Multilayer bottle

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer bottle intended for tea, juices or carbonated drinks. Proposed bottle comprises outer layer, inner layer and barrier layer arranged there between. Outer and inner layer are made from polyether (A) produced y polymerisation of dicarboxylic acid component that contains 80 mol %, or more, of terephthalic acid with diol component containing 80 mol %, or more, of ethylene glycol. Barrier layer comprises polyamide (B) produced by polycondensation of 70 mol %, or more, of meta-xylylenediamine with 70 mol %, or more, or α,ω-collinear aliphatic dicarboxylic acid with 4-20 carbon atoms, and thermoplastic polymer (C).The latter is selected from the group consisting of phenoxy resin in the form of poly hydroxyl ester, polyglycol acid and polyamide oligomer with low molecular weight other than polyamide (B).

EFFECT: multiplayer bottle without delamination in flatwise fall.

8 cl, 3 tbl, 8 ex

 

The present invention relates to a method of preventing delamination of the multilayer bottle having excellent gas-tightness, and more specifically to methods for protection of multilayer bottles from exposure to stratification, even when they are subjected to shock from filling their contents during transportation or in the fall, by increasing the strength midplains coupling between the inner and outer layer and the intermediate layer created between them. In addition, the present invention relates to a multilayer bottles, which are generally not subject to delamination between the layers, even without giving the bottle form with fewer bumps and curves, and provide more degrees of freedom in the choice of their design.

Currently, plastic containers (bottles etc), mostly made of such polyesters as polyethylene terephthalate (PET), increasingly used as containers for tea, fruit juices, carbonated drinks, etc. Among these plastic containers share of small plastic bottles is growing from year to year. In General, decreasing the size of the bottle against the surface area per unit of volume of its content tends to increase. Therefore, the period of time to protect taste with the hold small bottles tends to decrease. In recent years, the market is flooded beer, susceptible to the effects of oxygen and light, and hot tea, which was filled with plastic bottles. Thus, when the resent trend towards increasingly widespread plastic containers, there is a need to further improve performance of the permanence of plastic containers.

To satisfy the above needs to give good gas-tightness of plastic bottles were developed multilayer bottles, made of thermoplastic polyester polymer and gas-tight polymer, "sandwich" bottle made of several polymeric materials, bottles with barrier coating layer produced by forming a carbon coating deposited coating or coating of the barrier polymer layer bottle, made of thermoplastic polyester polymer, etc.

Have been introduced multilayer bottles, such as bottles, which are produced by processing conditions for blow molding with biaxial stretching three - or five-layer preform (draft form), obtained by the injection into the cavity of the mold thermoplastic polyester polymer, such as PET, for shaping their most HV the inner and the outer layers, and gas-tight thermoplastic polymer, such as poly-meta-xylylenediamine (polyamide MXD6).

Further, for multi-layer bottles were developed and applied polymers having the ability to absorb oxygen, which is capable of capturing oxygen inside the container, at the same time preventing the penetration of oxygen into the container from outside. From the viewpoint of the degree of absorption of oxygen, transparency, strength, formemost etc., absorbing oxygen bottles are suitable in the form of a multilayer bottle containing the gas-tight layer made of polyamide MXD6, which blended with the catalyst based on a transition metal.

The above-mentioned multilayer bottles used as containers for beer, tea, carbonated drinks, etc. due to their good characteristics of gas-tightness. When multilayer bottles are used in these areas, fill them with content can keep good quality for extended shelf life. On the other hand, multilayer bottles tend to be separation between the different polymer layers, for example between the inner and outer layer and the intermediate layer, resulting in a significant deterioration in their commercial value.

In order to solve the aforementioned problems, has been proposed such a method in which, when the polymer is La forming the innermost and the outermost layers in conclusion, is injected into the mold cavity, a certain amount of the polymer allow to flow in the opposite direction towards the gas-tight intermediate layer using a counter-current regulator, for the formation of the preform, containing roughly mixed polymer inserted between the layers, improving the stability of the obtained multilayer bottle to stratification (see patent document 1). However, this method requires the use of special equipment. In addition, there was proposed a method of manufacturing a multilayer bottle oriented blow molding, in which the preform after a single blow molding shrinks when heated and then subjected again inflatable molding under high pressure (see patent document 2). However, in this method, there are conditions for the occurrence of problems such as distortion of the obtained molded product, complicated and time-consuming procedure and the deterioration in the resistance to delamination.

Patent document 1: JP 2000-A.

Patent document 2: JP 2001-A.

The present invention is to solve the above conventional problems and to create multi-layer bottles, which is not affected by stratification in the fall or shock, do not require the giving of certain forms with fewer irregularities or less bends avoid the abolition of stratification and provides more degrees of freedom in the choice of its design.

In the extended and intensive research in terms of the stability of multilayer bottles to stratification, the authors of the present invention have found that when forming the barrier layer having a specific composition, the impact energy is deposited on the barrier layer, is greatly reduced and the obtained multilayer bottle increases the strength of midplains clutch and prevents the possibility of stratification in the fall, etc. of the Present invention was made on the basis of the above-mentioned detected.

Thus, the present invention relates to a multilayer bottle containing outer layer, inner layer and at least one barrier layer, located between the outer layer and inner layer, in which the outer layer and inner layer are made each mainly of polyester (A)obtained by polymerization decarbonisation component containing 80 mol.% or more of terephthalic acid with a diol component containing 80 mol.% or more of ethylene glycol; and the barrier layer includes at least the polyamide (B), obtained by polycondensation of diamines component containing 70 mol.% or more meta-xylylenediamine, with decarbonisation component containing 70 mol.% or more α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms, and thermoplastic poly the EP (S), srednekislye molecular weight which is from 10 to 65% from srednekamennogo molecular weight of the polyamide (B).

The preferred embodiment of the invention

Thermoplastic polyester polymer used for forming the outermost layer, the innermost layer and the optional part of the intermediate layer of the multilayer bottle according to the invention is a polyester polymer (hereinafter referred to as "polyester"), which is obtained by polymerization decarbonisation component containing terephthalic acid in the amount of 80 mol.% or more, and preferably 90 mol.% or more (including 100 mol.%), with a diol component containing ethylene glycol in the amount of 80 mol.% or more, and preferably 90 mol.% or more (including 100 mol.%).

The polyester (A)used in the present invention, preferably is a polyethylene terephthalate, since the polyethylene terephthalate is excellent for all parameters such as transparency, mechanical strength, processability in injection molding and formability blown and hood.

Examples of dicarboxylic acids other than terephthalic acid which may be contained in decarbonatization component include terephthalic acid, 4,4-dicarboxyphenoxy ether, naphthalene-1,4-dicarboxylic acid, NAF is Aline-2,6-dicarboxylic acid, adipic acid, sabotinova acid, decane-1,10-dicarboxylic acid and hexahydroterephthalate acid. Examples of diols other than ethylene glycol, which may be contained in the diol component include propylene glycol, 1,4-butanediol, neopentylglycol, diethylene glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxyethoxyphenyl)propane. Next, hydroxy acids, such as para-hydroxybenzoic acid, can also be used as a raw material monomer for the polyester (A).

