Multilayer bottle

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer bottle intended for beer, tea, juices or carbonated drinks. Proposed bottle comprises inner and outer layers, each made from polyether (A), and, at least, one barrier layer arranged there between. Polyether (A) is thermoplastic resin produced by polymerisation of dicarboxylic acid containing 80 gram-mol or more of terephthalic acid with diol component containing 80 gram-mol or more of ethylene glycol. Barrier layer contains the mix of polyamide (B) and polyamide (C). Polyamide (B) is produced by polycondensation of diamine component containing 70% gram-mol or more of m-xylylenediamine with dicarboxylic acid containing 70 gram-mol or more of α,ω-linear aliphatic dibasic acid with C4-C20. Polyamide (C) consists of poly(6-aminocaproic acid) and/or poly(hexamethylene diamine of adipinic acid), and amorphous semi-aromatic - copolymer of hexamethylene isophthalamide/hexametgyleneamide of terephthalic acid.

EFFECT: stronger interlayer adhesion, higher resistance to lamination, good gas tightness.

12 cl, 2 tbl, 8 ex

 

Technical area

The present invention relates to a technology of preventing delamination of the multilayer bottle having an improved property of the gas barrier, and particularly to a multilayer bottles, which protect against the appearance of stratification, even if they are exposed to a blow during the filling of the contents during transport or when dropped by improving the interlaminar bonding strength between the inner layer or outer layer, and an intermediate layer formed between them, as well as not causing stratification and located between these layers, without the need of education of the bottle shape, with less heterogeneity and fewer kinks and bends, and have a lot of freedom for design work.

The level of technology

Currently, plastic containers (bottles etc), made mainly from polyesters, such as polyethylene terephthalate (PET), are widely used as containers for tea, fruit juices, carbonated drinks, etc. Among these plastic containers plastic bottles small increase in quantity from year to year. In General, as the size of the bottle is reduced, the surface area per unit volume of content tends to increase. Therefore, the retention period of the content in the bottle is lcah small size tends to decrease. In recent years, began to sell beer, which are exposed to oxygen and light, as well as hot tea, which are filled in plastic bottles. Thus, in accordance with the modern trend, the plastic containers were used in a broader application, therefore, it became necessary to plastic containers were further improved in respect of their properties to serve as a gas barrier against oxygen, carbon dioxide, etc.

To provide a plastic bottle having a good ability to be a gas barrier have been developed multilayer bottles, made of thermoplastic polyester resin, and resin, which is a gas barrier, mixed bottles, bottles with a protective coating made through the formation of carbon coatings deposited coating or a protective coating of resin on a single layer bottles, made of thermoplastic polyester resin, etc.

Were put into circulation multilayer bottles, for example, produced by the influence of three - or a five-layer preform (blank)obtained by injecting a thermoplastic polyester resin such as PET, for forming the inner and outer layers and a thermoplastic resin, which is a gas barrier, such as poly-m-xylylene diamide adipic acid (polyamide MXD), in the slot of the mold, for biaxial stretching and pneumaturia.

In addition, have been developed and applied in multilayer bottles resins having kislorodoprovoda functions, which are able to absorb oxygen inside the container and to prevent the penetration of oxygen into the container and outside. Kislorodoprovoda bottles, respectively, have the form of multilayer bottles, comprising a layer of a gas barrier, made of polyamide MXD6, which is mixed with the catalyst phase transition on the basis of metal from the viewpoint of the degree of absorption of oxygen, transparency, strength, ductility, etc.

The above-mentioned multilayer bottles used as containers for beer, tea, carbonated drinks, etc. because of their good ability to be a gas barrier. When multilayer bottles are used for this purpose, poured the contents can maintain good quality with increased shelf life. On the other hand, multilayer bottles tend to suffer from delamination between the different polymer layers, for example between the innermost or the outermost layer and the intermediate layer, resulting in significant damage to their commercial value.

In order to solve the aforementioned problems, there was disclosed a method of mixing the polyamide MXD6 with nylon 6 and nylon 6I/6T to PR is to prevent crystallization of the barrier layer in the multilayer bottle, to reduce the crystallization rate of the polyamide or convert the polyamide in recrystallizes polyamide, thereby improving the resistance to delamination of the bottle (see patent document 1). However, in this way to prevent crystallization of the polyamide MXD6 and consequently reduce the rate of crystallization in the mixture should be added a significant amount of nylon 6 and nylon 6I/6T, with a relatively weak ability to be a gas barriers in comparison with polyamide MXD6. As a consequence, the resulting multi-layer bottle was weak ability to be a gas barrier than the one which uses only the polyamide MXD6, and therefore she was unable to increase the shelf life of the contents therein to a sufficient limit. In addition, when you add a transition, on the basis of the metal catalyst in the polyamide, to compensate for weak ability to be a gas barrier, a problem arises, namely that the addition of catalyst causes an increase in cost. Also, even with the addition of the transition, based on the metal catalyst of the resulting multilayer bottle is not superior in its ability to serve as a barrier to carbon dioxide, and, consequently, is still unacceptable as a container for beer, carbonated soft drinks, etc. In the way, the description of the nom in the patent document 1, these polyamides must be mixed in molten form with each other using an extruder prior to extrusion of the bottle, which increases the cost of production.

Patent document 1: USP 2005/0009976A.

Disclosure of the invention

The aim of the present invention is to solve the above problems and providing a multilayer bottle having excellent ability to be a gas barrier, which is free from the occurrence of delamination after a fall or after exposure to shock, does not require the creation of special forms with fewer irregularities or fewer bends to slow stratification, has greater freedom in the choice of design and has low cost.

The result is a detailed, intensive studies on the resistance to delamination of multilayer bottles the present inventors have found that when forming the barrier layer, having a special composition, the barrier layer shows good plasticity and the resulting multilayer bottle has an improved strength of the interlayer connection and protected from the occurrence of delamination in the fall, etc. of the Present invention was made on the basis of the above data.

Thus, the present invention relates to a multilayer bottle, including internal is Ni and outer layers, made mainly of polyester (a) and at least one barrier layer, located between the inner and outer layers, with (I) the polyester (A) is a thermoplastic resin obtained by polymerization component, dicarboxylic acid containing 80 mol.% or more of terephthalic acid with valovym component containing 80 mol.% or more of ethylene glycol; and (II) the barrier layer comprises polyamide (B), obtained by polycondensation diamino component containing 70 mol.% or more m-xylylenediamine component dicarboxylic acid containing 70 mol.% or more α,ω-linear aliphatic dibasic acid having from 4 to 20 carbon atoms, and the polyamide (C)having a high content of absorbed water than the polyamide (C), measured at 23°C and 50% relative humidity at 1 ATM, and the content of the polyamide (C) in the barrier layer is 20% by weight or less based on the weight of the barrier layer.

The best option of carrying out the invention

Thermoplastic resin of ester used to produce the outer layer, inner layer and optionally an intermediate layer in a multilayer bottle, in accordance with the present invention is a polyester resin (hereinafter simply as "polyester"), which is obtained by polymerization of the component dicarboxylic acid, sod is rasego terephthalic acid in the amount of 80 mol.% or more, preferably 90 mol.% or more (including 100 mol.%), with valovym 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, because the polyethylene terephthalate component, excellent in everything: light transmission, mechanical strength, processability introduction of substances and oriented moulding.

Examples of dicarboxylic acids other than terephthalic acid which may be contained in a component of dicarboxylic acids include isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,-4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, adipic acid, sabotinova acid, decane-1,10-dicarboxylic acid and Aldrin terephthalic acid. Examples of other diols than ethylene glycol, which may be contained in the diol component include propylene glycol, 1,4-butanediol, neopentylglycol, diethylene glycol, cyclohexane of dimethanol, 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxy ethoxyphenyl)propane. Next, hydroxy acids such as p-oxybenzone acid, can also be used as the raw monomer of the complex of the polyester (A).

