JP2001031760A - Oxygen impermeable resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer which is light and good in moldability and may be transparent and which has reliable oxygen-capturing properties while maintaining moldability of conventional resins and which has improved oxygen barrier properties, and its manufacturing method. SOLUTION: The oxygen impermeable resin is a polycondensation-based polymer comprising a polyamide-based, polycarbonate-based or polyallylate-based polycondensation-based polymer segment which constitutes a major part and an olefin oligomer segment which constitutes a minor part whose skeleton is a homopolymer of butadiene, norbornene, dicyclopentadiene, or isoprene which has carbon-carbon unsaturated bonds or its copolymer with an olefin, wherein the olefin oligomer segment is linked to the main chain in a block manner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen barrier polymer having an olefin oligomer group having a carbon-carbon unsaturated bond in the main chain, having oxygen-scavenging properties and having a zero amount of oxygen permeation. The present invention relates to a production method and an oxygen barrier polymer composition using the same.

[0002]

2. Description of the Related Art Conventionally, chemicals that dislike contact with oxygen, such as pharmaceuticals, photographic drugs, and industrial chemicals, products that dislike moisture absorption, such as tea, coffee, wine, beer, and seaweed, and those that readily react with or dislike contact with oxygen As packaging materials for food and drink, aluminum foil, glass bottles, molded articles of synthetic resin, films or films on which metals such as aluminum are deposited,
Recently, various products such as paper products (products processed by resin processing, aluminum foil or metal vapor deposition) are used. Among them, thermoplastic resin, molded articles or films containing it are lightweight, moldable, packaging productivity such as heat sealing,
It is superior in cost and is the most heavily used.

[0003] However, although containers and molded articles made of thermoplastic resin are generally excellent as packaging materials, the resin itself is permeable to oxygen gas, no matter how good the sealing property is, and the contact between the contents and oxygen can be prevented. It is difficult to prevent. For this reason, saponified ethylene-vinyl acetate copolymer (also referred to as ethylene-vinyl alcohol copolymer; hereinafter referred to as "EVOH") having gas barrier properties, polyvinylidene chloride, polyacrylonitrile, polymethaxylylenediamine adipamide (Hereinafter referred to as “MXD6”) or a laminate film or laminate with an aluminum foil, or a thermoplastic resin molded product (including a film) having a gas barrier property improved by vapor deposition of a metal such as aluminum has been used. . Among the above gas barrier materials, EVOH has one of the highest gas barrier properties among thermoplastic resins, and is inexpensive and has good moldability.
It is an excellent material in terms of easy handling such as no problem in supply.

One of the drawbacks of this EVOH is that it has a strong hygroscopic property, and when it absorbs moisture, the gas barrier property is reduced. Therefore, polyethylene, polypropylene, polyethylene terephthalate (hereinafter referred to as “PE
T ". ), Both sides of which are coated with a hydrophobic resin such as polyamide. In addition, all of these gas barrier resins have a characteristic that gas permeability is extremely small, but the oxygen permeability is not zero like aluminum foil and glass, and is not as high as that of thermoplastic resin such as polyolefin. Oxygen permeation is unavoidable only by being able to be about 100 to 1/1000.

[0005] In addition, depending on the shape of the container, in the case of products that are easily reactive with oxygen and do not want to come into contact with oxygen, filling in the absence of oxygen gas in a nitrogen gas or carbon dioxide gas atmosphere, etc., must be performed. However, it is not easy to reliably prevent contact with oxygen gas for products that dislike contact with oxygen.
In particular, even when the gas barrier resin is laminated, it is considerably difficult to remove oxygen in the air and the like remaining in the thermoplastic resin container, and further long-term storage is required. In such cases, it is almost impossible to eliminate oxygen permeating from the entire surface of the package.