The polyester (A) preferably has a characteristic viscosity from 0.55 to 1.30, and more preferably from 0.65 to 1.20. When the polyester (A) has a characteristic viscosity of 0.55 or more, you receive not only transparent amorphous multilayer preform, but also a multilayer bottle having a satisfactory mechanical strength. In addition, the polyester (A)having a characteristic viscosity of 1.30 or less, does not show deterioration of fluidity during molding, the easier the manufacture of multilayer bottles.

Further, the polyester (A), from which are formed mainly of the outer or inner layer of the multilayer bottles, can also be blended with other thermoplastic polymers, or various additives, unless the addition thereof does not adversely impact on the target PA is ometry of the present invention. The outer or inner layer preferably contains a polyester (A) in an amount of 90 wt.% or more (including 100 weight%). Examples of other thermoplastic polymers include thermoplastic polyester polymers such as polyethylene-2,6-naphthalenyloxy, polymers based on polyolefins, polycarbonates, polyacrylonitrile, polyvinyl chloride and polystyrene. Examples of additives include ultraviolet absorbers of radiation, oxygen scavengers, dyes and absorbers of infrared radiation (Supplement for additional heat) for the rapid heating of the preform and reduce cycle time for formation.

The coefficient of the oxygen (OTR) of the barrier layer formed in the multilayer bottle according to the invention, measured at a temperature of 23°C and relative humidity (RH) 60%, preferably an average of 0.2 cm3·mm/(m2·day·ATM) or less, more preferably 0.15 cm3·mm/(m2·day·ATM) or less, more preferably 0.10 cm3·mm/(m2·day·ATM) or less, and further more preferably of 0.08 cm3·mm/(m2·day·ATM) or less. When the value of the OTR of the barrier layer is within the above range, the obtained multilayer bottle exhibits good characteristics of permanence and is capable of increase will continue inost shelf life frozen in her content.

In the multilayer bottle according to the invention the barrier layer is preferably made of a compounded mixture containing at least two components, comprising the polyamide (B), obtained by polycondensation of diamines component containing 70 mol.% or more (including 100 mol.%) meta-xylylenediamine, with decarbonisation component containing 70 mol.% or more (including 100 mol.%) α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms, and a thermoplastic polymer (C), srednekislye molecular weight which is from 10 to 65% from srednekamennogo molecular weight of the polyamide (B). When the mixture of the polyamide (A) with thermoplastic polymer (C)having a lower molecular weight than the polyamide (C), the obtained barrier layer has an improved flexibility and strength midplains clutch and exhibits good resistance to delamination.

The polyamide (B)used in the present invention, has a high barrier characteristics and exhibits excellent properties including processability when combined injection molding and joint conformance with the blow and the hood, when molded together with the polyester (a) to (mainly polyethylene terephthalate).

Diamines of the structural unit contained in the polyamide (B)contains meta-xylylenediamine unit in the amount of 70 mol.% or the more, preferably 75 mol.% or more and more preferably 80 mol.% or more. When the contents of the meta-xylylenediamine block diamines of the structural unit is less than 70 mol.%, the obtained polyamide (B) is prone to deterioration of characteristics of gas-tightness. Examples of diamines other than meta-xylylenediamine, which can be used in the diamines of the structural unit include, but are not limited to these, aliphatic diamines, such as tetramethylaniline, pentamethylene, 2-methylpentylamine, hexamethylenediamine were, heptamethylnonane, octamethylene, monomethylaniline, decamethylenediamine, documentrenderer, 2,2,4-trimethylhexamethylene-diamine and 2,4,4-trimethylhexamethylenediamine; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexane)methane, 2,2-bis(4-aminocyclohexane)propane, bis(aminomethyl)decalin and bis(aminomethyl)tricyclodecane; and aromatic diamines containing cycles, such as 4,4'-diaminodiphenyl ether, para-phenylenediamine, para-xylylenediamine and bis(aminomethyl)naphthalene.

Decarbonisation blocks contained in the polyamide (B)comprises units of the α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms in the amount of 70 mol.% or more, preferably 75 mol% or more, and more preferably 80 mol.% or more. When the content of the structural unit α,ω-linear aliphatic dicarboxylic acid unit dicarboxylic acid is within the above range, the obtained polyamide exhibits excellent characteristics of permanence and formemost. Examples of α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms, which can be used in the present invention include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, Emelyanova acid, cork (subernova) acid, azelaic acid, adipic acid, sabotinova acid, undemandingly acid and dodecandioic acid. Among these α,ω-linear aliphatic dicarboxylic acids are preferred is adipic acid.

In the present invention, the aromatic dicarboxylic acid, such as, for example, terephthalic acid, isophthalic acid and 2,6-natalijagolosova acid, may also be added as a dicarboxylic acid other than the α,ω-linear aliphatic dicarboxylic acid, in the amount of 30 mol.% or less.

Next, a small amount of molecular weight regulator, such as monoamines and monocarboxylic acids, can also be added during the polycondensation to obtain a polyamide. Component dick is Borovoy acid, used in the present invention, preferably contains from 100 to 70 mol.% α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms and more than 0 but not more than 30 mol.% other aromatic dicarboxylic acids.

The polyamide (A) can be obtained by way of polycondensation in the melt. For example, the polyamide (B) may be obtained by the method of heating the nylon salt prepared from meta-xylylenediamine and adipic acid, under pressure in the presence of water, and polymerization salt supported in the molten state, at the same time with the removal of her as the added water, and the water formed by condensation. Alternatively, the polyamide (B) may be also obtained by a method of directly adding meta-xylylenediamine to adipic acid is maintained in the molten state, for the introduction of these compounds into the polycondensation under normal pressure. In the latter method, the polycondensation, in order to maintain the reaction system homogeneous fluid, meta xylylenediamine continuously added to the adipic acid, and a polycondensation reaction between them occurs by heating the reaction system to a temperature not lower than the melting temperature of the formed oligoimide and polyamide.

The polyamide (B) may also be obtained by further introduction of the polyamide prepared what recondensation in the melt, in the polymerization reaction in the solid state. A method of producing polyamide is not particularly limited, and the polyamide can be obtained using well-known methods and conditions of polymerization.

Srednekislye molecular weight of the polyamide (C) is preferably from 18000 to 43500, and more preferably from 20000 to 30000. When srednekislye molecular weight of the polyamide (C) is within the above range, the formability of the polymer material for forming the multilayer bottle is improved, and the obtained multilayer bottle exhibits excellent resistance to delamination. Meanwhile, the polyamide (B)having srednekamennogo molecular weight of from 18000 to 43500, exhibits a relative viscosity of from about 2.3 to about 4.2, and the polyamide (B)having srednekamennogo molecular weight of from 20,000 to 30,000, exhibits a relative viscosity of from about 2,44 to about 3,19. The relative viscosity used here means a value obtained by measuring the viscosity of a solution prepared by dissolving 1 g of polyamide in 100 ml of 96%sulfuric acid, at a temperature of 25°C. using a viscometer Cannon-Fenske, etc.