The polyester (A) preferably has a characteristic elm is awn from 0.55 to 1.30 DL/g or more, preferably from 0.65 to 1.20 DL/g When the polyester (A) has a characteristic viscosity of 0.55 DL/g or more, you can produce not only translucent, amorphous, multi-layered pre-harvest, but also a multilayer bottle having a satisfactory mechanical strength. The polyester (A)having a characteristic viscosity of 1.30 DL/g or less, free from deterioration in a liquid state before pressing, resulting in a lightweight manufacture of multilayer bottles.

Further, the polyester (A), which is mainly formed of inner and outer layers of multilayer bottles, can also be smashin with other thermoplastic resins or various additives, while the introduction of these additives will not affect the intended effect of the present invention. The inner or the outer layer preferably contains a polyester (A) in an amount of 90% by weight or more (inclusive of 100% by weight). Examples of other thermoplastic resins include thermoplastic polyester resin such as polyethylene-2,6-naphthalenyloxy, resin-based polyolefins, polycarbonates, polyacrylonitrile, polyvinyl chloride and polystyrene. Examples of additives include absorbers of ultraviolet rays, oxygen scavengers, colorants and absorbers of infrared rays (supplements to re is agrimonia) for faster pre-heating the workpiece and reduce the period of time of pressing.

The rate of passage of oxygen (BTS) through the barrier layer obtained in the multilayer bottle of the present invention, measured at 23°C and relative humidity (0V) 60%, preferably 0.15 cm3×mm/(m2×day×bar) or less, more preferably of 0.12 cm3×mm/(m2×day×bar) or less, more preferably 0.10 cm3×mm/(m2×day×bar) or less, further still more preferably of 0.08 cm3×mm/(m2×day×bar) or less on average. As the barrier layer used in the present invention, has the ability to act as a barrier to oxygen, the obtained multilayer bottle demonstrates a good ability to be a gas barrier and can increase the shelf life of content that is stored in them.

The barrier layer obtained multilayer bottle, in accordance with the present invention, contains at least the polyamide (b) and the polyamide (C). The polyamide (C) is obtained by polycondensation diamino component containing 70 mol.% or more (inclusive of 100 mol.%) m-xylylenediamine component dicarboxylic acid containing 70 mol.% or more (inclusive of 100 mol.%) α,ω-linear aliphatic dibasic acid having from 4 to 20 carbon atoms. The polyamide (C) has a higher concentration of water than the polyamide (C), measured at 3°C and 50% relative humidity at 1 ATM.

Usually polyamides demonstrate the ability to absorb water. The content of absorbed polyamides water varies depending on the type of resin. In addition, the polyamides experience a change in various properties, such as increased softness on the basis of absorption of water. Thus, the polyamide (b) also becomes soft after absorption of water. When the polyamide (B)used for forming the barrier layer in a multilayer bottle, has absorbed a lot of water, the resultant multilayer bottle will exhibit good resistance to delamination. However, as the polyamide (B) has a low content of absorbed water, low rate of water absorption compared to other polyamides, obtained the barrier layer in the multilayer bottle tends to show insufficient absorption of water and weak resistance to delamination.

On the other hand, the use of polyamide MXD6 having a higher degree of water absorption than the polyamide (B), when the pressing of the multilayer bottle to increase the water absorption of the polyamide (C) in the bottle, the absorbed water has a tendency to foam due to the heat introduced during the pressing process, resulting in the low commercial value of the resulting multilayer bottles. For this reason, polyami the (In) usually dried until until the water content is reduced to approximately several hundred parts per million or less, in order to prevent foaming of the polyamide after pressing.

Thus, it was found that by mixing the polyamide (C) polyamide (S), with a higher content of water uptake than that of the polyamide (C), the resulting barrier layer improved the water absorption after pressing multilayer bottles and superior softness and durability interlayer connection, allowing, thus, the multilayer bottle to demonstrate good resistance to delamination.

In the present invention, the content of absorbed water by the polyamide (b) and the polyamide (C) was measured at 23°C and 50%humidity at 1 ATM in the following way.

(1) single-layer film made of polyamide or the polyamide (C), devuono was extended from 8 to 18 times the ratio of the areas (without curing when heated).

(2) the resulting stretched film was stored at 23°C and 50% humidity at 1 ATM over 4 weeks.

(3) the water Content of the stretched film after storage was measured by the method of Karl Fischer at 235°C for 30 minutes, and the thus obtained value was defined as the water content of the polyamide.

The content of absorbed water in the polyamide (B), measured at 23°C and 50% relative humidity at 1 ATM, is predpochtitel is about 2.5 to 5% by weight, and more preferably from 3 to 4% by weight, while the content of absorbed water in the polyamide (C), measured at 23°C and 50% relative humidity at 1 ATM is preferably from 3 to 13% by weight, and more preferably from 3.5 to 11% by weight. When the content of absorbed water in the polyamide (C) is higher than in the polyamide (B), and it is within the previously determined range, the water goes from polyamide (C) in the polyamide (b), the polyamide (B) becomes soft. As a result, when applied to the bottle effect, the barrier layer has a good following ability to influence internal and external layers, resulting in excellent resistance multilayer bottles to the bundle.

The polyamide (B)used in the present invention has a high ability to act as a barrier and demonstrates excellent ability, including two-component injection molding and extrusion when pneumotonometry, when molded under pressure together with the polyester (A) (preferably polyethylene terephthalate).

Diamino component used for production of the polyamide (B), includes m-xylylenediamine in an amount of 70 mol.% or more, preferably 75 mol.% or more, and more preferably from 80 mol.% or more (including 100 mol.%). When the content of m-xylylenediamine in the diamino component is less than 70 mo is.%, the obtained polyamide (C) has a tendency to deterioration of its ability to serve as a gas barrier. Examples other than m-xylylenediamine, diamines, which can be used in a diamino component include, but are not limited to, aliphatic diamines, such as tetramethylaniline, pentamethylene, 2-methylpentylamine, hexamethylenediamine were, heptamethylnonane, octamethylene, monomethylaniline, decamethylenediamine, documentrenderer, 2,2,4-trimethylhexamethylenediamine 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 diamines containing aromatic ring, such as bis(4-AMINOPHENYL)ether, p-phenylenediamine, p-xylylenediamine and bis(aminomethyl)naphthalene.

Component of dicarboxylic acid used for the production of polyamide (B)contain α,ω-linear aliphatic dicarboxylic acid having from 4 to 20 carbon atoms in the amount of 70 mol.% or more, preferably 75 mol.% or more and more preferably 80 mol.% or more (inclusive of 100 mol.%). When the content of α,ω-linear aliphatic dicarboxylic acid component decarbonisation lies within the previously determined range, the resulting polyamide (B) demonstrates an excellent capacity of the gas barrier and formability. Examples of α,ω-linear aliphatic dicarboxylic acid having from 4 to 20 carbon atoms, which can be used in the present invention include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, Emelyanova acid, cork acid, azelaic acid, adipic acid, sabotinova acid, undestandably acid and dodecadienol acid. Among these α,ω-linear aliphatic dicarboxylic acids are preferred is adipic acid.