As described above, in order to eliminate oxygen in the package, oxygen scavengers that actively adsorb (react with and remove) oxygen have been developed. The main component is often an iron metal-based material, and the powder or the molded product is used by wrapping it in a nonwoven fabric such as paper or gauze and enclosing the package. Although this oxygen absorber is inexpensive and can be used easily, it is rare that infants and the like misidentify it as food when using it for packaging food and the like. The oxygen scavenger of this system cannot exert its removal ability at low humidity, and can only exhibit its ability effectively under a fairly high humidity atmosphere. There is a problem such as loss of water, and the ability cannot be exhibited in an aqueous solution or the like. In addition, this type of oxygen absorber cannot be uniformly encapsulated in the entire package, and because it is locally encapsulated, the removal of oxygen is not uniform, and products that do not want to come into contact with oxygen are removed. Depending on the type, there may be cases where it cannot be used or the effect cannot be expected.

Accordingly, a means for blending a deoxidizing agent into the oxygen gas barrier polymer itself to give it oxygen scavenging properties, making it oxygen scavenging properties in the oxygen gas barrier polymer, and laminating or laminating this with a thermoplastic resin is as follows. It is considered to be extremely effective, and Japanese Patent Publication No. 4-60826, Japanese Patent Publication No. 4-60827, Japanese Patent Application Laid-Open No. 7-67594,
JP-A-7-171194 JP-A-7-309323
Many proposals have been made, for example, Japanese Patent Application Laid-Open No. Hei 9-40024 and Japanese Patent Application Laid-Open No. 9-40024. However, the incorporation of a deoxidizer into the thermoplastic resin inevitably reduces the workability of the resin and the physical properties, and the development of other means capable of solving this problem was required.

On the other hand, in WO98 / 12127, the polyester segment and the oxygen trapping amount (2
An oxygen-resistant bottle using a copolyester comprising a polyolefin oligomer segment (polybutadiene segment) of about 12% by weight is proposed.

[0009]

DISCLOSURE OF THE INVENTION The present invention is light in weight, has good moldability, is capable of selecting transparency, and has a conventionally known oxygen content while having moldability of a conventional resin. Has oxygen scavenging properties compared to barrier polymers,
An object of the present invention is to develop a polymer having a remarkably improved oxygen barrier property and a method for producing the polymer. The present oxygen barrier polymer is reactive with oxygen, albeit slightly, and is an oxygen barrier polymer capable of capturing oxygen without being affected by moisture or carbon dioxide gas.

The present invention relates to [1] a polyamide (hereinafter, referred to as "NY"), a polycarbonate (hereinafter, referred to as "PC"), or a polyarylate (hereinafter, referred to as "PAR") which constitutes most of the components. Oxygen impermeability in a polycondensation polymer comprising a polycondensation polymer segment and an olefin oligomer segment having a carbon-carbon unsaturated bond constituting a small portion, wherein the olefin oligomer segment is bonded to the main chain in a block shape. [1] The olefin oligomer segment having a carbon-carbon unsaturated bond is a segment having a skeleton of a homopolymer of butadiene, norbornene, dicyclopentadiene or isoprene or a copolymer with olefin. Oxygen impermeable resin according to,
[3] 0.5 to 15% by weight of the polycondensation polymer
A carbon-carbon unsaturated bond olefin oligomer segment having a molecular weight of 1,000 to 10,000 corresponding to
The oxygen-impermeable resin according to the above [1], comprising 9.5% to 85% by weight of a polycondensation polymer segment;

[4] In the production of a polycondensation polymer, an olefin oligomer having a reactive functional group at both ends and having a carbon-carbon unsaturated bond in the molecule is allowed to coexist and simultaneously subjected to a polycondensation reaction. A method for producing an oxygen-impermeable resin, comprising bonding a polyolefin oligomer segment in a block shape to the inside of a main chain,

[5] In the synthesis of a polycarbonate or polyarylate, an esterification reaction is carried out by coexisting a polyolefin oligomer having a carboxyl group or a hydroxyl group at both ends having a carbon-carbon unsaturated bond having a molecular weight of 1,000 to 10,000, and carrying out an esterification reaction. The method for producing an oxygen-impermeable resin according to the above [4], wherein the segment is bonded to the inside of the main chain, [6] In the synthesis of the polyamide, a carboxyl group, an amino group, or a hydroxyl group is present at both ends, and the carbon-carbon The method for producing an oxygen-impermeable resin according to the above [4], wherein an amidation reaction is carried out in the coexistence of a polyolefin oligomer having an unsaturated bond and a molecular weight of 1,000 to 10,000 to bond a polyolefin oligomer segment inside the main chain,