The polyamide (b) may also contain a compound of phosphorus to improve process stability during molding of the melt or to prevent unwanted staining of polyamide (Century. Examples of phosphorus compounds include phosphoric compounds containing alkali metals or alkaline earth metals. Specific examples of phosphorus compounds include phosphates, hypophosphites and phosphites of alkali metals or alkaline earth metals such as sodium, magnesium and calcium. Among these phosphorus compounds are mainly used hypophosphite alkali metals or alkaline earth metals, because they are perfectly manifest themselves, in particular, in preventing staining of polyamide. The concentration of phosphorus added to the polyamide (B)is preferably from 1 to 500 million-1more preferably 350 million-1or less, and more preferably 200 million-1or less in terms of phosphorus atoms in the calculation of the polyamide (B). Even when the concentration of added phosphorus atoms exceeds 500 million-1the effect of preventing coloration of the polyamide is no longer increases, and rather there is an increasing tendency to undesirable haze of the films produced from polyamide.

Srednekislye molecular weight thermoplastic polymer (C) is preferably from 10 to 65%, and more preferably from 20 to 50%, from srednekamennogo molecular weight of the polyamide (B). When srednekislye molecular weight thermoplastic polymer (C) is within vishey the above range, the formability of the polymer material for forming the multilayer bottle is improved. Then, the obtained barrier layer exhibits a good ability to follow coating layers (inner and outer layers), when the obtained multilayer bottle is strike, the more providing excellent stability bottles to stratification. In addition, when srednekislye molecular weight thermoplastic polymer (C) is within the above range, thermoplastic polymer (C)having a lower modulus than that of the polyamide (B), exhibits good dispersibility in the barrier layer, providing an excellent effect of improving the resistance to delamination of the obtained bottle.

Bending modulus thermoplastic polymer (C) is preferably from 30 to 80% of modulus of bending polyamide polymer (B), on the measurement of both ASTM D790. When bending modulus thermoplastic polymer (C) is within the above range, the obtained barrier layer has good flexibility and therefore shows good ability to follow coating layers, providing excellent resistance made of multilayer bottles to stratification. Bending modulus of the polyamide (C) is preferably from 3 to 5 GPA.

Thermoplastic polymer (C) may be made of one the first grade polymer or compounded mixture of several polymers. Thermoplastic polymer (C) is not particularly limited, and preferably is selected from those polymers that are able to show good transparency when mixed with the polyamide (B). Examples of thermoplastic polymer (C) include polyesters, polyamides, proximally in the form of a simple polyhydroxyether having a terminal α-glycol fragment at one or both ends of their chains, polyglycolide acid and a variety of elastomers.

Among these polymers as thermoplastic polymer (C) particularly preferred proximally in the form of a simple polyhydroxyether having a terminal α-glycol fragment at one or both ends of its chain as compounded mixture of thermoplastic polymer (S) and polyamide (B) shows the excellent transparency, when stretched, and the obtained multilayer bottle exhibits excellent resistance to delamination due to the good interaction between the polyamide (b) and the polyester (A), which provides hydroxyl groups contained in the molecular chain, simple polyhydroxyether.

In addition, polyglycolide acid is preferably used as thermoplastic polymer (S). Polyglycolide acid are in the form of a polymer containing recurring structural units of the, represented by the formula [-O-CH2-CO-]. The content of the repeating structural units in polyglycolic acids is preferably 60 wt.% or more, more preferably 70 wt.% or more, and still more preferably 80 wt.% or more. Examples of the repeating structural units other than the above repeating structural unit [-O-CH2-CO-]that may be contained in polyglycolic acids include-O-(CH2)n-O-CO-(CH2)m-O-, in which the index n is a number from 1 to 10 and the index m is a number from 0 to 10; -O-CH[(CH2)jH]-CO-, in which the index j is a number from 1 to 10; -O-(CR1R2)k-CO-in which R1and R2each independently represent a hydrogen atom or alkyl group having from 1 to 10 carbon atoms, and the index k is a number from 2 to 10; -O-CH2-CH2-CH2-O-CO-; and-O-CH2-O-CH2-CH2-. The melting temperature, molecular weight and viscosity polyglycolic acids can be regulated by introducing in the last of these repeating structural units.

Thermoplastic polymer (C) is particularly preferably is a polyamide thanks to the excellent transparency of the compounded mixture with a polyamide (B) tensile and parki is th compatibility with the polyamide (B). Examples of the polyamide applicable as a thermoplastic polymer (C)include, but are not specifically limited to those of the homopolymers, such as poly (6-aminocaproic acid (RA-6), also known as polycaprolactam, polyhexamethylenediamine (PA-6,6), poly-7-lineamenta acid (RA-7), poly-10-aminocapronic acid (RA-10), poly-11-aminoundecanoic acid (RA-11), poly-12-aminododecanoic acid (RA-12), polyhexamethyleneguanidine (RA-6,10), polyhexamethylenediamine (PA-6,9) and polytetramethylene (PA-4,6); aliphatic polyamides, such as a copolymer of caprolactam and hexamethylenediamine (PA-6,6/6), the copolymer hexamethylenediamine and caprolactam (PA-6/6,6), and poly-meta-xylylenediamine (PA-MXD6); and amorphous polyaromatics polyamides, such as polyhexamethylenediamine (PA-6I), the copolymer hexamethylenetetramine and hexamethylentetramine (PA-6I/6T), poly-meta-xylylenediamine (PA-MXDI), a copolymer of caprolactam and meta-xylylenediamine (PA-6/MXDI) and a copolymer of caprolactam and hexamethylenetetramine (PA 6/6I).

Thermoplastic polymer (C)used in the present invention, preferably is a polyamide oligomer or polyamide with a low molecular weight, which is obtained by polycondensation of diamines component containing 70 mol.% or more (including 100 mol.%) meta is chillindilin, with decarbonisation component containing 50 mol.% or more (including 100 mol.%) α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms.

The method of mixing the polyamide (A) with thermoplastic polymer (C) is not particularly limited. The polyamide (b) and thermoplastic polymer (C) can be mixed together in the dry state in the preparation of preforms bottles. Alternatively, the polyamide (b) and thermoplastic polymer (C) can be mixed together in the molten state using a single screw extruder, twin screw extruder, etc. before making preforms bottles, or can be mixed together in the molten state to obtain uterine mixture of these polymers.

The barrier layer preferably is made mainly of polyamide (B). From the point of view of good barrier characteristics, the content of the polyamide (C) in the barrier layer is more preferably 70 wt.% or more, and still more preferably 80 wt.% or more. Depending on the variety of polymers or the like, is added to the polyamide (B), if the content of the polymers or the like in the barrier layer is more than 30 wt.%, the above-mentioned index OTR of the barrier layer tends to exceed the value of 0.2 cm3·mm/(m2·day·ATM), with the result of hudsonia its barrier characteristics.

In the present invention, the content of thermoplastic polymer (C) in the barrier layer is preferably from 1 to 20 wt.%, more preferably from 2 to 15 wt.%, and even more preferably from 2 to 10 wt.%, the weight of the barrier layer. When the content of thermoplastic polymer (C) in the barrier layer is within the above range, the formability of the polymer material for forming the multilayer bottle is improved, and the obtained multilayer bottle exhibits excellent resistance to delamination.