In the present invention, the aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid, can also be added, as the dicarboxylic acid, with the exception of α,ω-linear aliphatic dicarboxylic acid. The amount of aromatic dicarboxylic acid, if it is added, will be preferably from 0.5 to 30 mol.% on the basis of component dicarboxylic acid. Next, a small amount of molecular weight regulator, such as monoamines and monocarboxylic acids, can also be added after the polycondensation for producing the polyamide. Component of dicarboxylic acid used in the present invented and, preferably contains from 100 to 70 mol.% α,ω-linear aliphatic dicarboxylic acid having from 4 to 20 carbon atoms and not less than 0, but less than 30 mol.% other aromatic dicarboxylic acids.

The polyamide (A) can be produced by melt polycondensation. For example, the polyamide (B) may be produced by heating nylon salt obtained from m-xylylenediamine and adipic acid under pressure, in the presence of water, and polymerization of the salt in the molten state, despite the removal of the added water, and the condensed water obtained. Alternatively, the polyamide (B) may be obtained according to the method of directly adding the m-xylylenediamine to adipic acid in the molten state, to expose these substances polycondensation under normal pressure. In the latter method, the polycondensation, in order to keep the reaction system in a uniform liquid state, m-xylylenediamine continuously added to the adipic acid, and a polycondensation reaction begins as heating the reaction system to a temperature not lower than the melting point of the obtained oligoimide and polyamide.

The polyamide (B), obtained by the method of melt polycondensation, then may be subjected to polymerization in the solid state. The production method of polyamide (C) is e especially limited to the above method, and the polyamide (B) may be made using traditionally known methods and conditions of polymerization.

Srednetsenovoj molecular weight of the polyamide (b) is preferably from 18000 to 43500 and more preferably from 20000 to 30000. When srednetsenovoj molecular weight of the polyamide (C) is within a previously determined range, the ductility of the polymer material, after receiving multilayer bottles, superior, and the resulting multilayer bottle shows excellent resistance to delamination. Meanwhile, the polyamide (B)having srednetsenovoj molecular weight from 18000 to 43500, demonstrates the relative viscosity of from about 2.3 to about 4.2, and the polyamide (B)having srednetsenovoj molecular weight of from 20,000 to 30,000, demonstrates the relative viscosity of from about 2,44 to about 3,19. The relative viscosity used herein means the value obtained by measuring the viscosity of a solution prepared by dissolving 1 g of polyamide in 100 ml of 96% sulfuric acid at 25°C. using a viscometer cannon-Fenske etc.

The polyamide (C)used in the present invention, preferably prepared from aliphatic polyamide and/or amorphous polyaromatics polyamide, due to the high content of absorbed water of these polyamides. As described above, it is important that the water content, my absorption is Noah aliphatic polyamide and amorphous polyaromatics polyamide, used as the polyamide (C) in the present invention is accordingly higher than that of the polyamide (B).

Examples of aliphatic polyamide (polyamide (C1)) include homopolymers such as poly(6-amino hexanoic acid)(PA-6), also known as poly(caprolactam), poly(hexamethylene diamide adipic acid)(PA-6,6), poly(7-lineamenta acid)(PA-7), poly(10-amino Caprylic acid)(PA-10), poly(11-amino undecisive acid)(PA-11), poly(hexamethylene amide sabatinovka acid)(PA-6,10), poly(hexamethylene amide azelaic acid)(PA-6,9) and poly(tetramethylene diamid adipic acid)(PA-4,6); and copolymers such as a copolymer of caprolactam/hexamethylene diamide adipic acid (PA-6,6/6) and the copolymer hexamethylen diamid adipic acid/caprolactam (PA-6/6,6). Among these aliphatic polyamides are preferred PA-6 and PA-6,6. Srednetsenovoj molecular weight of the polyamide (C1) is preferably from 10000 to 30000, and more preferably from 12500 to 25000.

Examples of amorphous polyaromatics polyamide (polyamide(C2)include poly(hexamethylene isophthalamide)(PA-6I), the copolymer of hexamethylene isophthalamide/hexamethylene phthalamide (PA-6I/6T), poly(m-xylylenediamine)(PA-MXDI), a copolymer of caprolactam/m-xylylenediamine(RA-6/MXDI) and a copolymer of caprolactam/hexamethylenediamine(RA-6/6I). Among these amorphous haloaromatic polyamides particularly preferred is PA-6I/6T. Srednetsenovoj molecular weight of the polyamide (C2) is preferably from 5,000 to 40,000, and more preferably from 10000 to 30000.

Polyamide (C1) and polyamides (C2), respectively, are used separately or in combination of any two of them or more. Adding only polyamide (C1) to the polyamide (B) the resulting polyamide mixture has a tendency from time to time to demonstrate a high crystallization rate, depending on the type and amount of added polyamide (C1), resulting in difficulty in forming the bottle. Conversely, adding only polyamide (C2) to the polyamide (B) the resulting polyamide mixture has a tendency to demonstrate from time to time, a low crystallization rate, depending on the type and amount of added polyamide (C1), resulting in difficulty in forming the bottle. Because of this, in some cases, polyamide (C1) and polyamide (C2) are preferably used in combination as the polyamide (C).

The rate of water absorption of the polyamide (C) (polyamide (C1) and polyamide (C2)) is preferably higher than the polyamide (B). In the present invention the rate of water absorption was measured at 23°C and 50% relative humidity at 1 ATM in the following way.

(1) Pellets of polyamide, pre-dried, stored at 23°C and 50% relative humidity at 1 ATM within 24 hours.

(2) the Amount of water in the granules before and after storage was measured by the method of Karl Fischer at 235°C for 30 minutes. The difference between the amount of water in the granules, measured before and after storage to absorb them in water, divided the T1/2(T:retention time=24 hours), and the calculated value was defined as the rate of water absorption of the polyamide.

Meanwhile, the reason for dividing the difference between the amount of water for T1/2is that because the absorption rate immediately after the start of water absorption gradually decreases and changes every moment, the rate of water absorption shall be the average, to avoid adverse effects. However, the value obtained by dividing the difference between the quantity of water for T1/2and on T, essentially has the same meaning as the above-mentioned value, although both values are different from each other.

The rate of water absorption of the polyamide (C), measured at 23°C, 50%relative humidity at 1 ATM, is preferably from 100 to 500 parts per million/hour-1and more preferably from 150 to 400 ppm/h-1.

While the rate of water absorption of the polyamide (C), measured at 23°C and 50%relative humidity at 1 ATM is preferably from 250 to 1500 ppm/h-1more PR is doctitle from 300 to 1300 ppm/h -1and still more preferably from 500 to 1200 ppm/h-1. When the rate of water absorption of the polyamide (C) is within a previously determined range, the water polyamide quickly absorbed and after pneumaturia bottle immediately transferred to the polyamide (b), the polyamide (B) becomes soft. As a result, the barrier layer demonstrates a good ability to follow inner and outer layers, when a force is applied to the bottle, to deliver excellent resistance to delamination of the multilayer bottle.

The method of mixing the polyamide (C) polyamide (C) is not restricted especially. The polyamide (b) and the polyamide (C) can be shoesmelanie with each other after harvesting of the bottle. Alternatively, the polyamide (b) and the polyamide (C) can be mixed with each other in the melt, using a single screw extruder, twin screw extruder, etc. to prepare preforms bottles, or can be mixed with each other in the melt to prepare the uterine mixture of these resins. However, since the preparation is simply mixed in the melt mixture is costly, bearing in mind the difficult procedure of preparation of the mixture, to prepare masterbatches it is preferable to use a dry mixing method or a method of mixing in the melt with the purpose of the floor is ready to be placed mixtures of these polyamides inexpensive way.

