, and the effect is lost. On the other hand, if it is less than 53% by weight, the mechanical strength of the barrier layer is deteriorated, the price is increased, and the practicality becomes poor, which is not preferable.

Below, the manufacturing method of the barrier layer by the melt-extrusion molding method is demonstrated as an example.
Thermoplastic polyester resin A (hereinafter abbreviated as resin component A), which is a base resin, and thermoplastic resin B (hereinafter abbreviated as resin component B), which is a secondary resin, are charged into different extruders A1 and B1, respectively. And melt. The melting temperature is not particularly limited as long as it does not cause deterioration or alteration for each resin component. As one index, in the case of a resin component exhibiting crystallinity, the melting point + (5 ° C. to 30 ° C.), and in the case of an amorphous resin component, the softening temperature + (20 ° C. to 150 ° C.).

  The molten resin component A and resin component B are guided to a static mixer in a molten state, and a laminate of an X layer containing the resin component A and a Y layer containing the resin component B is formed. In order to facilitate the charging of the molten resin component A and resin component B into the static mixer, a feed block is installed in front of the static mixer, and once the resin component A and the resin component B are merged with the feed block, You may lead to a static mixer.

The static mixer in the present invention is adjacent to an element having a shape obtained by twisting and bending a horizontally long rectangular plate so that an angle (torsion angle) between its short sides is 45 degrees to 270 degrees. It is the in-pipe mixing device arranged alternately so that the short sides of the elements intersect. When the molten resin passes through one element, the resin is divided into two layers, and each resin layer is twisted in the direction opposite to the turning direction of the element. Further, when passing through the next element, the resin is divided and twisted in the same manner, and divided into four layers. Therefore, when the resin component A and the resin component B are laminated one by one and introduced into the static mixer, theoretically, if the short side of the first element is horizontal to the lamination surface, it passes through n elements. Then the 2 ⁿ layer, but the short side of the first element is 2 ^{n + 1} layer as long perpendicular to the laminated surface, in fact, the flow channel diameters and lengths, twist angles of the element, the torsional gradient, the discharge of the resin The amount may change due to the influence of melting characteristics such as the viscosity and surface tension of each resin, and may not be a continuous layer. In order to increase the number of continuous layers as much as possible, it is preferable to optimize the melt viscosity and extrusion conditions of the resin used.

The L / D (pipe length / pipe inner diameter) ratio of the elements of the static mixer is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.4 to 2.0. If the L / D ratio is smaller than 1.0, the resin dividing efficiency is deteriorated, and if it exceeds 3.0, the residence time of the resin passing through the mixer becomes longer, which is not practical.
The torsion angle of the static mixer element is 45 degrees or more. This is because if the twist angle is less than 45 degrees, the twist of the resin layer becomes insufficient. The twist angle is more preferably 90 degrees or more, and further preferably 135 degrees or more. The upper limit of the twist angle is preferably 315 degrees. If it exceeds 315 degrees, a uniform laminated structure cannot be obtained due to excessive twisting. The twist angle is preferably 270 degrees or less, and more preferably 215 degrees or less. The phrase “a uniform laminated structure cannot be obtained” means that the resin component B is dispersed in a non-layered state such as a spherical shape or an elliptical shape.

  Further, when the side surface of the static mixer pipe is cut and developed in the resin traveling direction, the angle formed by the straight line following the joint between the pipe inner wall and the element and the resin traveling direction, that is, the torsional gradient of the element is 27 More than the degree is preferable. If this twist gradient is less than 27 degrees, the twisting effect of the resin layer is small, and the L / D ratio must be increased in order to give a sufficient twist to the resin, which is not practical. The twist gradient is more preferably 38 degrees or more, and further preferably 42 degrees or more. On the other hand, when the torsional gradient exceeds 65 degrees, the turbulent flow of the resin becomes violent and the laminated structure is disturbed. The twist gradient is more preferably 54 degrees or less, and further preferably 50 degrees or less.

  The preferred shape of the elements of the static mixer can be appropriately selected according to the discharge amount and melting characteristics of the resin, and a plurality of elements having different shapes corresponding to changes in the melting characteristics of the resin passing through the static mixer. Can also be used in combination. The most preferred elements have L / D = 1.5, a twist angle of 180 degrees, and a twist gradient of 46 degrees.