Thermoplastic polymer (C) is dispersed in the barrier layer, for example, in the form of particles shaped Central portion which has a greater thickness than that of the edge part (disc-shaped form), in the form of Islands, in the form of short rods or flattened shape of the Rugby ball. Shape (area, major axis and minor axis) of individual domains of thermoplastic polymer (C)dispersed in the barrier layer, as visible on the cut of the barrier layer preferably satisfies the following requirements (1) to (3):

Area (average value) < 0,054 μm2(1)
The major axis (average value) < 0.6 μm(2)
The minor axis (average value) < 0,09 ám(3)

Area, the major axis and the minor axis can be measured by visual microscopic examination of ultra-thin slice having a thickness of about 0.1 μm, which cut horizontally installed vertically laminated bottle, about a vertical axis, a vertically standing multilayer bottles. In the multilayer bottle according to the invention thermoplastic polymer (C) is usually dispersed in the barrier layer in the form of flat plates due to stretching of the barrier layer. Therefore, when the observation of the barrier layer from the vertical axis standing multilayer bottle form separate domains of thermoplastic polymer (S)dispersed in it, satisfies the above requirements (1)to(3). The area of the individual domains of thermoplastic polymer (C)dispersed in the barrier layer is more preferably from 0.01 to 0,054 μm2, the major axis is more preferably not less than 0.1 μm but less than 0.6 μm, and the minor axis, more preferably not less than 0.01 μm but less than 0,09 ám. The ratio of major axis to minor axis (major axis/minor axis) is preferably from 1.1 to 100, more preferably from 2 to 50, and more preferably from 3 to 1.

When the form of separate domains of thermoplastic polymer (S)dispersed in the barrier layer satisfies the above requirements, the impact energy caused by the bottle, easily reduced inside of the barrier layer and is easily absorbed by the dispersed therein thermoplastic polymer (S). In the obtained multilayer bottle exhibits excellent resistance to delamination.

In addition, the barrier layer may also contain a polymer (D)other than the polyamide (B) or thermoplastic polymer (S), for example one of many types of polymers, such as nylon 6, nylon 66, nylon 6,66, nylon 6I/6T, polyesters, polyolefins and proximally, if only these polymers do not have any adverse effect on the target parameters of the present invention. In addition, the barrier layer may also contain various additives. Examples of additives include inorganic fillers such as glass fiber and carbon fiber; inorganic fillers plate, such as glass flakes, talc, kaolin, mica, montmorillonite, organogeny; shock absorbers, such as various elastomers; nucleators; lubricants, such as compounds with aliphatic amides, compounds based on metal salts of aliphatic acids; antioxidants, such as connect the deposits of copper, organic or inorganic halogen-containing compounds, compounds based on spatial difficult phenols, compounds based on spatial difficult amines, compounds with hydrazine, sulfur-containing compounds and phosphorus-containing compounds; thermal stabilizers; anticogulant; absorbers of ultraviolet radiation, such as compounds based on benzotriazole; lubricating means for the mold; plasticizers; colorants; flame retardant means; compounds capable of imparting barrier layer capable of absorbing oxygen, such as cobalt containing compounds; and compounds capable of preventing gelation of the polyamide.

The multilayer bottle according to the invention could sometimes be the part having a low degree of stretch (from 1 to 2.5 times) depending on the shape of the preform or bottle. Part of having such a low degree of tension, tends to buy the white color in the absorption of water. So, if you want to barrier layer can be added to the tool against the clenched to prevent clenched barrier layer, the providing a multilayer bottle having good transparency.

Remedy clenched obtained from the metal salt of aliphatic acid having from 18 to 50 carbon atoms, and preferably from 18 to 34 the volume of carbon. It is assumed that the metal salt of aliphatic acid having 18 or more carbon atoms, exhibits good activity against clenched, while the metal salt of aliphatic acid having 50 carbon atoms or less uniformly dispersed in the barrier layer. Aliphatic acid may be branched or may contain a double bond. Examples of preferred aliphatic acids include linear saturated aliphatic acids such as stearic acid (C18), Aksenova acid (C20), Bekenova acid (C22), montanoa acid (s) and triacontanoic acid (C30). Examples of metals that can form a salt with these aliphatic acids include, but are not limited to such, sodium, potassium, lithium, calcium, barium, magnesium, strontium, aluminum, and zinc. Of these preferred metals are sodium, potassium, lithium, calcium, aluminum and zinc.

Metal salts of aliphatic acids may be used individually or in combination of two or more of them. In the present invention, although the particle size of the metal salts of aliphatic acids is not particularly limited, a metal salt of aliphatic acids preferably have a particle size of 0.2 mm or less, because such small particles easily uniformly dispersed in the barrier with the second.

The amount of added metal salt of aliphatic acid is preferably 0.005 to 1.0 part by weight, more preferably from 0.05 to 0.5 parts by weight, and even more preferably from 0.12 to 0.5 parts by weight, per 100 parts by weight of the total amount of the barrier layer. It is assumed that the barrier layer exhibits good effect against clenched, when the amount of metal salt of aliphatic acid to be added to the barrier layer ranges from 0.005 part by weight or more, per 100 parts by weight of the total amount of the barrier layer. When the amount of metal salt of aliphatic acid to be added to the barrier layer is 1.0 part by weight or less, per 100 parts by weight of the total amount of the barrier layer, the obtained multilayer bottle maintains a low haze.

Alternatively, instead of the above-mentioned metal salt of aliphatic acid as a remedy against clenched may be added a compound selected from the group consisting of the following demigny and diapiric compounds. Diamine connection and diepiriye compounds can be added separately or in the form of a mixture of any two or more of them, or one or more diamedix compounds may be used in combination with one or more deternime with what disiniame.

Diamine compounds can be obtained by the reaction of aliphatic acids having from 8 to 30 carbon atoms, with a diamine having from 2 to 10 carbon atoms. It is assumed that diamidine compounds derived from aliphatic acid having 8 or more carbon atoms and a diamine having 2 or more carbon atoms, exhibit good activity against clenched, while diamidine compounds derived from aliphatic acids having 30 or less carbon atoms and a diamine having 10 or less carbon atoms, uniformly dispersed in the barrier layer. Aliphatic acids may be branched or may have a double bond. Of these aliphatic acids are preferred linear saturated aliphatic acid.

Examples of aliphatic acids as component diamedix compounds include stearic acid (C18), Aksenovo acid (C20), beenbuy acid (C22), montanabuy acid (s) and triacontanoic acid (C30). Examples of diamines component diamedix compounds include Ethylenediamine, butylenediamine, hexanediamine, xylylenediamine and bis(aminomethyl)cyclohexane. In the present invention can be advantageously applied diamidine compounds derived from the combination of these components. Of these diamedix compounds are preferred diamine connect the Oia, derived from aliphatic acids having from 8 to 30 carbon atoms, and a diamine, consisting mainly of Ethylenediamine, and diamine compounds derived from aliphatic acids, consisting mainly of montenovo acid, and a diamine having from 2 to 10 carbon atoms.