In the present invention, the content of the polyamide (C) in the barrier layer is 20% by weight or less, preferably from 1 to 20% by weight, more preferably from 1.5 to 15% by weight and still more preferably from 2 to 10% by weight, based on the weight of the barrier layer. When the content of the polyamide (C) in the barrier layer is within a previously specified range, the ductility of the polymer material after production of the multilayer bottle is increased, and the resulting multilayer bottle demonstrates excellent resistance to delamination, and a good ability to serve as a gas barrier.

Preferably, the barrier layer is made mainly of polyamide (B). From the point of view of the ability to serve as a good barrier, the content of the polyamide (C) in the barrier layer is preferably 70% by weight or more, more preferably 80% by weight or more, yet more preferably 90% by weight or more (upper limit: 99% by weight, respectively). Depending on the type of resin or the like, is added to the polyamide (B), if the tar or similar barrier layer is more than 30% by weight, the previously mentioned speed of oxygen (BTS) through the barrier layer tends to be higher than 0.15 cm3×mm/(m2×day×bar), resulting in a deterioration of the ability to act as a barrier.

When aliphatic shall oleamide (polyamide (C1)) and amorphous poliaromaticheskikh polyamide (polyamide (C2)) are used in combination, polyamide (C2) is preferably used in an amount of from 0.25 to 4 parts by weight, more preferably from 0.35 to 2.9 parts by weight, yet more preferably from 0.45 to 2.2 parts by weight to 1 part by weight of polyamide (C1). When the number of these used polyamides are within the previously set range, the molding of the bottle is held in a lightweight manner, and receiving in the bottle has significantly improved resistance to delamination without compromising the ability to act as a barrier.

The barrier layer may also contain one or many other kinds of resins, such as polyesters, olefins, proximally, while the addition of these resins will not adversely affect the target effect of the present invention. In addition, the barrier layer may also contain various additives. Examples of additives include inorganic fillers such as glass and carbon fibers; sheet-like inorganic particles such as glass flakes, talc, kaolin, mica, bentonite, and organic clay; converters impacts, such as various elastic resin; nucleating agents; lubricants such as fatty compounds with amide and compounds based on metal salts and fatty acids; antioxidants, such as copper compounds, organic or inorganic halogenated the passed connection phenolpropionate unrelated compounds, gray - and phosphorus-containing compounds; depletability; decolorizing agents; ultraviolet radiation absorbents, such as compounds based on benzotriazole; release lubricant; plasticizing agents; dyes; flame retardant additive; kislorodoprovoda agents, such as cobalt containing compounds; and protivoleprosnami agents, such as alkali compounds.

The multilayer bottle of the present invention may have areas with low elongation (from 1 to 2.5 times), depending on the shape of the preform or bottle. Part having a low elongation at break, have a tendency to lighten after absorption of water. The polyamide (C), mixed with the polyamide (S), with a higher content of water uptake than that of the polyamide (B), shows increased absorption of water. Therefore, if necessary, a barrier layer can be added agents, preventing whitening, to prevent whitening of the barrier layer, thereby enabling to produce a multilayer bottle having good transparency.

Agent, preventing whitening, made from a metal salt and an aliphatic acid having from 18 to 50 carbon atoms and preferably from 18 to 34 carbon atoms. It is expected that the salt of the metal and Alif the political acids, having 18 or more carbon atoms, show good preventing the whitening effect, because metal salt and an aliphatic acid having 50 or less carbon atoms, uniformly dispersed in the barrier layer. Aliphatic acid may be branched or may be a double bond. Examples of preferred aliphatic acids include straight saturated aliphatic acids such as stearic acid (C18), arachnid acid (C20), Bekenova acid (C22), montanoa acid (s) and medicinova acid (C30). Examples of metals that can form a salt with these aliphatic acids include, but are not limited to these metals, sodium, potassium, lithium, calcium, barium, magnesium, strontium, aluminum, and zinc. Preferred of these metals are sodium, potassium, lithium, calcium, aluminum and zinc.

Metal salts and aliphatic acids may be used singly or in combination of any two or more of them. Also in the present invention the particle size and metal salts of aliphatic acids is not particularly limited to, metal salts and aliphatic acids preferably have a particle size of 0.2 mm or less, because such small particles easily and uniformly dispersed in the barrier layer.

The amount of added metal salt and an aliphatic acid, preferably about what is 0.005 to 1.0 part by weight, more preferably from 0.05 to 0.5 parts by weight, yet more preferably from 0.12 to 0.5 parts by weight based on 100 parts by weight of the total amount of the barrier layer. When the amount of metal salt and an aliphatic acid, is added to the barrier layer, are 0.005 parts by weight or more based on 100 parts by weight of the total amount of the barrier layer, it is expected that the barrier layer will show good against clenched effect. When the amount of metal salt and an aliphatic acid, is added to the barrier layer, will amount to 1.0 part by weight or less based on 100 parts by weight of the total amount of the barrier layer, the resultant multilayer bottle retains a slight turbidity.

Alternatively, a compound selected from the group consisting of the following diamedix compounds and ether compounds dibasic acid may be added as preventing the whitening agent instead of the above-mentioned metal salt and an aliphatic acid. Diamine compounds and compounds of the ester of the dibasic acid can be added separately or in the form of a mixture of any two or more, or one or more diamedix compounds may be used in combination with one or more connection ester of the dibasic acid.

Diamine compounds can be obtained by the reaction of aliphatic to the slots, having from 8 to 30 carbon atoms, with a diamine having from 2 to 10 carbon atoms. It is expected that diamidine compounds derived from aliphatic acid having 8 or more carbon atoms and a diamine having 2 or more carbon atoms, show good preventing the whitening effect, because 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. Preferred of these aliphatic acids are linear, saturated aliphatic acid.

Examples of the component aliphatic acid diamedix compounds include stearic acid (18), arachnid acid (C20), beenbuy acid (C22), montanabuy acid (s) and melissinos acid (C30). Examples of the diamino component diamedix compounds include Ethylenediamine, butylenediamine, hexanediamine, xylylenediamine and bis(aminomethyl)cyclohexane. In the present invention diamidine compounds derived from the combination of these components can be respectively used. Of these diamedix compounds are preferred diamine compounds derived from aliphatic acids having from 8 to 30 carbon atoms, and dia is on, mainly consisting of ethylene diamine, and diamine compounds derived from aliphatic acids, consisting mainly of montenovo acid, and a diamine having from 2 to 10 carbon atoms.

Compounds of the ester of the dibasic acid 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 expected that the compounds of the ester of the dibasic acid derived from an aliphatic acid having 8 or more carbon atoms, and a diol having 2 or more carbon atoms, show good preventing the whitening effect, because the connections ester of the dibasic acid derived from aliphatic acids having 30 or less carbon atoms, and a diol having 10 or less carbon atoms uniformly disperse into the barrier layer. Aliphatic acids may be branched or may have a double bond. Preferred of these aliphatic acids are linear, saturated aliphatic acid.

Examples of the component aliphatic acid compounds of the ester of the dibasic acid include stearic acid (18), arachnid acid (C20), beenbuy acid (C22), montanabuy acid (s) and melissinos acid (C30). Examples delovogo component compounds of the ester of the dibasic acid include ethyl shall glycol, propandiol, butanediol, hexanediol, xylylene glycol, and cyclohexane of dimethanol. In the present invention compounds of the ester of the dibasic acid derived from combinations of these components can be respectively used. Of these compounds ester of the dibasic acid are preferred compounds of the ester of the dibasic acid derived from aliphatic acids, consisting mainly of montenovo acid and diol, consisting mainly of ethylene glycol and/or 1,3-butanediol.