[7] These polycondensation polymers have a molecular weight of 100 with respect to polycarbonate or polyarylate.
Production of an oxygen-impermeable resin in which a polyolefin oligomer having a carboxyl group or a hydroxyl group at both ends having a carbon-carbon unsaturated bond of 0 to 10000 is reacted, a transesterification reaction is performed, and a polyolefin oligomer segment is bonded inside the main chain. [8] A polyamide having a carboxyl group, an amino group or a hydroxyl group at both terminals and a carbon-carbon unsaturated bond, and a molecular weight of 1,000 to 1, based on the polyamide.
0000, a method for producing an oxygen-impermeable resin in which a polyolefin oligomer is reacted, transamidated or transesterified, and a polyolefin oligomer segment is bonded inside the main chain.

[9] A polycondensation polymer comprising a NY-based, PC-based or PAR-based polycondensation polymer segment that constitutes a major part and an olefin oligomer segment having a carbon-carbon unsaturated bond that constitutes a minor part, An oxygen-impermeable resin composition characterized in that 50 to 500 ppm of a transition metal compound is blended with an oxygen-impermeable resin in which an olefin oligomer segment is bonded to a main chain in a block shape, and [10] an oxygen-barrier polymer. A resin composition comprising an oxygen-barrier polycondensation polymer segment constituting the majority of the polymer and a polyolefin oligomer segment constituting the minor portion, and further comprising a catalytic amount of a transition metal compound and a photooxidation promoter. The problem has been solved by developing a barrier resin composition.

[0015]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, polycondensation polymers, particularly PC, PAR and NY, are used. Each of these resins is a polymer having higher heat resistance and rigidity than polyolefin and the like, and a polymer having processability such as injection molding and extrusion molding. NY
Is produced by polycondensation of a divalent carboxylic acid and a diamine or by ring-opening polymerization of a lactam, and has an amide bond in the main chain. Various types of NY (= nylon)
Is manufactured, but not only aliphatic but also aromatic nylons such as xylylenediamine adipamide (= MXD6) which is a polycondensate of meta-xylylenediamine and adipic acid are included.

PC has a carbonate ester bond (—O—
It is a linear polymer having (RO-CO-) and is excellent as a resin like PAR. PAR is
It is a polycondensate of aromatic dicarboxylic acid and dihydric phenol, and has higher transparency than PET, low oxygen permeability, low water vapor permeability, high heat resistance, high impact strength, high elastic modulus, etc. It has excellent physical properties, excellent flame retardancy, high dimensional stability in molding, UV impermeability and UV stability, and is generally superior to PET.

When synthesizing a polycondensation-based polymer, a molecular weight having a polycondensable functional group at both terminals and a carbon-carbon unsaturated bond as a part of a raw material such as diamine, dicarboxylic acid or glycol. By using an olefin oligomer of 1,000 to 10,000, a polyamide-based, polycarbonate-based or polyarylate-based polycondensation-based polymer segment that constitutes a large part and a carbon-carbon unsaturated bond-containing olefin oligomer segment that constitutes a small part are NY, P bonded to the main chain in block form
It can be a polycondensation polymer such as C or PAR. That is, in the above-mentioned synthesis of NY, a carboxyl group, an amino group, and in some cases, a hydroxyl group at both terminals, and a molecular weight of 1,000 to 1,000 having a carbon-carbon unsaturated bond.
10,000 olefin oligomer segments are
Can be produced by mixing and reacting a dicarboxylic acid, which is a raw material of the above, with a diamine (a nylon salt is also acceptable) or a lactam.

Further, a small amount of an olefin oligomer having a molecular weight of 1,000 to 10,000 having an amino group, a hydroxyl group or a carboxyl group at both ends and having a carbon-carbon unsaturated bond is mixed with a polycondensation polymer of NY, PC or PAR. Then, a polycondensation polymer having a polyolefin oligomer segment in the main chain of NY, PC or PAR can be produced by transamidation or transesterification reaction while melting.