Diepiriye compounds can be obtained by the reaction of aliphatic acids having from 8 to 30 carbon atoms, with diola having from 2 to 10 carbon atoms. It is assumed that diepiriye compounds derived from aliphatic acid having 8 carbon atoms or more, and a diol having 2 carbon atoms or more, have a good action against clenched, while diepiriye compounds derived from aliphatic acids having 30 carbon atoms or less, and a diol having 10 carbon atoms or less uniformly dispersed in the barrier layer. Aliphatic acids may be branched or may have a double bond. Of these aliphatic acids are preferred linear saturated aliphatic acid.

Examples of aliphatic acid as component diapiric compounds include stearic acid (C18), Aksenovo acid (C20), beenbuy acid (C22), montanabuy acid (s) and triacontanoic acid (C30). Examples of the diol component diapiric compounds include ethylene glycol, propandiol, butandiol, hexanediol, Killington and cyclohexanedimethanol. In the present invention can be effectively used diepiriye compounds derived from the combination of these components. Of these preferred compounds are compounds derived from aliphatic acids, consisting mainly of montenovo acid, and diol, consisting mainly of ethylene glycol and/or 1,3-butanediol.

The number of added dumenigo connection and/or defimage connection is preferably 0.005 to 1.0 part by weight, more preferably from 0.05 to 0.5 parts by weight, and even more preferably from 0.12 to 0.5 parts by weight, per 100 parts by weight of the total amount of the barrier layer. When the number dumenigo connection and/or defimage compounds that are added to the barrier layer ranges from 0.005 part by weight or more, per 100 parts by weight of the total amount of the barrier layer, it is assumed that the barrier layer exhibits good effect against clenched. When the number dumenigo connection and/or defimage compounds that are added to the barrier layer is 1.0 part by weight or less, per 100 parts by weight of the total amount of the barrier layer, the obtained multilayer bottle maintains a low haze.

Remedy clenched may be added to the barrier layer is beinvested ways of mixing. For example, pellets of the polyamide (b) and an anti-clenched can be loaded into a rotating hollow container and mixed it together. Alternatively, it may be attracted to such a method in which after the preparation of compositions containing polyamide (C) and an anti-clenched with a high concentration, thus formed polymer composition is diluted with pellets of the polyamide (B)that does not contain anti-clenched, to obtain a polymer composition having a predetermined concentration of anti-clenched, followed by kneading the obtained diluted composition in the melt in plasticators; or a method in which after mixing in the melt in plasticators the resulting polymer composition is subjected to consecutive molding method of molding, etc.

When you use the clenched against the barrier layer can be protected from the appearance clenched directly after manufacturing the multilayer bottle. Further, even after protection clenched over a long period of time in conditions that do not cause clenched, and when a strong contribution to that, the barrier layer may also be protected from the appearance clenched. More specifically, even when the multilayer bottle, which was protected in the long lane is an ode to time under such conditions, which bottle do not show clenched or exposed to a strong whitening, even without adding to it the funds against clenched, for example, at a temperature of 23°C and 50%relative humidity, it is exposed to high humidity, contact with water or boiling water or by being heated to a temperature higher than the glass transition temperature of the polymer, the appearance in her clenched suppressed in a similar way as immediately after molding.

The multilayer bottle according to the invention can be manufactured by the following method. That is, for example, using a machine for injection molding under pressure, equipped with two hydraulic injection cylinder, the polyester (A) is injected from the hydraulic injection cylinder for the top layer, and compounded mixture of the polyamide (b) and thermoplastic polymer (C) is injected from the hydraulic injection cylinder for the core layer in the cavity of the metal mold through the respective hot sprue metal mold for forming a multilayer preform, and then the obtained multilayer preform is subjected inflatable molding with biaxial stretching of well-known ways to obtain multilayer bottles.

In General, the multilayer preform may be subjected inflatable is the well-known molding methods, such as the so-called method of cold draft form and the so-called method of hot rough shape. For example, there may be used a method in which after heating the surface of the multilayer preform to a temperature of from 80 to 120°With a multi-layer preform is subjected to stretching in its axial direction by mechanical means, such as the introduction of a center rod, and then compressed air under high pressure, usually compressed to the level from 2 to 4 MPa, in multilayer blown into the preform to exposure of the preform to stretch and inflatable form in its transverse direction, or a method in which after crystallization Golovino part of a multilayer preform, and heating the surface of the multilayer preform to a temperature of from 80 to 120°C multilayer the preform is subjected inflatable molding in a metal mold heated to a temperature of from 90 to 150°C.

In the present invention the temperature of the heating of the preforms is preferably from 90 to 110°C., and preferably from 95 to 108°C. When the temperature of the heating of the preforms is 90°C or higher, the barrier layer or the layer of polyethylene terephthalate (PET) are protected from being subjected to cold stretching and whitening due to heating. When the temperature of the heating of the preforms is 110°C. or below, the barrier layer protect the puppy from the course of crystallization and clenched, and the obtained multilayer bottle next is protected from reduction of resistance to delamination.

From the position of the great barrier characteristics and formemost, the multilayer bottle according to the invention preferably has a three-layer structure, sequentially composed of a polyester (A) layer, the barrier layer and the polyester (A) layer or five-layer structure composed sequentially of a polyester (A) layer, barrier layer, a polyester (A) layer, the barrier layer and the polyester (A) layer.

Multilayer bottle having a three-layer structure or a five-layer structure can be produced by exposure to a multilayer preform having a three-layer structure or a five-layer structure, the inflatable molding with biaxial stretching using well-known methods. The method of obtaining a multilayer preform having a three-layer structure or a five-layer structure is not particularly limited, and can be applied to any suitable well-known means. For example, using a machine for injection molding under pressure with a hydraulic injection cylinder from the outer layer to the injection of the polyester (A)forming the inner and outer layers in a multilayer preform, and a hydraulic injection cylinder for the core layer drawpicture compounded polymer mixture, forming the barrier layer, the polyester (A) is first injected from the machine for injection molding under pressure and then compounded polymer mixture forming the barrier layer, and the polyester (A) inject at the same time from the machine for injection molding under pressure and then the required amount of the polyester (A) injected from the past to fill the cavity of the metal mold, the forming a multi-layer preform having a three-layer structure composed sequentially of a polyester (A) layer, the barrier layer and the polyester (A) layer.

In addition, using the same machine for injection moulding, as used above, the polyester (A) is first injected from the machine for injection molding under pressure and then only compounded polymer mixture forming the barrier layer, injected from the machine for injection molding under pressure, and finally the polyester (A) injected from the past to fill the cavity of the metal mold, the forming a multi-layer preform having a five-layer structure composed sequentially of a polyester (A) layer, barrier layer, a polyester (A) layer, the barrier layer and the polyester (A) layer.

Meanwhile, the method of obtaining a multilayer preform is not limited only to the above-mentioned methods.

the thickness of the polyester (A) layer in the multilayer bottle is preferably from 0.01 to 1 mm, and the thickness of the barrier layer, it is preferably 0.005 to 0.2 mm (from 5 to 200 microns). The thickness of the multilayer bottle is not necessarily constant across its part and usually varies in the range from 0.2 to 1.0 mm

In the multilayer bottle obtained by exposure of the multilayer preform inflatable molding with biaxial stretching, the barrier layer can be created at least in the cylindrical part of the multilayer bottle to give the bottle a good characteristics of gas-tightness. However, when the barrier layer is extended up to the edge Golovino of the bottle, the characteristics of the permanence of multilayer bottles can be even more improved.