The number dumenigo connection and/or connection added ether dibasic acid is preferably 0.005 to 1.0 part by weight, more preferably from 0.05 to 0.5 parts by weight, yet more preferably from 0.12 to 0.5 parts by weight based on 100 parts by weight of the total amount of the barrier layer. When the number dumenigo connection and/or connection added ester of the dibasic acid to the barrier layer is 0.0005 parts by weight or more based on 100 parts by weight of the total amount of the barrier layer, it is expected that the barrier layer will show good, preventing the whitening effect. When the number dumenigo connection and/or added to the barrier layer connection ester of the dibasic acid is 1.0 part by weight or less based on 100 parts by weight of BEGO the number of the barrier layer, the resulting multilayer bottle retains a slight turbidity.

Preventing the whitening agent may be added to the polyamide (barrier layer) is traditionally known method of mixing. For example, pellets of the polyamide resin and preventing the whitening agent can be loaded into the blank, rotating the container and mixed it together. Alternatively, it may be selected such method, in which after obtaining the composition of a polyamide resin containing a high concentration of preventing the whitening agent, the thus obtained resin composition is diluted with pellets of polyamide resins that do not contain interfering whitening agent, to prepare a resin composition having a predetermined concentration of preventing whitening agent, followed by mixing in the melt obtained is diluted composition; or a method in which after mixing in the melt, the resulting resin composition is formed by sequentially pouring of the material into the mold under pressure injection etc.

When using preventing the whitening agent barrier layer can be protected from the appearance clenched immediately after fabrication of multilayer bottles. Further, even after storage for a long period of time under conditions that are free from pobel the tion, or at a very low whitening of the barrier layer may also be protected from clenched. More specifically, even when the multilayer bottle, which was preserved for a long period of time under such conditions, in which the bottle was free from clenched or barely been whitening, even without adding preventing the whitening agent, for example, at a temperature of 23°C and 50% relative humidity were exposed to high humidity, caused by contact with water, or boiling water, or has been heated to a temperature higher than the transition temperature in the glassy state of the resin, the appearance clenched in her suppressed in the same way as immediately after molding.

In the present invention an antistatic agent may be added in an amount of from 1 to 1000 parts per million to a stirred mixture of the polyamide (b) and the polyamide (C). When the polyamide (b) and the polyamide (C) is dry blended together, they tend to be divided or separated from each other due to the static electricity produced depending on the surrounding conditions, when the difference between the dielectric constants. As a result, the obtained molded product tends to degrade its properties due to changes in mixing ratios between portions of the component is in, thereby allowing to obtain a molded bottle having the expected properties. Thus, with the addition of an antistatic agent to the barrier layer of polyamide (b) and the polyamide (C) is uniformly mixed with each other, thereby providing the possibility of producing a multilayer bottle having good properties.

In the present invention can be used known antistatic agents, such as nonionic surfactants, anionic surfactants and cationic surfactants. Examples of nonionic surfactants include surfactants polyethyleneglycol class of esters, class diethyl ether or class of alkylphenol, a surfactant based on a polyhydric alcohol and partially of ester class sorbitnogo of the air; they do not have any restrictions. In the present invention among these surfactants preferably used polyoxyethylene sorbitan monolaurate as one of the surface-active substances, based on the ester alkoxylate class polyoxyethylene sorbitan of ester, because of their excellent antistatic effect with the polyamide (b) and the polyamide (C).

Antistatic agents can be used alone or in combination of any two and the and more. The added amount of the antistatic agent is preferably from 1 to 1000 ppm, more preferably from 10 to 500 ppm, and still more preferably from 20 to 100 parts per million based on the total amount of the barrier layer. When the added amount of the antistatic agent is within the previously set range, the polyamide (b) and the polyamide (C) is uniformly mixed with each other, thereby producing a bottle having a stable quality.

The multilayer bottle of the present invention can be produced in accordance with the following technology. I.e. using an injection molding machine equipped with two injection cylinders, the polyester (a) and the mixture of the polyamide (b) and the polyamide (C) injected from the hydraulic cylinder of the outer injection and hydraulic cylinder of the internal injection respectively in a metal mold cavity through the corresponding metal hot sprue, to obtain a multilayer preform, and then the obtained multilayer preform to send blanvalet the moulding traditionally known method, to obtain a multilayer bottle.

Typically, multi-layer preform can be blow molded traditionally known means, such as the so-called method of cold zag is training for blowing and the so-called method of hot billet to blow. 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°C multilayer preform is stretched in the axial direction by mechanical means, such as pivot pin of the mold, and then the high pressure air usually creates excessive pressure from 2 to 4 MPa and injected into the multilayer preform to expose the workpiece to the stretching and moulding in the longitudinal direction, or a method in which after crystallization part of a multilayer preform neck finish and heat the surface of the multilayer preform to a temperature of from 80 to 120°C multilayer preform is subjected to moulding in a metal mold heated to a temperature of from 90 to 150°C.

In the present invention, the heating temperature of the preform is preferably from 90 to 110°C and more preferably from 95 to 108°C. When the heating temperature of the preform is lower than 90°C, the barrier layer or the polyester (A) may be subjected to cold stretching and whitening due to insufficient heating. When the heating temperature of the preform is higher than 110°C, the barrier layer may deteriorate from crystallization, and then the resultant multilayer bottle may deteriorate the resistance to delamination.

From the point of view of the improved ability to serve what arera and plasticity of the multilayer bottle of the present invention preferably has a three-layer structure, built sequentially from the layer of polyester (A), the barrier layer and the layer of polyester (A), or five-layer structure constructed sequentially from the layer of polyester (A), a barrier layer, a layer of polyester (A), the barrier layer and the layer of polyester (A).

Multilayer bottle having a three-layer or five-layer structure can be produced from a multilayer preform having a proper sandwich or the corresponding five-layer structure in the biaxial stretching and blow molding traditionally known ways. Method of manufacturing a multilayer preform having a three-layer or five-layer structure is not restricted especially, and this can be used in any convenient traditionally known methods. For example, the polyester (A), forming the inner and outer layers in a multilayer preform, first injected from the hydraulic cylinder of the outer injection molding machines. Then, the resin material forming the barrier layer, and the polyester (A) injected simultaneously from the hydraulic cylinder of the internal injection and hydraulic cylinder outer injection, respectively, and then the required amount of the polyester (A) is injected from the hydraulic cylinder of the outer injection to fill the cavity of the metal mold, thereby producing a multilayer the reform having a three-layer structure constructed sequentially from the layer of polyester (A), the barrier layer and the layer of polyester (A).

The polyester (A) is first injected from the hydraulic cylinder of the outer injection molding machine, and then the resin material forming exclusively the barrier layer, is injected from the hydraulic cylinder of the internal injection in conclusion, a polyester (A) is injected from the hydraulic cylinder of the outer injection to fill the cavity of the metal mold, thereby producing a multilayer preform having a five-layer structure constructed sequentially from the layer of polyester (A), a barrier layer, a layer of polyester (A), the barrier layer and the layer of polyester (A).

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

The thickness of the layer of polyester (A) 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 μm). The thickness of the multilayer bottle is not necessarily constant along its entire length and is typically in the range from 0.2 to 1.0 mm

In the multilayer bottle obtained by biaxial stretching and blow molding a multilayer preform, the barrier layer may be provided in the cylindrical part of the multilayer bottle, with the goal of d is to be the possibility of the bottle to show the ability to serve as a good gas barrier. However, when the barrier layer continues until the end of the bottle mouth, the ability of multilayer bottles to serve as a gas barrier can be further strengthened.

The weight percent of the barrier layer in the multilayer bottle of the present invention is preferably from 1 to 20% by weight, more preferably from 2 to 15% by weight and still more preferably from 3 to 10% by weight based on the total weight of the multilayer bottle. When the weight percent of the barrier layer is within a previously defined range, the resulting multilayer bottle demonstrates a good ability to serve as a gas barrier multilayer preform as the previous product is easily formed in the multilayer bottle.