The olefin oligomer derivative used in the above polycondensation reaction needs to have a carbon-carbon unsaturated bond in the olefin oligomer segment chain. Such oligomers include butadiene, a diene having a conjugated double bond such as isoprene, or a homo-oligomer of a non-conjugated diene such as norbornene or dicyclopentadiene, or a copolymerized oligomer of a diene compound with an olefin such as ethylene or propylene. Can be mentioned. For these oligomers, it is necessary to introduce a functional group having a reactivity with a functional group bonded to the polycondensation polymer main chain. For this purpose, an oligomer containing a diene compound is formed by metathesis polymerization or anion living polymerization. Can be synthesized by introducing a functional group into the compound.

The amount of the olefin oligomer segment having a carbon-carbon unsaturated bond to be introduced into the polycondensation polymer having a reactive functional group is 0.5 to 15% by weight, preferably 3 to 7% by weight of the polycondensation polymer. % Is preferably introduced. When the introduction amount of the olefin oligomer segment is less than 0.5% by weight, the oxygen scavenging ability is small, and the retention time of the oxygen barrier property is short (at the present time, the expiration date could not be confirmed, but it is considered to be short). I cannot demonstrate enough ability. Also 15
It is not preferable to introduce an olefin oligomer segment in an amount exceeding the weight% because the processability and physical properties of the polycondensation polymer decrease. The oxygen barrier polymer of the present invention understands that the mechanism of the oxygen barrier reaction is that oxygen dissolved in the polymer reacts directly with the olefin oligomer segment of the polymer to capture oxygen. In this case, since the polymer itself has a gas barrier property, the amount of oxygen permeation is very small, but the small amount of permeated oxygen is captured in the resin layer. Although it has, it is considered that the performance as an oxygen barrier resin appears more remarkably than as an oxygen-scavenging polymer.

In the polymer of the present invention, when the polycondensation polymer segment that constitutes most of the polymer is transparent, there is a high possibility that the polycondensation oxygen scavenging polymer is also a transparent polymer. When an oxygen barrier polymer such as MXD6 nylon is used as the polycondensation polymer segment that makes up the majority, the moldability is almost the same as that of the oxygen barrier resin, unlike a resin blended with a reduced iron-based oxygen scavenger. It is. In particular, a reduced iron-based oxygen scavenger has a humidity dependency and cannot exhibit its activity without humidity, but has a characteristic that it can effectively deoxidize even in a dry state without humidity. In addition, when a polycondensation polymer having high gas permeability such as PC is used, oxygen scavenging property is remarkably exhibited, and when inserted into a container, it absorbs oxygen in the container and also functions as an oxygen scavenger. It became clear to have. In this case, the oxygen scavenging performance is not affected by the humidity and carbon dioxide concentration of the environment. Therefore, in combination with the function as an oxygen barrier resin, the oxygen scavenging agent for a dried product or the oxygen scavenging agent for a beverage containing carbon dioxide is used. It can be used effectively as an oxygen agent.

Since the oxygen barrier polymer of the present invention alone has low reactivity with oxygen alone, it is preferable to add a catalytic amount of a transition metal compound to the resin in order to increase the reactivity. Suitable transition metal compounds include manganese, cobalt, nickel, copper, rhodium, ruthenium, and the like, most preferably cobalt. Preferred counterions for these metals are chloride, acetate, stearate, palmitate,
Examples include, but are not limited to, 2-ethylhexanoate ion, neodecanoate ion, and naphthenate ion. Particularly preferred are cobalt stearate, 2-
Cobalt ethylhexanoate and cobalt neodecanoate are exemplified. Alternatively, the transition metal compound may be an ionomer, which are well known in the art. The amount of the transition metal compound is in the range of 0.001 to 1%, preferably 0.01 to 0.3% of the weight of the oxygen-scavenging resin as a metal. Below the lower limit, the effect of promoting the reaction is not recognized, and even if it exceeds 1%, the effect is saturated and does not increase the reaction rate with oxygen, but merely lowers the physical properties and increases the cost. Only.

It is preferable to add a photooxidation accelerator (sensitizer) to the oxygen barrier polymer layer in addition to the transition metal compound. As the photooxidation promoter, benzophenone, o-methoxybenzophenone, acetophenone, o
-Methoxyacetophenone, acenaphthenequinone, methyl ethyl ketone, valerophenone, hexanophenone,
α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, benzoin, benzoin methyl ether and the like can be used, but are not limited thereto.