The arrangement of the elements of the static mixer is preferably changed alternately so that the twisting directions of the elements are right turn, left turn, and right turn. This is because a uniform laminated structure can be obtained. It is also preferable to arrange adjacent elements so as to intersect at right angles in order to obtain a uniform laminated structure.
The number of elements of the static mixer is preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more. On the other hand, if the number of elements becomes too large, the laminated structure is disturbed and a spherical structure tends to be formed. Therefore, the number of elements is preferably 24 or less, more preferably 18 or less, and 14 or less. More preferably.

  The structure of the static mixer described above is one typical example, the shape and arrangement are changed without departing from the object of the present invention, and another device is arranged before and after the static mixer and between the elements. Of course, it is possible. For example, two or more rows of static mixers smaller in diameter than the resin pipe may be arranged in parallel in the pipe. Another resin can be joined and laminated on the laminated resin obtained by laminating the resin component A and the resin component B through a static mixer.

In addition, it is also possible to use a plurality of feed blocks and lead the laminated resin laminated in three or more layers to a static mixer to further increase the number of layers. In this case, the number of static mixer elements can be reduced by the number of layers in the feed block, and the number of layers in the feed block is preferably within 10 layers.
The temperature of the static mixer is set to the melting point + (5 ° C. to 30 ° C.) when the resin component exhibits crystallinity, and the softening temperature + (20 ° C. to 150 ° C.) when the resin component exhibits amorphousness. Most preferably, it is set to the same temperature as the temperature adopted as the melting temperature.

When the barrier layer is obtained alone as a sheet-like material, the laminate is extruded from a T-die and is brought into close contact with a cooling roll having a surface temperature of 10 to 40 ° C., thereby obtaining an unstretched sheet-like material of the laminate. The unstretched sheet is laminated as it is on the paper base material layer by the following method, or is laminated in the same manner after stretching in at least one direction.
Further, the barrier layer can be directly laminated on the paper base material layer by a writing method.

(Barrier paper laminate)
The barrier paper laminate is a paper laminate in which the barrier layer and the paper substrate are laminated.
The production method of the barrier paper laminate will be specifically described. For example, a dry lamination method in which a paper base layer and the barrier layer are laminated via an adhesive layer by an adhesive for lamination, a melt-extrusion adhesive polyester The method of laminating | stacking by the melt extrusion lamination method laminated | stacked through the melt extrusion resin layer by resin is mentioned. Moreover, the base resin component containing the thermoplastic polyester resin A and the auxiliary resin component containing the thermoplastic resin B are made into a melt laminated through the static mixer as described above, and this is used as a die for the paper base material layer. It can also be carried out by a direct melt extrusion lamination method or the like in which the layers are laminated.

In the laminated structure, the outermost layer may be either an X layer or a Y layer.
Moreover, the layer which consists of thermoplastic polyester resin A may be sufficient as the innermost layer which contacts a content and becomes a sealant layer.

  When the flavor retention of the contents of the barrier paper laminate of the present invention is a problem, the acetaldehyde content of the innermost barrier layer is 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less. When the acetaldehyde content exceeds 50 ppm, the flavor retention of the paper laminate is deteriorated. Moreover, the lower limit of the acetaldehyde content in the paper laminate is 3 ppm, and reducing it below this is a problem in terms of economy.

When obtaining the paper laminate of the present invention, polyamides, polyesteramides, low molecular weight amino group-containing compounds, hydroxyl group-containing compounds, hindered phenyl compounds, hindered amine compounds, benzotriazole compounds, benzophenone compounds as aldehyde reducing agents Compounds, polyphenol compounds, phosphorus stabilizers, sulfur stabilizers, and alkali metal salts can be blended in the thermoplastic polyester resin A, preferably polyamide, benzophenone compounds, polyester amides, phosphorus stabilizers, low molecular weight An amino group-containing compound, a hydroxyl group-containing compound, a benzophenone compound, a hindered phenyl compound, and a hindered amine compound can be blended in the barrier layer.
These polyamide compounds, low molecular weight amino group-containing compounds, hydroxyl group-containing compounds and other aldehyde reducing agents may be used alone or in admixture at an appropriate ratio.
The aldehyde reducing agent can be used, for example, in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. .