In the present invention, the multilayer preform is particularly preferably made by filing in the injection molding machine shomisani mixture of the polyamide (b) and the polyamide (C). When using such shomisani mixture can avoid an increase in cost required for preparing the molten mixture; thus, the bottle is made inexpensive way. The polyamide (b) and the polyamide (C) in the molten mixture also have a tendency to quality degradation due to excessive heat, depending on the applied conditions, resulting in the difficult manufacture of the preforms when p is constant stable conditions, or yellowing of the polyamide. When the dry mixing of the polyamide (C) polyamide (C) is also preferred additive to him antistatic agent.

In addition, the connection of phosphorus is preferably added to the polyamide (b) and/or polyamide (C) to improve the stability of the processing after formation of the melt or to prevent unwanted staining polyamides. Examples of the phosphorus compounds include phosphorus compounds containing alkaline or alkaline earth metals. Specific examples of phosphorus compounds used in the present invention include phosphates, hypophosphites and phosphites alkaline or alkaline earth metals such as sodium, magnesium and calcium. Among these phosphorus compounds are preferred hypophosphite alkaline or alkaline earth metals, because they are particularly excellent effect of preventing unwanted staining. The concentration of phosphorus compounds in the polyamide (b) and/or the polyamide (C) is preferably from 1 to 500 ppm, more preferably 350 ppm or less, and still more preferably 200 ppm or less in terms of phosphorus atom. Even when the concentration of added phosphorus atoms exceeds 500 ppm, the effect of preventing coloration no longer improves, and most likely, the resulting film has a tendency of becoming who I am worse than from increased turbidity.

The multilayer bottle of the present invention are protected from the appearance of stratification, even when dropped or exposed to it. Also, unlike the conventional multi-layer bottles, multilayer bottle of the present invention is improved in the resistance to delamination without compromising the barrier properties. In addition, the multilayer bottle has a large degree of freedom for design work without restriction to the particular forms with fewer imperfections or fewer bends because of the emergence of stratification, even when the bottle of this form has imperfections or bends. The multilayer bottle of the present invention, respectively, is used for storage and protection in various products. Examples of products that are stored and kept in the multilayer bottle, include liquid beverages, such as sodas, juice, water, milk, whiskey, coffee, tea, jelly and healthy drinks, seasonal condiments, such as liquid seasonal condiments, sauces, soy sauce, side dishes, soup, liquid prepared foods, such as soup, liquid medicines, cosmetic products, such as detergents, milk lotions and styling products hair care products hair care products, such as dyes for hair and shampoos etc.

Examples

The present image is the buy will be described in more detail with reference to the following examples and comparative examples. However, these examples are only illustrative and do not limit the invention. Meanwhile, various properties of the multilayer bottle was evaluated by the following methods.

(1) the height of the separation.

The resistance to delamination of the multilayer bottle was evaluated by measuring the height of the separation, subjecting the container to test for impact resistance in accordance with ASTM D2463-95 Procedure B. the greater the height is recorded, the higher the resistance to delamination. Namely: first, a multilayer container, which was to be tested was filled with water, closed and abandoned, to visually observe the appearance of any bundle. At this time, the multilayer container vertically falling, so that the lower part of the multilayer bottle hit the floor. Test the resistance of the blow was repeated, and at the same time, the drop height of the multilayer bottle was increased and decreased in the range of 15 centimeters. The number of trials multilayer bottles on the impact resistance was equal to 30.

(2) the Penetrating ability of the oxygen/air flow oxygen.

The penetrating ability of oxygen in a multi-layer bottle was measured at 23°C and a relative humidity of 100% for the inner part of the bottle and 50% relative humidity to the outside of the bottle in accordance with ASTM D3985. Measurement planicauda the ability of oxygen was carried out, using the measuring apparatus “OX-TRAN 2/61”available from Modern Controls Corp. Lower penetration ability of oxygen indicates a higher ability of the bottle to act as a barrier to oxygen. Meanwhile, on the basis of a measurement of the rate of passage of oxygen (BTS) through the barrier layer of the bottle the bottle was carefully subjected to phase separation to separate and take out only samples of the barrier layer, and the rate of passage of oxygen through the thus obtained barrier layer was measured at 60% relative humidity and 23°C. the Measurement of the speed of passage of oxygen was carried out using the measuring apparatus “OX-TRAN 2/61”available from Modern Controls Corp.

(3) the Ability to be a barrier for carbon monoxide (decrease CO2).

Bottle (500 ml) was filled with carbonated water containing carbon dioxide in the number 4 (gas volume, four-bottle capacity; normal conditions). Thus, the bottle was prepared at 23°C and 50% relative humidity for continuous measurement of time changes of the internal pressure in the bottle. As carbon dioxide inside the bottle over time penetrates through the wall of the bottle, the internal pressure in the bottle decreases over time. The property of the bottle to act as a barrier for carbon monoxide was about enano of the number of days which was the ultimate term of office, which will expire before the value of the initial internal pressure equal to 100%, will drop to 90%. A greater number of elapsed days indicates a higher ability of the bottle to serve as a barrier to carbon dioxide.

(4) the Content of absorbed water.

A stretched polyamide film (stretched 10 times in the ratio of squares) was kept at 23°C, 50% relative humidity and 1 ATM for more than 4 weeks, and the water content of the film after storage was measured by the method of Karl Fischer using “AQ-2000”available from Hiranuma Sangyo Co., Ltd. Measured thus is determined the content of absorbed water in the polyamide. Temperature measurement was 23°C and the measurement time was 30 minutes. In addition, the bottle was carefully subjected to phase separation to separate and take samples of the barrier layer, and the amount of absorbed barrier layer of water was measured in the same way that was described earlier.

Example 1

Under the following conditions raw polymeric materials were obtained by injection molding for the production of three-layer preform (27 g), successively created from a layer of polyester (A), barrier layer, and again a layer of polyester (A). After cooling, the resulting preform was heated and exposed to biaxial stretching and is formowaniu blown, and thus, the multilayer bottle.

The layer of polyester (A).

Polyethylene terephthalate “RT543C”, available from Nippon Unipet Co., Ltd.

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

The barrier layer.

The polyamide (B): poly-m-xylylene diamidino acid “MX Nylon S6007”, available from Mitsubishi Gas Chemical Co.,Inc., 95% by weight.

The polyamide (S): Nylon 6 “V”available from Ube Kosan Co., Ltd., 5% by weight.

When mixing resin 50 parts per million of polyoxyethylene sorbitan of monolaurate “NONION LT-221”, available from Nippon Oils &Fats Co., Ltd., was added as an antistatic agent, and the resulting mixture was dry mixed for 30 minutes using the rocker mechanism. After casting granules obtained for the production of preforms, neither sticking nor was glued to the wall surface of the feeder or separated due to the static electricity, and the resulting preform had a stable quality. The weight percent of the barrier layer was equal to 5% by weight based on the total weight of the resultant multilayer bottle. The results of the evaluation of the multilayer bottle is presented in table 1.

View of the three-layer preform.

Overall length: 95 mm; external diameter is: 22 mm; wall thickness: 4,2 mm

Three-layer preform was produced using a molding machine (model: “M200”; class four-point casting), available from Meiki Seisakusko Co., Ltd.

Conditions of molding a three-layer preforms.

The temperature of the hydraulic cylinder surface injection280°C
The temperature of the middle of the hydraulic cylinder of the internal injection250°C
The temperature of the mold280°C
The temperature of cooling water for the mold15°C
Content barrier resin in stocking5% by weight

Type multilayer bottles

Overall length: 223 mm; outer diameter: 65 mm; packaging: 500 ml; the bottom of the form: the form of champagne; no dents in the cylindrical part.