The weight percentage of the barrier layer in the multilayer bottle according to the invention is preferably from 1 to 20 wt.%, more preferably from 2 to 15 wt.%, and even more preferably from 3 to 10 wt.%, calculated on the total weight of the multilayer bottle. When the weight percentage of the barrier layer is within the above range, the obtained multilayer bottle exhibits good characteristics of gas-tightness, and a multilayer preform as a precursor is easily formed in the multilayer bottle.

The multilayer bottle according to the invention is protected from the occurrence of stratified is even if I fall or impact. In addition, the multilayer bottle provides a greater degree of freedom to design without limitations in terms of specific forms with fewer irregularities or less bends due to lesser the possibility of stratification, even when the bottle has such a shape that have discontinuities and bends. The multilayer bottle according to the invention is predominantly used for the storage and preservation in her range of products. Examples of products that are stored or Packed in multilayer bottle, include liquid beverages, such as sodas, juice, water, milk, sake, whiskey, Shochu, coffee, tea, generowanie drink and health drink, seasoning, such as liquid seasonings, sauces, soy sauce, dressing and liquid soup mix, liquid processed foods, such as liquid soup, liquid medicines, cosmetic detergent, milk lotion, remedy for hair styling, hair dye, shampoo, etc.

EXAMPLES

The present invention will be described below in more detail with the involvement of the following examples and comparative examples. However, these examples are only illustrative and are not intended to limit the invention as such. Meanwhile, various properties of multi-layer bottle were evaluated by the following methods.

(1) Sustainable is here to stratification

The stability of multilayer bottles to stratification was estimated height (cm) bundle, measured when the exposure of the bottle drop test for containers according to the standard ASTM D2463-95, Procedure Century high altitude stratification indicate a higher resistance to delamination. Specifically, first, the tested multilayer bottle was filled with water and closed the lid, and then subjected to a vertical drop to the bottom part of the multilayer bottle hit the floor for the visual detection of the occurrence of any stratification in it. The drop test was repeated at the same time increasing the drop height of multilayer bottles at intervals of 15 cm and a minimum height of fall, which was observed the occurrence of delamination of the multilayer bottle was defined as the height of the lamination of the multilayer bottle. The number of multilayer bottles subjected to the drop test was 30.

(2) the Coefficient of the oxygen (OTR)

The coefficient of the oxygen (OTR) was measured at 23°C and 50% relative humidity according to ASTM standard D3985 using a measuring instrument “OX-TRAN 10/50A”, manufactured by Modern Controls Corp. Meanwhile, the value of OTR for the barrier layer was measured by separating and sampling only the barrier layer of the multilayer bottle. In the case when the Department is tion and sampling only the barrier layer from the bottle was difficult the value of the OTR of the barrier layer was determined as follows. That is, the cylindrical part of the bottle, consisting of layers of polyester (a) and the barrier layer, cut and unfold the sheet and the value of the OTR only the barrier layer are calculated according to the measured value OTR sheet, the thickness of the respective layers, measured with a microscope, etc. and separately measured values OTR layers of polyester (A). In addition, the value of the OTR only the barrier layer can also be calculated from the magnitude of OTR bottle, the surface area of the bottle and thicknesses of the respective layers.

(3) the State of dispersion of thermoplastic polymer (C)

Only the barrier layer was separated from the cylindrical part of the multilayer bottle made inflatable molding, and filled it with epoxy resin. After hardening the epoxy resin multilayer bottle cut vertically in its longitudinal direction (MD) using ultramicrotome “CR-X Power Tome XL”, manufactured by Boeckeler Instruments Corp., for preparation of the test slice having a thickness of about 0.1 μm. Thus prepared test slice was placed on a copper grid and observed under the microscope. At the same time, the obtained hyperfine test cut was painted in pairs of ruthenium chloride, and it was observed to determine the state of dispersion therein is termoplasticheskie polymer (S) tone or contrast staining. Microscopic examination was performed using a transmission electron microscope for surface observations “S4800”, manufactured by Hitachi Limited, when the observation conditions including an accelerating voltage of 30 kV, a current of 10 mA, the measured increase of 25,000 times and the measurement mode (transmission electron microscopy, TEM).

EXAMPLE 1

Under the following conditions raw polymeric materials were subjected to the injection molding with the formation of a three-layer preform (27 g), arranged sequentially from a polyester (A) layer, the barrier layer and the polyester (A) layer. After cooling, the resulting preform was heated and subjected inflatable molding with biaxial stretching, having the multilayer bottle.

The polyester (A)

The polyethylene terephthalate “RT543C”, manufactured by Nippon Unipet Co., Ltd.

Characteristic viscosity: 0,75 measurement at a temperature of 30°C in a mixed solvent containing phenol and tetrachlorethane at a weight ratio of 6/4.

The polyamide (B)

Poly-meta-xylylenediamine “MX Nylon S6007 (product of polymerization in the solid state)”produced by Mitsubishi Gas Chemical Co., Inc.

Srednekislye molecular weight: 23500.

Relative viscosity: 2,70 measurement at 25°C in a solution prepared by dissolving 1 g of the polymer is 100 ml of 96%sulfuric acid.

Bending modulus: a 4.5 GPA (ASTM D790).

Thermoplastic polymer (C)

Paroxysmal Grade PKHB”manufactured by InChem Corp.

Srednekislye molecular weight: 9500.

The glass transition temperature (Tg): 84°C.

Bending modulus: a 2.9 GPA (ASTM D790).

Polyamide ()/Thermoplastic polymer (C)

95/5 (weight ratio)

Form a three-layer preforms

Full length: 95 mm; outer diameter: 22 mm; wall thickness: 4,2 mm

Three-layer preform was fabricated using the machine for injection moulding under pressure (model: "M200"; type four-point formation), manufactured by Meiki Seisakusho Co., Ltd.

Conditions of forming three-layer preforms

The temperature of the hydraulic injection cylinder for top layer: 280°C.

The temperature of the hydraulic injection cylinder for the core layers: 260°C.

The temperature of the Gating system of the mold: 280°C.

The water temperature for cooling the mold: 15°C.

Content barrier polymer in the preform: 5 wt.%

The shape of the multilayer bottle

Full length: 223 mm; outer diameter: 65 mm; packaging: 500 ml; the bottom of the form: the shape of the bottle of champagne; without grooves on the cylindrical part.

However, inflatable molding with biaxial stretching was performed using the machine for injection molded who I am under pressure (model: “EFB100ET”), manufactured by Frontier Inc.

Conditions for blow molding with biaxial stretching

The temperature of the heating preforms: 108°C.

The pressure applied to the extendable rod: 0.5 MPa.

The pressure of the primary blow: 1.1 MPa.

The pressure of the secondary blowing: 2.5 MPa.

The lag time of the primary blow: 0,34 C.

The time of the primary blow: 0,30 C.

The time of the secondary blowing: 2,0 C.

The reset time of the bulge: 0,6 C.

The temperature of the mold: 30°C.

The weight percentage of the barrier layer was 5 wt.% calculated on the total weight of the obtained multilayer bottle. The results of the evaluation of multilayer bottles are shown in Table 1.