  The aldehyde reducing agent can be blended by adding a predetermined amount of aldehyde reducing agent at any reaction stage from the production of a low-polymerization oligomer of thermoplastic polyester to the production of polyester polymer. For example, the aldehyde reducing agent may be added to a reactor such as an esterification reactor or a polycondensation reactor in an appropriate form such as a fine granule, powder, or melt, or from the reactor to a reactor in the next step. The aldehyde reducing agent or a mixture of the polyester and the polyester may be introduced in a molten state into a transport pipe for the polyester reactant. Furthermore, if necessary, the obtained chip can be subjected to solid phase polymerization in a high vacuum or in an inert gas atmosphere.

  Moreover, it can also obtain by the method etc. which mix a thermoplastic polyester resin and an aldehyde reducing agent by a conventionally well-known method. For example, polyamide chips and polyester chips are dry blended with a tumbler, V-type blender, Henschel mixer, etc., and the dry blended mixture is melt-mixed once or more with a single screw extruder, twin screw extruder, kneader, etc. Furthermore, the thing etc. which solid-phase-polymerized the chip | tip from a molten mixture as needed under a high vacuum or inert gas atmosphere etc. are mentioned.

  Further, a method in which a solution in which the polyamide or the like is dissolved in a solvent such as hexafluoroisopropanol is adhered to the surface of the polyester chip, and the polyester is collided with the member in a space where the polyamide member is present. Examples include a method of attaching the polyamide to the surface of the polyester chip.

  The barrier paper laminate of the present invention is used as a barrier multi-layer container for packaging containers filled with various contents, so that soft drinks (carbonated drinks, fruit juice drinks, sports drinks, etc.), alcoholic drinks, coffee drinks, Effective for long-term preservation of foods and beverages such as tea beverages, mineral water, dressings, grilled meat, seasoning sauces, mayonnaise, salad oil and sesame oil, pharmaceuticals, agricultural chemicals, etc. is there.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The main characteristic value measurement methods will be described below. The composition and characteristics of the polyester are measured after the chips are frozen and ground and mixed thoroughly.

(1) Intrinsic viscosity of polyester (IV)
It calculated | required from the solution viscosity at 30 degreeC in a 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio) mixed solvent. The IV of the polyester composition was a weighted average value calculated from the IV of the constituent polyester.

(2) Glass transition temperature The glass transition temperature was measured with a DSC220 model manufactured by Seiko Denshi Kogyo Co., Ltd. at a temperature rising rate of 20 ° C./min.

(3) Extrudability
Polyester resin (A) was formed into a 40 mmφ extractor, die slit width 200 mm × die gap 0.8 mm, air gap 100 mm, temperature 280 ° C., and the difference between the die width and the obtained film width was defined as the neck-in width. .
The wider the neck-in width, the better the extrudability, with 200 mm to 180 mm being O, 180 mm to 160 mm being Δ to O, and less than 160 mm being X.

(4) Number of layers of multilayer molded body The number of barrier layers was determined by observation using a transmission electron microscope. First, a section was cut from the center so that the entire cross section was included, and embedded in an epoxy resin. As the epoxy resin used, a mixture of Luabeck 812, Luavec NMA (manufactured by Nacalai Tesque) and DMP30 (manufactured by TAAB) in a ratio of 100: 89: 3 was used. Next, after embedding the sample in the above-mentioned mixed resin, the sample was left in an oven adjusted to a temperature of 60 ° C. for 16 hours to cure the resin and obtain an embedded block.
The obtained embedding block was attached to an ultra cut N manufactured by Nissan Sangyo Co., Ltd., and an ultrathin section was prepared. First, trimming was performed using a glass knife until a cross section of a portion desired to be observed for the multilayer molded article appeared on the resin surface. Next, an ultrathin section was cut out using a diamond knife (Sumitomo Electric Sumiknife SK2045). The cut sections were collected on a mesh and then stained by standing in a ruthenium tetroxide vapor for 30 minutes at room temperature, followed by thin carbon deposition.
Electron microscope observation was performed using JEM-2010 manufactured by JEOL under conditions of an acceleration voltage of 200 kV and 40,000 times. The obtained image was recorded on an imaging plate (FDL UR-V manufactured by Fuji Photo Film). The signal recorded on the imaging plate was read using digital luminography (Pixsys TEM manufactured by JEOL), recorded as digital image information on a Windows (registered trademark) personal computer, and the number of layers to be confirmed was counted. In addition, the number of layers counted the number of the layers which exist in the layer form which exists in the visual field of the width of 100 micrometers in the center of the electron micrograph of the ultra-thin slice from a multilayer molded object, and made this the number of layers. This operation was repeated 10 times, and the average value of the number of layers was determined.