Biaxial stretching and blow molding was performed using a blow-molding machine (model: “EFB100ET”), available at Frontier Inc.

Conditions biaxial stretching and blow molding

The temperature of heating the billet 103°C
The pressure applied to the tension rod0.5 MPa
The pressure of the primary blast1.0 MPa
The pressure of the secondary blast2.5 MPa
The deceleration time primary blast0,35
Time primary blast0,28
The time of the secondary blast2,0
The time of termination blast0.6
The temperature of the mold30°C

Examples 2-5 and comparative examples 1-3

The same procedure as in example 1 was repeated except that the composition of the barrier layer was changed to the composition shown in table 1, and thus, the multilayer bottle. The evaluation results thus obtained multilayer bottle shown in table 1.

Acronyms are polyamides, are presented in table 1, as follows:

(1)S6007: poly-m-xylylene diamide adipic acid “MX Nylon S6007” (product of polymerization, which is in a solid when standing), available from Mitsubishi Gas Chemical Co., Inc.

Srednetsenovoj molecular weight23500
The relative viscosity2,70 (measured at 25°C in a solution prepared by dissolving 1 g of resin in 100 ml of 96% sulfuric acid; this is the same as is used in the following descriptions)
The content of absorbed water3,4% by weight
The rate of water absorption280 parts per million/hour1/2

(2)S6121: poly-m-xylylene diamide adipic acid “MX Nylon S6121” (product of polymerization, which is in a solid state), available from Mitsubishi Gas Chemical Co., Inc.

Srednetsenovoj molecular weight40000
The relative viscosity3,94
The content of absorbed water3,4% by weight
The rate of water absorption270 ppm/h1/2

(3)V: Nylon 6 Grade: 1015B”available from Ube Kosan Co., Ltd.

Srednetsenovoj molecular weight15000
The content of absorbed water7.1% weight
The rate of water absorption1090 ppm/h1/2

(4)V: Nylon 6 Grade: 1020B”available from Ube Kosan Co., Ltd.

Srednetsenovoj molecular weight20000
The content of absorbed water7.1% weight
The rate of water absorption1070 ppm/h1/2

(5)V: Nylon 66 Grade: 2020B”available from Ube Kosan Co., Ltd.

Srednetsenovoj molecular weight20000
The content of absorbed water6.3% weight
The rate of water absorption1000 ppm/h1/2

(6)X21F07: Nylon 6I/6T Grade: NOVAMID X21F07”, available from Mitsubishi Engineering Plastics CO., Ltd.

The content of absorbed water11% by weight
The rate of water absorption910 ppm/h1/2

(7)3024: Nylon I2 Grade: 3024NUX”available from Ube Kosan Co., Ltd.

The content of absorbed water1,2% by weight
The rate of water absorption100 ppm/h1/2

As shown previously, in the examples and comparative examples, the bottles obtained in accordance with the present invention, in which the barrier layer was composed of polyamides of different types, is able to provide the specific content of absorbed water, showed excellent resistance to delamination, and a good ability to serve as a gas barrier, while the bottles are not able to meet the requirements of the present invention, has worsened their resistance to delamination or its ability to serve as a gas barrier.

Table 1-1
Examples
1 2345
Polyamide ()S6007S6007S6007S6007S6121
The content of the barrier layer (wt.%)9585909090
The polyamide (C)
Aliphatic polyamideW-W1020BW
The content of the barrier layer (wt.%)5-6,754
Amorphous semi - aromatic polyamide-X21F07X21F07X21F07 X21F07
The content of the barrier layer (wt.%)-153,356
Height stratification (cm)250270319308310
The rate of passage of oxygen (BTS) through the barrier layer
(cm3×mm/(m2×day×bar)
0,060,080,070,070,06
The penetrating ability of the oxygen in the bottle (cm3/bottle×day×0,21 bar)0,0110,0130,0120,0120,011
The loss of CO2(day)120105115112119
The content of absorbed water in the barrier layer (wt.%)3,64,5 the 3.84,04,0

Table 1-2
Comparative examples
123
Polyamide ()S6007S6007S6007
The content of the barrier layer (wt.%)1005080
The polyamide (C)
Aliphatic polyamide1015B3024
The content of the barrier layer (wt.%)-4020
Amorphous poliaromaticheskikh polyamide-X21F07-
The content of the barrier layer (wt.%) -10-
Height stratification (cm)150302180
The rate of passage of oxygen (BTS) through the barrier layer (cm3×mm/(m2×day×bar)0,060,190,16
The penetrating ability of the oxygen in the bottle
(cm3/bottle×day×0,21×ATM)
0,0110,020,019
The loss of CO2(day)1206370
The content of absorbed water in the barrier layer (wt.%)3,45,63,0

Industrial applicability

In accordance with the present invention a multilayer bottle, independent of the shape and having an excellent property of the gas barrier is produced with low cost, since the bottle is essentially free from delamination. Thus, the present invention is significantly useful from the industrial point of view.

1. Many who ply the bottle, includes inner and outer layers, each made mainly of polyester (A), and at least one barrier layer between the inner and outer layers,
when the polyester (A) is a thermoplastic resin obtained by polymerization component, dicarboxylic acid containing 80 mol.% or more of terephthalic acid with valovym component containing 80 mol.% or more of ethylene glycol; and
the barrier layer contains
the polyamide (B), obtained by polycondensation diamino component containing 70 mol.% or more m-xylylenediamine component dicarboxylic acid containing 70 mol.% or more α,ω-linear aliphatic dibasic acid having from 4 to 20 carbon atoms, and
the polyamide (C), which is a combination of aliphatic polyamide consisting of poly(6-aminocaproic acid) and/or poly(hexamethylene diamide adipic acid), and amorphous polyaromatics polyamide consisting of the copolymer hexamethylen isophthalamide/hexamethylene terephthalic acid, and poliaromaticheskikh polyamide is contained in an amount of from 0.25 to 4 parts by weight to 1 part by weight of aliphatic polyamide
when the polyamide (C) has a high content of absorbed water than the polyamide (C), measured at 23°C and 50% relative humidity at 1 ATM, and the content of the polyamide (C) the barrier layer is 20% by weight or less, based on the weight of the barrier layer.

2. The multilayer bottle according to claim 1, in which the content of absorbed water by the polyamide (b) is from 2.5 to 5% by weight.

3. The multilayer bottle according to claim 1, in which the content of absorbed water by the polyamide (C) is from 3 to 13% by weight.

4. The multilayer bottle according to claim 1, in which the content of the polyamide (C) in the barrier layer is from 1 to 20% by weight based on the weight of the barrier layer.

5. The multilayer bottle according to claim 1, in which the barrier layer contains a metal salt and an aliphatic acid having from 18 to 50 carbon atoms in the amount of 0.005 to 1.0 part by weight based on 100 parts by weight of the total amount of the barrier layer.

6. The multilayer bottle according to claim 1, in which the barrier layer contains an antistatic agent in an amount of from 1 to 1000 parts per million.

7. The multilayer bottle according to claim 1, in which the polyamide (C) has srednetsenovoj molecular weight from 18000 to 43500.

8. The multilayer bottle according to claim 1, which has a three-layered structure sequentially including a layer of polyester (A), the barrier layer and the layer of polyester (A).

9. The multilayer bottle according to claim 1, which has a five-layered structure sequentially including a layer of polyester (A), the barrier layer, the layer of polyester (A), the barrier layer and the layer of polyester (A).