The photo-oxidation promoter enhances the oxygen-scavenging rate of the oxygen-barrier polymer upon exposure to light, and varies depending on the type of the oxygen-barrier polymer, the wavelength and intensity of light, and the like. If the transparency of the resin is low, it is necessary to increase the amount of the photo-oxidation accelerator used. Usually, 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the whole resin composition.
It is about 1% by weight. The transition metal compound and the photo-oxidation accelerator are described in detail in JP-A-5-194949. Other methods for activating the oxygen-scavenging properties of the oxygen-barrier polymer include irradiation with radiation such as electron beams, γ-rays, and X-rays, ultrasonic waves for applying α-hydrogen extraction energy, high-frequency waves, heat (high The application of energy from the outside such as temperature) is also effective, and the combination thereof can shorten the induction period and increase the oxygen capturing speed and the oxygen capturing amount.

Such an oxygen barrier polymer may be used alone, or may be diluted with another resin in order to reduce the cost. Preferably, the type of resin to be diluted is preferably the same type of resin because the compatibility is high and the resin layer is likely to be transparent. In this case, the compounding amount of the oxygen barrier polymer is also related to the thickness of the oxygen barrier polymer layer, but a compound having an oxygen barrier polymer concentration of at least 5%, preferably 20% or more can be used.

[0026]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Co-rotating twin screw extruder manufactured by Toshiba Machine Co., Ltd. (TEM37BS, 37
mmφ, L / D = 45) to produce an oxygen-scavenging resin.