(5) Scent retention test (d-limonene adsorption)
The formed polyester resin A (sealant) having a thickness of 50 μm was placed in a sample bottle, d-limonene, which is one of the flavor components of the fruit juice drink, was added, and left at 25 ° C. and 40 ° C. for 2 weeks. The amount of adsorbed d-limonene was determined by determining the weight difference between the sealing materials before and after the immersion, and the relative value when the amount of absorbed low density polyethylene was taken as 100 was obtained.
Relative value: 21 or more was evaluated as x, 10-20 as ◯, and less than 10 as ◎.

(6) Bag drop test Using a polyethylene terephthalate film with a thickness of 25 μm as a protective layer, a polyester resin A (seal material) with a thickness of 50 μm was thermally bonded to a size of 10 cm × 10 cm to make a bag, 100 ml of water was put into a sample. This was dropped from a height of 5 m, the bag was visually observed, and evaluated as follows.
○: No change △: Some peeling was observed ×: Delamination occurred

(7) Oxygen permeability The laminates produced in the examples and comparative examples were measured under a 25 ° C., 65% RH atmosphere using Modern Control (MOCON OXTRAN, 10 / 50A).

(8) Taste test A 150 x 150 mm pouch was produced from the laminates produced in the examples and comparative examples, and oolong tea was injected into the pouch, and a taste test after storage for 403 days was performed. A three-level evaluation was performed: excellent, good, and impossible.

(Synthesis example of thermoplastic polyester resin A-1)
In a reaction vessel equipped with a stirrer, a thermometer, and an outflow condenser, 5096 parts of terephthalic acid, 566 parts of isophthalic acid, 32.7 parts of trimellitic acid, and 4370 parts of ethylene glycol are added at 230 to 240 ° C. The esterification reaction was carried out under a pressure of 0 kgf / cm 2 for 2.5 hours. After completion of the esterification reaction, 1.7 parts of tetrabutyl titanate was added, and the reaction system was heated from 220 ° C. to 275 ° C., while the pressure in the system was slowly reduced to 5 Torr at 275 ° C. over 60 minutes. Further, a polycondensation reaction was performed for 90 minutes or less at 3 Torr or less to obtain pale yellow transparent polyester A. The resin properties are shown in Table 1.
Polyesters A-2 to A-7 were synthesized in the same manner as the thermoplastic polyester resin A-1.

(Partial aromatic polyamide resin used = Ny-MXD6)
Table 2 shows the characteristics of the partially aromatic polyamide used in the test.
Ny-MXD6 (a) is prepared from a raw material preparation step, an amidation reaction step, an initial polycondensation reaction step and a late polycondensation reaction step using an aqueous solution having a concentration of about 80% by weight or more of metaxylylenediamine and adipic acid. This was obtained by appropriately changing the polycondensation time within a production time of about 120 minutes by the constituted batch-type polycondensation reaction apparatus. Sodium hypophosphite was added as a phosphorus atom-containing compound (P residual amount = 200 ppm, Na content = 440 ppm). The total amount of sodium hypophosphite and sodium hydroxide was about 3 times mol of phosphorus atoms.
Ny-MXD6 / MXDI (b) is a raw material composition in which metaxylylenediamine, adipic acid, and isophthalic acid are adjusted to correspond to the compositions in Table 2 using the same apparatus as Ny-MXD6 (a). Using an aqueous solution having a concentration of about 80% by weight or more, the product was obtained by polycondensation within a production time of about 120 minutes.