10. The multilayer bottle according to claim 1, in which the percentage of the weight of the barrier layer which is from 1 to 20% by weight based on the total weight of the multilayer bottle.

11. The multilayer bottle according to claim 1, in which the barrier layer is a layer obtained from shomisani mixture of the polyamide (b) and the polyamide (C).

12. A multilayer container comprising inner and outer layers, each made mainly of polyester (A), and at least one barrier layer between the inner and outer layers,
when the polyester (A) is a thermoplastic resin obtained by polymerization component, dicarboxylic acid containing 80 mol.% or more of terephthalic acid with valovym component containing 80 mol.% or more of ethylene glycol; and
the barrier layer contains
the polyamide (B), obtained by polycondensation diamino component containing 70 mol.% or more m-xylylenediamine component dicarboxylic acid containing 70 mol.% or more α,ω-linear aliphatic dibasic acid having from 4 to 20 carbon atoms, and
the polyamide (C), which is a combination of aliphatic polyamide consisting of poly(6-aminocaproic acid) and/or poly(hexamethylene diamide adipic acid), and amorphous polyaromatics polyamide consisting of the copolymer hexamethylen isophthalamide/hexamethylene terephthalic acid, and poliaromaticheskikh polyamide is contained in an amount of from 0.25 to 4 parts by weight to 1 part by weight of aliphatic polyamide
the ri that the polyamide (C) has a high content of absorbed water, than the polyamide (C), measured at 23°C and 50% relative humidity at 1 ATM, and the content of the polyamide (C) in the barrier layer is 20% by weight or less, based on the weight of the barrier layer.



 

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2 cl, 1 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: polymeric mixed composition is obtained through co-extrusion of polyamide in a melt with a modifying additive. The modifying additive is a mixture of polyethylene with a copolymer of ethylene with C3-8 olefin in ratio of components (pts. wt) between 1:9 and 9:1. Before co-extrusion in a melt with polyamide 6, the modifying additive undergoes reaction extrusion. 0.3-3 wt % polar monomer and 0.1-0.6 wt % organic peroxide are further added to the composition at the co-extrusion step at reaction extrusion temperature of 170-240°C and the following ratio of components in the polyamide composition, wt %: polyamide 6 - up to 100, modifying additive 15-45. Co-extrusion temperature 235-275°C.

EFFECT: invention reduces melt flow index of the molten mass, enables to obtain impact resistant and petroleum product-resistant polyamide materials and also simplifies technology of producing said materials.

4 cl, 2 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: polyamide can be obtained through polymerisation in the presence of at least: (i) monomers of dibasic carboxylic acids and diamines, or salts thereof; (ii) 0.05-0.5 mol % polyfunctional compound containing at least 3 functional groups XI, with respect to the total number of moles of monomers which form polyamide; (iii) 0.2-2 mol % monofunctional compound containing one functional group X2, with respect to the total number of moles of monomers which form polyamide. Functional groups X1 and X2 are functional groups of carboxylic acids or amine groups which can react with monomers of dibasic carboxylic acids and diamines (i) and form an amide bond. When the polyfunctional compound (ii) contains functional groups X1 of the carboxylic type, the monofunctional compound (iii) contains a functional group X2 of the carboxylic type; and when the polyfunctional compound (ii) contains functional groups X1 of the amine group type, the mononfunctional compound (iii) contains a functional group X2 of the amine group type.

EFFECT: obtained polyamide has high fluidity and improved mechanical properties.

21 cl, 5 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a thermoplastic elastomeric composition and preparation method thereof and can be used as a fluid impermeable layer in pneumatic tyres and tubes. The composition contains a halogenated isobutylene-containing elastomer and a nylon resin, having melting point between 170°C and 230°C. Said elastomer in form of vulcanised or partially vulcanised particles through dynamic vulcanisation is contained in form of a dispersed phase in a continuous phase of nylon in amount greater than 60 vol. % of overall content of elastomer and resin. Said period of time for dynamic vulcanisation is equal to or less than the defined holding time of the mixer. The method involves steps for mixing the elastomer with a vulcanising system thereof with fractional addition thereof into the nylon resin. The step for dynamic vulcanisation of the fractionally added amount of elastomer in the presence of a vulcanised composition from the previous step is repeated several times necessary to obtain total amount of halogenated elastomer in the said composition.

EFFECT: invention enables to achieve excellent longevity and elasticity properties with excellent air-tightness.

20 cl, 1 dwg, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to coating, specifically to tribotechnical coating compositions. The composition is a mixture of polytetrafluoroethylene nanoparticles combined with a fluorine-containing oligomer in a polyamide matrix.

EFFECT: composition provides simultaneous increase in wear-resistance and reduction of the friction coefficient of the coating during use without an external lubricant.

1 cl, 1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: composition contains a polymer mixture which contains at least one polysulphide component and at least one component based on polythioether and a mixture of additives which possibly contains equal amount of mica and polyamide. In certain versions, the premoulded compositions are electroconductive and can screen electromagnetic and radio frequency radiation.

EFFECT: simple technology of sealing and increasing effectiveness of screening electromagnetic and radio frequency radiation with minimal corrosion of conducting surfaces.

38 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing nanocomposites based on polymers and nanosilicates modified with organic compounds with better strength characteristics, designed for making articles in electrical engineering and mechanical engineering. The method involves mixing in molten mass of polymer - polysulfone or polyamide and filler - montmorrilonite or bentonite with cation exchange capacity of 60 - 150 mg-eq/100 g. The filler which is in form of an aqueous dispersion with concentration of 1-7% is pre-modified with organic cations through mixing and then drying. The ionic surfactant used is alkylbenzyldimethylammonium chloride taken in amount of 40-150% of the cation exchange capacity of the filler.

EFFECT: method provides improved technological parametres, including higher modulus of elasticity.

3 cl, 1 tbl, 3 ex

Multilayer bottle // 2411129

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

FIELD: medicine.

SUBSTANCE: invention relates to medicine and to packing cover for absorbing product, cover includes protective layer. Invention differs because of the fact that cover includes also first functional layer, connected to protective layer, which gives to cover multifunctionality.

EFFECT: invention allows to improve process of changing absorbing product.

15 cl, 4 dwg

FIELD: construction.

SUBSTANCE: ventilation panel made of multilayer material comprises a layer having the first hole and adjacent layer having the second hole. Besides the first and second holes do not match with each other and are not substantially overlapping, forming ventilation channel. At the same time this channel mutually joins the first and second holes, thus providing for passage of fluid medium both from hole to hole and through ventilation panel outside. Device also comprises insulating channel connected to one of holes, thus providing for insulation as a result of fluid medium passage along and inside of insulating channel. Invention also relates to ventilation system, method of ventilation panel manufacturing, and also to method of box manufacturing and to insulating panel made of multilayer material. Besides application of this panel is also possible in other areas of equipment, where it may be useful.

EFFECT: creation of ventilation panel, which preserves heat of hot products and prevents formation of undesirable moisture inside package.

46 cl, 49 dwg

FIELD: paper industry.

SUBSTANCE: cardboard contains at least two layers: the first layer made of raw materials having high density and high module of elasticity; and the second layer to provide voluminousness for cardboard, in which the second layer contains chemical-thermomechanical pulp (CTMP) of broadleaf wood, cellulose and/or CTMP of coniferous wood at the specified ratio of components. At the same time coherence by Scott is achieved, making at least 80 J/m2; index of bending resistance making at least 5 Nm6/kg3 and strength in direction z, making at least 200 kPa. Invention also relates to products made of cardboard.

EFFECT: expansion of multilayer cardboard range and improvement of its quality.

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

Multilayer bottle // 2411129

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

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