(Production of polyamide-based oxygen-scavenging resin) [Polyamide-based oxygen-scavenging resin- (PA-)] Nylon 6 (Novamid 1020, manufactured by Mitsubishi Chemical Corporation)
96 parts by weight having a relative viscosity of 3.4) were introduced from a hopper. The resin temperature was set to 260 ° C., and an octadiene oligomer having a carboxyl group at both ends was synthesized (an octadiene oligomer was synthesized by ordinary metathesis polymerization using octadiene, and a carboxyl group at both ends was converted to a carboxyl group). This time, the molecular weight is 2000.) A mixture of 4 parts by weight of liquid material and 200 ppm of cobalt stearate based on the total amount of nylon 6 and carboxy group octadiene oligomer at both ends is introduced into the extruder using a liquid injection machine. Then, the mixture was melt-kneaded for a residence time of about 5 minutes to carry out a reaction. After the unreacted substances and low-molecular substances were removed from the vacuum vent, the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum drier at a temperature of 80 ° C. for 4 hours. After confirming that the moisture content was 0.05% by weight or less, the pellets were used for subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
−)] Nylon 6 (Novamid 1020, manufactured by Mitsubishi Chemical Corporation)
92 parts by weight having a relative viscosity of 3.4) were introduced from a hopper. The resin temperature was set to 260 ° C., and an octadiene oligomer having a carboxyl group at both ends was synthesized (an octadiene oligomer was synthesized by ordinary metathesis polymerization using octadiene, and a carboxyl group at both ends was converted to a carboxyl group). This time, the molecular weight is 5000.) A mixture of 8 parts by weight of liquid material and 200 ppm of cobalt stearate based on the total amount of nylon 6 and carboxy group octadiene oligomer at both terminals is introduced into the extruder using a liquid injector. Then, the mixture was melt-kneaded for a residence time of about 5 minutes to carry out a reaction. After the unreacted substances and low-molecular substances were removed from the vacuum vent, the molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum drier at a temperature of 80 ° C. for 4 hours. After confirming that the moisture content was 0.05% by weight or less, the pellets were used for subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
-)] 730 g of adipic acid chloride and 103 g of a norbornene oligomer having both ends of carboxylic acid chloride were added to ethylene tetrachloride 20
Dissolve in liters and place in a tall 100 liter stainless steel reaction vessel. 450
g of hexamethylenediamine and 300 g of caustic soda are dissolved in 10 liters of water and poured into the previously made ethylene tetrachloride solution. The two liquids do not mix and form two layers, but a white film is immediately formed at the boundary between the two layers. The film was continuously taken out, washed with water, dried in a vacuum dryer at 80 ° C. for 12 hours to remove unreacted substances, low molecular weight substances, and moisture, and further pulverized into flakes, which were used for the subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
-)] Nylon 66 (manufactured by Showa Denko KK, Systema-A21)
88 parts by weight of 6) were introduced from a hopper. The resin temperature was set to 280 ° C., and a carboxyl group at each terminal was norbornene oligomer (a norbornene oligomer was synthesized by normal metathesis polymerization using norbornene, and a carboxyl group at each terminal was converted to a carboxyl group. The molecular weight is 5000.) Liquid 1
A mixture of 2 parts by weight of cobalt stearate and 200 ppm based on the total amount of nylon 66 and carboxy-terminal octadiene oligomer at both ends was introduced into the extruder using a liquid injector, and the mixture was melted and kneaded for about 5 minutes. After unreacted substances and low molecular weight substances were removed from the vacuum vent, the molten strand was rapidly cooled and cut in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum drier at a temperature of 80 ° C. for 4 hours. After confirming that the moisture content was 0.05% by weight or less, the pellets were used for subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
-)] 96 parts by weight of nylon MXD6 (manufactured by Mitsubishi Gas Chemical Company, Inc., MX nylon 6007, relative viscosity 2.7) were introduced from a hopper. A resin temperature is set to 280 ° C., and a butadiene oligomer having carboxyl groups at both terminals (a butadiene is synthesized by anion living polymerization to form a butadiene oligomer, and two initiators having two anion terminals as an initiator to obtain carboxyl groups at both terminals) Initiator α-methylstyrene was used, carbon dioxide gas was used in the termination reaction, and the molecular weight was 5000 in this case.
A mixture obtained by mixing 200 ppm of cobalt stearate with respect to the total amount of the nylon MXD6 and the carboxyl group-butadiene oligomer at both ends was introduced into an extruder using a liquid injection machine, and the mixture was melt-kneaded for a residence time of about 5 minutes to carry out a reaction. After removing unreacted substances and low molecular substances from the vacuum vent,
The molten strand was quenched in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. Further, the pellets were dried in a vacuum dryer at a temperature of 120 ° C. for 4 hours to obtain a moisture content of 0.05% by weight.
After confirming the following, it was used for subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
-)] 92 parts by weight of nylon MXD6 (manufactured by Mitsubishi Gas Chemical Company, Inc., MX nylon 6007, relative viscosity 2.7) were introduced from a hopper. A resin temperature is set to 280 ° C., butadiene oligomer having carboxyl groups at both ends (butadiene is synthesized by anion living polymerization to form a butadiene oligomer, and two initiators having two anion terminals in the initiator to obtain carboxyl groups at both ends) The initiator used was α-methylstyrene, and carbon dioxide gas was used in the termination reaction.The molecular weight was 10,000 in this case, and cobalt stearate was added to 8 parts by weight of the nylon MXD6 and the total amount of the butadiene oligomer at both terminal carboxyl groups. 20
A mixture of 0 ppm is introduced into an extruder (in the present invention, it is preferable to introduce the base polymer from the second supply port after the base polymer is different from the base polymer as a raw material,
Dry blending with the base polymer may be introduced from the hopper. Then, the mixture was melt-kneaded for a residence time of about 5 minutes to carry out a reaction. After unreacted substances and low-molecular substances were removed from the vacuum vent, the molten strand was rapidly cooled and cut in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum drier at a temperature of 120 ° C. for 4 hours, and confirmed to have a water content of 0.05% by weight or less, and used for subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
-)] Amorphous polyamide (manufactured by EMS, Grillamide TR5
5, glass transition temperature 160 ° C.) 94 parts by weight were introduced from a hopper. The resin temperature was set to 280 ° C., and an octadiene oligomer having amino groups at both terminals was used (an octadiene oligomer was synthesized by metathesis polymerization of octadiene and both terminals were substituted with amino groups. The molecular weight was 3000 in this case). A mixture obtained by mixing 200 parts by weight of cobalt stearate with respect to the total amount of the amorphous polyamide and the octadiene oligomer having both terminal amino groups at 6 parts by weight of the liquid material was introduced into an extruder using a liquid injector, and the residence time was about The reaction was carried out by melt-kneading for 5 minutes. After removing unreacted substances and low molecular substances from the vacuum vent, the molten strand was rapidly cooled and cut in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand.
The pellets were further dried in a vacuum drier at a temperature of 120 ° C. for 4 hours, and confirmed to have a water content of 0.05% by weight or less, and used for subsequent molding.