EXAMPLES 2-8 AND COMPARATIVE EXAMPLES 1-3

Repeating the same procedure as in Example 1 except that the composition of the barrier layers was changed to that shown in Tables 1-3, the receiving multilayer bottles. The evaluation results thus obtained multilayer bottle shown in Tables 1-3.

Values abbreviations for polymers shown in Tables 1-3, are as follows.

(1) 6007

Poly-meta-xylylenediamine “MX Nylon S6007” (product of polymerization in the solid state), produced by Mitsubishi Gas Chemical Co., Inc.

Srednekislye molecular weight: 23500.

Relative viscosity: 2,70.

Bending modulus: a 4.5 GPA.

(2) 6121

Poly-IU the a-xylylenediamine “MX Nylon S6121” (product of polymerization in the solid state), produced by Mitsubishi Gas Chemical Co., Inc.

Srednekislye molecular weight: 40000.

Relative viscosity: 3,94.

Bending modulus: a 4.5 GPA.

(3) PKHB

Paroxysmal Grade PKHB”manufactured by InChem Corp.

Srednekislye molecular weight: 9500.

The glass transition temperature (Tg): 84°C.

Bending modulus: a 2.9 GPA.

(4) PKFE

Paroxysmal Grade PKFE”manufactured by InChem Corp.

Srednekislye molecular weight: 16000.

The glass transition temperature (Tg): 98°C.

Bending modulus: a 2.9 GPA.

(5) Oligomer

Polyamide oligomer, obtained by polycondensation of meta-xylylenediamine with adipic acid

Srednekislye molecular weight: 5000.

Bending modulus: a 3.5 GPA.

(6) V

Nylon 6 "Class: V"manufactured by Ube Kosan Co., Ltd.

Srednekislye molecular weight: 15000.

Bending modulus: a 2.5 GPA.

(7) V

Nylon 66 "Class: V"manufactured by Ube Kosan Co., Ltd.

Srednekislye molecular weight: 15300.

Relative viscosity: 2,5.

Bending modulus: a 3.0 GPA.

(8) V

Nylon 66 "Class: V"manufactured by Ube Kosan Co., Ltd.

Srednekislye molecular weight: 19800.

Relative viscosity: 2,9.

Bending modulus: a 3.0 GPA.

The relative strength and bending modulus were measured in the same manner as described above.

TABLE 1
Examples
1234
Polymers for barrier layer
Polyamide ()6007600760076121
Thermoplastic polymer (C)RKNWRKNWoligomerPKFE
The polymer (D)----
The composition of the barrier layer (weight%)
Polyamide ()95909393
Thermoplastic polymer (C)61077
The polymer (D)----
Attitude srednekamennogo molecular weight thermoplastic polymer (C) to srednekamennogo molecular weight of the polyamide (C) (%)40402141
Attitude srednekamennogo molecular weight of the polymer (D) to srednekamennogo molecular weight of the polyamide (C) (%)----
The ratio of the modulus thermoplastic polymer (S) to the module polyamide (In) (%)64647864
The state of dispersion of thermoplastic polymer (C)
Size (μm2)0,0160,024-0,022
The major axis (μm) 0,3640,523-0,440
The minor axis (μm)0,0550,058-0,061
Resistance to delamination (cm)300325270307
The value of the OTR of the barrier layer (cm3·mm/(m2·day·ATM)0,0090,0080,0100,009

Note 1) Mn: srednekislye molecular weight.

TABLE 2
Examples
5678
Polymers for barrier layer
Polyamide ()612160076121 6007
Thermoplastic polymer (C)RKNW2015B2015B2015B
The polymer (D)---2020B
The composition of the barrier layer (weight%)
Polyamide ()97909090
Thermoplastic polymer (C)310106,7
The polymer (D)---3,3
Attitude srednekamennogo molecular weight thermoplastic polymer (C) to srednekamennogo molecular weight of the polyamide (C) (%)24643864
Attitude srednekamennogo molecular weight of the polymer (D) to srednica the military molecular weight of the polyamide (C) (%) ---85
The ratio of the modulus thermoplastic polymer (S) to the module polyamide (In) (%)64646456
The state of dispersion of thermoplastic polymer (C)
Size (μm2)0,0160,045to 0.0320,020
The major axis (μm)0,2980,5840,4390,400
The minor axis (μm)0,0670,0700,065to 0.060
Resistance to delamination (cm)303240260318
The value of the OTR of the barrier layer (cm3·mm/(m2·day·ATM)0,0090,0140,013 0,011

Note 1) Mn: srednekislye molecular weight.

10
TABLE 3
Comparative Examples
123
Polymers for barrier layer
Polyamide ()600760076007
Thermoplastic polymer (C)---
The polymer (D)-PKFE2020B
The composition of the barrier layer (weight%)
Polyamide ()1009090
Thermoplastic polymer (C)---
The polymer (D)-10
Attitude srednekamennogo molecular weight thermoplastic polymer (C) to srednekamennogo molecular weight of the polyamide (C) (%)---
Attitude srednekamennogo molecular weight of the polymer (D) to srednekamennogo molecular weight of the polyamide (C) (%)-6885
The ratio of the modulus thermoplastic polymer (S) to the module polyamide (In) (%)---
The state of dispersion of thermoplastic polymer (C)
Size (μm2)-0,054to 0.060
The major axis (μm)-0,6800,710
The minor axis (μm)-0,0940,092
Resistance to delamination (cm)150 92150
The value of the OTR of the barrier layer (cm3·mm/(m2·day·ATM)0,0100,0100,015

Note 1) Mn: srednekislye molecular weight.

As shown in the above Examples and Comparative Examples, it was confirmed that the multilayer bottle according to the invention showed extremely excellent resistance to delamination, whereas the bottle, unable to meet the requirements according to the invention, had deteriorated resistance to delamination.

INDUSTRIAL APPLICABILITY

In accordance with the present invention has the ability to produce multi-layer bottle, providing a high degree of freedom in the form of a container and excellent gas-tightness, since the bottle is essentially not affected by stratification. Thus, the present invention is extremely useful from the industrial point of view.

1. Multilayer bottle containing outer layer, inner layer and at least one barrier layer, located between the outer layer and inner layer, and above the outer layer and the inner layer is made, every, mainly of the polyester (A)obtained by polymerization dicarbonate to the PCI-e slot component, containing 80 mol.% or more of terephthalic acid with a diol component containing 80 mol.% or more of ethylene glycol; and the barrier layer includes at least the polyamide (B), obtained by polycondensation of diamines component containing 70 mol.% or more meta-xylylenediamine, with dicarbonate acid component containing 70 mol.% or more α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms, and a thermoplastic polymer (C)selected from the group consisting of proximally in the form of a simple polyhydroxyether with terminal a-glycolic acid fragment at the end of his chain, polyglycolic acid and a polyamide oligomer or polyamide with a low molecular weight, obtained by polycondensation of diamines component containing 70 mol.% or more meta-xylylenediamine, with dicarbonate acid component containing 50 mol.% or more α,ω-linear aliphatic dicarboxylic acid having 4-20 carbon atoms.