(Used ethylene vinyl alcohol copolymer resin (EVAL))
Kuraray Eval Co., Ltd., T101 was used.
(Polyglycolic acid (PGA) used)
Glycolide was obtained by ring-opening polymerization at 170 ° C. using a tin chloride catalyst.
The resin properties are shown in Table 2.
(Polycaproamide used (Ny6))
Ny6 having a melt viscosity of 5000 Pa · s manufactured by Toyobo Co., Ltd. was used.

Hereinafter, Examples 5, 7, and 10-12 are read as Reference Examples 5, 7, and 10-12, respectively.
<Example 1>
A chip of PET (A-1) was put into the extruder A and melted at 280 ° C. On the other hand, Ny-MXD6 (a) chip B was put into extruder B and melted at 260 ° C. The resin melted by both extruders is guided to a feed block at 280 ° C. so that the resin ratio is A / B = 60/40 (mass ratio), and further a static mixer at 280 ° C. (12 elements manufactured by Noritake Company) And an inner diameter of 38.4 mm, L / D of one element = 1.5, a twist angle of 180 degrees of one element, and a twist gradient of 46 degrees). Next, this melt was extrusion-coated on one side of a paper having a basis weight of 84.9 g / m 2 to produce a barrier paper laminate in which a multilayer resin layer (barrier layer) having a thickness of 20 μm was laminated. The results are shown in Table 3. The result was no problem.

(Example 2)
A paper laminate was formed in the same manner as in Example 1 except that Ny-MCD6 / MXDI (b) was used instead of Ny-MXD6 (a) and the structure shown in Table 3 was adopted.
The results are shown in Table 3. The result was no problem.

Example 3
Using EVAL resin, a paper laminate was formed in the same manner as in Example 1 except that the structure shown in Table 3 was used.
The results are shown in Table 3. The result was no problem.

Example 4
Using PGA resin, a paper laminate was formed in the same manner as in Example 1 except that the structure shown in Table 3 was used.
The results are shown in Table 3. The result was no problem.

(Example 5)
Using a polycaproamide (Ny6) resin, a paper laminate was molded in the same manner as in Example 1 except that the structure shown in Table 3 was used.
The results are shown in Table 3. The result was no problem.

(Examples 6 to 11)
Similarly, a paper laminate was molded in the same manner as in Example 1 except that PET (A-2) to PET (A-7) were used instead of PET (A-1), and the structure shown in Table 4 was used.
The results are shown in Table 4. The result was no problem.

(Example 12)
Similarly, a paper laminate was molded in the same manner as in Example 1 except that PET (A-1) was used and the configuration shown in Table 4 was adopted.
The results are shown in Table 4.

(Comparative Example 1)
A PET (A) chip alone was charged into a single extruder A and melted at 280 ° C., and a hollow container was formed in the same manner as in Example 1 without using a static mixer.
The results are shown in Table 5. The oxygen transmission rate was high, and the taste test was poor, which was a problem.

The barrier multi-layer polyester molded article of the present invention has no gas barrier property and delamination and is excellent in mechanical properties, and is particularly suitable as a beverage container for milk beverages, fruit juice beverages and the like.

Claims (2)

A barrier paper laminate comprising at least a paper layer and a barrier layer, wherein the barrier layer comprises a base resin component containing a thermoplastic polyester resin A and a sub resin component containing a thermoplastic resin B, respectively. A barrier polyester layer mainly comprising a multilayer structure layer obtained by melting the base resin component and the auxiliary resin component through a static mixer while being melted in an extruder of
The thermoplastic polyester resin A is a thermoplastic polyester obtained mainly from an aromatic dicarboxylic acid component and a glycol component,
As an aromatic dicarboxylic acid component that comprises terephthalic acid and isophthalic acid, the proportion of terephthalic acid is 75 mol% or more,
It is a polyester resin obtained by copolymerizing a tricarboxylic or polyfunctional polycarboxylic acid or polyol in an amount of 0.1 mol% to 10 mol % ,
The thermoplastic resin B is at least one selected from partially aromatic polyamide resins, ethylene vinyl alcohol copolymer resins, polyglycolic acid resins, and resins containing conjugated double bonds,
A barrier paper laminate, wherein the content of the thermoplastic polyester resin A in the barrier layer is 80 to 60% by weight. 2. The barrier paper laminate according to claim 1, further comprising a layer containing the thermoplastic polyester resin A as an innermost layer as a sealant layer.