[Polyamide-based oxygen-scavenging resin- (PA
-)] Amorphous polyamide (manufactured by EMS, Grillamide TR5
5, glass transition temperature 160 ° C.) 90 parts by weight were introduced from a hopper. An octadiene oligomer having an amino group at both terminals was set at a resin temperature of 280 ° C. (an octadiene oligomer was synthesized by metathesis polymerization of octadiene and both ends were substituted with amino groups. The molecular weight was 6000 in this case). 10 parts by weight of the liquid material, a mixture of 200 ppm of cobalt stearate with respect to the total amount of the amorphous polyamide and the octadiene oligomer having amino groups at both terminals was introduced into an extruder using a liquid injector, and the residence time was about The reaction was carried out by melt-kneading for 5 minutes. After removing unreacted substances and low molecular substances from the vacuum vent, the molten strand was rapidly cooled and cut in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum drier at a temperature of 120 ° C. for 4 hours, and confirmed to have a water content of 0.05% by weight or less, and used for subsequent molding.

[Polycarbonate oxygen scavenging resin-
(PC-)] PC (Mitsubishi Gas Chemical Co., Ltd., Iupilon S2000,
90 parts by weight (glass transition temperature = 150 ° C.) were introduced from a hopper. The resin temperature was set to 280 ° C., and a butadiene oligomer having hydroxyl groups at both ends (manufactured by Elatochem, Inc.
RHT45, Mw = 2800) A mixture obtained by mixing 200 parts by weight of cobalt stearate with 10 parts by weight of the liquid material based on the total amount of the PC and the butadiene oligomer having hydroxyl groups at both ends was introduced into an extruder using a liquid injector. ,
The transesterification was carried out by melt-kneading for a residence time of about 5 minutes, and unreacted substances and low molecular substances were removed from the vacuum vent. Next, the molten strand was quenched in water and cut to obtain pellets.
The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum dryer at a temperature of 80 ° C. for 6 hours. After confirming that the water content was 0.005% by weight or less, the pellets were used for subsequent molding.

[Polycarbonate oxygen scavenging resin-
(PC-)] PC (Mitsubishi Gas Chemical Co., Ltd., Iupilon S2000,
(Glass transition temperature = 150 ° C.) 85 parts by weight were introduced from a hopper. The resin temperature was set to 280 ° C., and both ends of the hydroxyl group butadiene oligomer (manufactured by ELFA Atochem, RLM
20, Mw = 1230) A mixture obtained by mixing 200 parts by weight of cobalt stearate with respect to the total amount of the above-mentioned PC and butadiene oligomer having hydroxyl groups at both ends to 15 parts by weight of a liquid material was introduced into an extruder using a liquid injector, and the residence time was measured. Unesterified and low molecular weight substances were removed from the vacuum vent by melt kneading and transesterification for about 5 minutes. Next, the molten strand was quenched in water and cut to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand.
The pellets were further dried in a vacuum dryer at a temperature of 80 ° C. for 6 hours, and confirmed to have a water content of 0.005% by weight or less, and were used for subsequent molding.

[Polyarylate-based oxygen-scavenging resin-
(PAR-)] 92 parts by weight of PAR (U-Polymer 100, manufactured by Unitika Ltd., glass transition temperature: 193 ° C.) were introduced from a hopper. The resin temperature was set to 320 ° C., and a dicyclopentadiene oligomer having hydroxyl groups at both ends (a dicyclopentadiene oligomer was synthesized by metathesis polymerization using dicyclopentadiene, and converted to hydroxyl groups by alkali hydrolysis at both ends) The molecular weight this time is 2.
000) Cobalt stearate is added to 8 parts by weight of liquid
A mixture of 200 ppm with respect to the total amount of the AR and the dicyclopentadiene oligomer having hydroxyl groups at both ends was introduced into an extruder using a liquid injection machine, and the mixture was melted and kneaded for a residence time of about 5 minutes to carry out a reaction. After removing low-molecular substances from the vacuum vent, the molten strand was quenched and cut in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets were further dried in a vacuum drier at a temperature of 120 ° C. for 4 hours, and confirmed to have a water content of 0.05% by weight or less, and used for subsequent molding.