2. The multilayer bottle according to claim 1, in which the content of thermoplastic polymer (C) in the barrier layer is from 1 to 20 wt.% the weight of the barrier layer.

3. The multilayer bottle according to claim 1, in which srednekislye molecular weight of the polyamide (b) is from 18000 to 43500.

4. The multilayer bottle according to claim 1, in which the ratio of the modulus of bending thermoplastic polymer (S) to the module and the bending of the polyamide (b) is from 30 to 80%, when both modules bending measured according to ASTM D790.

5. The multilayer bottle according to claim 1, in which the individual domains of thermoplastic polymer (C)dispersed in the barrier layer have a shape satisfying the following requirements (1) to (3), as seen in cross-section of the barrier layer:


6. The multilayer bottle according to claim 1, having a three-layer structure, sequentially containing a layer of polyester (A), the barrier layer and the layer of polyester (A).

7. The multilayer bottle according to claim 1, having a five-layer structure, sequentially containing a layer of polyester (A), the barrier layer, the layer of polyester (A), the barrier layer and the layer of polyester (A).

8. The multilayer bottle according to claim 1, in which the weight percentage of the barrier layer is from 1 to 20 wt.% calculated on the total weight of the multilayer bottle.



 

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15 cl, 8 tbl

FIELD: transport, package.

SUBSTANCE: invention relates to system of producing laminar plastic, packing device to produce laminar plastic and method to produce packages made from packing laminar plastic. Laminar plastic comprises layer of particles that can be magnetised. System comprises at least one magnetisation appliance to apply magnetic field to magnetise certain amount of magnetic particles in forming magnetic mark in packing laminar plastic indicating damage location, for example joint or single local defect. System comprises scanner to detect damages and activate first magnetisation appliance on revealing damage for forming magnetic mark indicating damage location. Packing device comprises magnetic pickup to perceive magnetic marks indicating damage location of package or packing laminar plastic. Method consists in applying magnetic field for forming at least one magnetic mark in packing laminar plastic to mark location of damage and perceive the presence of at least one magnetic mark indicating damage.

EFFECT: efficient detection of damages in packing material.

8 cl, 6 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to multi-component structure, for example multi-layer film that comprises at least first and second components with jointing layer arranged directly there between. Note here that jointing layer comprises at least one copolymer of olefine and unsaturated ether of carbonate acid and at least one photoinitiator wherein at least first component comprises vinylidene chloride polymer or combination of vinylidene chloride polymers that make prevailing ingredient with structure that features increased interlayer adhesion as measured in compliance with ASTM F904-98 at 93 °C after irradiation by UV-radiation and as compared with interlayer adhesion prior to irradiating by UV radiation. Invention relates to method of preparing food that comprises enveloping food in multi-layer packing structure to be subjected to increased temperature sufficient for food preparation, and to method of gluing first layer to second layer in multi-layer film that comprises extruding first and second layer together. Note here that first layer comprises at least 80% of vinylidene chloride polymer and third layer arranged between said first and second layers. Third layer comprises basic polymer including olefine copolymer and that of unsaturated carbonate acid ether and at least one photoinitiator. Said method comprises also forming film and UV irradiation of the latter.

EFFECT: increased adhesion between first and second layer.

18 cl, 5 tbl, 21 ex

FIELD: packing industry.

SUBSTANCE: standing pack, according to invention, has body and bottom, first of all, stable bottom, at the same time, at least material of packet body comprises at least one uniaxially oriented film, besides uniaxially oriented film is part of layer material and has high thickness compared to other layers of material. Thickness of uniaxially oriented film may be more than thickness of all other layers of layer material.

EFFECT: packet may be opened in a simple manner without complete damage or uncontrolled rupture of the whole pack and may be used further after opening.

11 cl

FIELD: packing industry.

SUBSTANCE: inventions are related to packages for food products. Multilayer film consists of the first layer made of plastic material and at least one second layer made of material selected from number of plastic material, metal material, material that is similar to paper, or equivalent materials. Each layer is connected to adjacent layer by means of intermediate layer of adhesive material. Multilayer film at least on one surface of more rigid layer of plastic material has multiple continuous parallel cuts arranged in rows next to each other for reduction of breaking load at the right angles to direction of cuts. Cuts are produced by means of material removal and partially reduce thickness of more rigid layer.

EFFECT: invention provides for easy rectilinear rupture in specified direction of weakened package section.

15 cl, 10 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to fabrication of workpiece from thermally sealed and foldable laminate for packing container resisting SHF heating. Endless ribbon (1) of starting laminate (10) moves in packing laminate conversion line. Endless workpieces for aforesaid packing containers are directed from top to bottom and across machine processing direction in conversion line and top-to-bottom interface (51). Starting laminate (10) is made with bents and cuts for workpieces (50a, 50b). Endless ribbon (2) from heat and electrically conducting material is applied along machine processing direction above aforesaid interface (51) and in combination with stage (a). Elongated indication (53) of hole is effected prior to or after applying ribbon (2). Hole indicator stays within the limits of aforesaid ribbon. Packing container is formed by folding, is filled and sealed by workpiece (50a, 50b).

EFFECT: higher density, reliability and tightness.

23 cl, 8 dwg

FIELD: packing industry.

SUBSTANCE: laminated material comprises a substrate layer and an additive transfer layer. The additive transfer layer contains thermoplastic polymer and an additive which is water-soluble granules of a colouring agent, flavour additive and aromatiser. The additive transfer layer is contacting the food product subject to packing.

EFFECT: package comprising such laminated material gives the packed product improved taste, aroma or colour when being heated or cooked.

22 cl, 12 ex, 4 tbl, 8 dwg

FIELD: packing industry.

SUBSTANCE: casing is produced by the coextrusion of at least two layers including the outer layer (Z). At least one layer which is not an outer one (Z) contains more than 50 wt % of thermoplastic components on the (co)polyamide(s) basis. The outer layer (Z) contains more than 50 wt % of thermoplastic components and inorganic particles distributed in them with at least part of the particles having the diametre of the equivalent sphere exceeding 20 mcm. At least one of the layers (not the outer one (Z)) performs the carrying function.

EFFECT: as per their appearance and roughness the obtained casings for food products are similar to the collagen, protein, reinforced with fibers cellulose and natural casings.

14 cl, 1 tbl, 4 ex

Container // 2397123

FIELD: transport, package.

SUBSTANCE: invention relates to packages intended to store medical and domestic substances. Proposed container has casing with nose and cover arranged on lateral sealing wall that enters container inner space to shut off said nose and to turn therein. Casing and cover comprise appliances for locking the latter on the former and limiting cover turn relative to nose. Cover has cutout made on said sealing wall to form channel closed in the cover first position when said nose is shut off by lateral sealing wall and completely open in second extreme position when said cutout is located opposite the nose to extract vessel content therefrom. Said channel may be slightly opened with cover at other positions on the casing when part of cutout is shut off by casing lateral wall. Turn of the cover from one extreme position to another displaces cutout relative to nose to completely shut off cutout by casing lateral wall for complete shutting off of the channel.

EFFECT: ease of transfer, protection of medical staff from becoming infected, lower costs and suitability for commercial production.

17 cl, 4 dwg

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