[Polyarylate-based oxygen-scavenging resin-
(PAR-)] PAR (manufactured by Unitika Ltd., U-Polymer (U-10)
0), glass transition temperature: 193 ° C.) 88 parts by weight were introduced from a hopper. The resin temperature was set to 320 ° C., and a dicyclopentadiene oligomer having hydroxyl groups at both terminals (a dicyclopentadiene oligomer was synthesized by metathesis polymerization, and both terminal groups were alkali-hydrolyzed into hydroxyl groups. The molecular weight was 5000 in this case. ) Cobalt stearate was added to 12 parts by weight of the liquid material in an amount of 200 to the total amount of the PAR and the dicyclopentadiene oligomer having hydroxyl groups at both ends.
ppm was introduced into the extruder using a liquid injector, and the mixture was melt-kneaded for a residence time of about 5 minutes to carry out the reaction. After the unreacted substances and low-molecular substances were removed from the vacuum vent, the molten strand was removed. It was rapidly cooled in water to obtain pellets. The treatment was performed under a nitrogen atmosphere until pellets were obtained from the molten strand. The pellets are further dried at a temperature of 1 in a vacuum dryer.
After drying at 20 ° C. for 4 hours, it was confirmed that the water content was 0.05% by weight or less, and used for subsequent molding.

Table 1 shows the composition of the resin composition using the above oxygen barrier polymer.

[Table 1]

* 1: PA6 = polyamide 6 * 2: PA66 = polyamide 66 * 3: MXD6 = meta-xylylenediamine adipamide * 4: TR55 = amorphous polyamide * 5: POD = octadiene oligomer * 6: PNB = Norbornene oligomer * 7: PBD = butadiene oligomer * 8: PDCPD = dicyclopentadiene oligomer

(Examples 1 and 12, Comparative Examples 1 and 2) A film having a thickness of 50 μm was formed from the above resin composition by T-die molding. Table 2 shows the resin used and the molding temperature used for each molding.

[0042]

[Table 2]

[Evaluation Method] (Oxygen permeability) The equipment used was OX-TRAN manufactured by Mocon Corporation.
Measured using 2/20 ML. The measurement was performed under the conditions of a temperature of 25 ° C. and an inner surface of 65% RH.

(Oxygen absorption amount) 1) Change in oxygen concentration in the pouch after filling with air (1) A four-sided pouch (150 mm × 200 mm) was formed from an aluminum foil multilayer sheet by heat sealing. This pouch is filled with 400 ml of a gas in which dry nitrogen and dry oxygen are mixed at a ratio of 98: 2, and an oxygen barrier polymer film (thickness: 50 μm × 100 mm × 100 m)
m) was inserted and sealed. The pouch was stored at a temperature of 23 ° C., and the oxygen concentration in the pouch was measured over time. The oxygen concentration at the start was 2.0%.

[0045]

[Table 3]

[0046]

The oxygen-impermeable resin of the present invention is a polymer having a remarkable characteristic that the oxygen permeability is completely zero. EVOH, which has been called a conventional oxygen barrier resin
(Ethylene-vinyl alcohol copolymer resin), vinylidene chloride resin, polyacrylonitrile resin and the like all have extremely excellent characteristics as compared with their oxygen permeability being not zero. When the base polymer (the polymer segment that constitutes the majority) is a polymer segment that does not have oxygen barrier properties, it is a polymer having excellent oxygen scavenging performance at the same time. Also, when the base polymer is an oxygen barrier polymer, it is a polymer that has a higher oxygen barrier property than that of the base polymer and cannot measure any amount of oxygen permeation, and also has a weak oxygen scavenging performance. This is presumed to be because the oxygen-impermeable resin of the present invention traps oxygen that dissolves and diffuses in the polymer in the polyolefin oligomer segment having a carbon-carbon unsaturated bond to have zero oxygen permeability. ing. Therefore, when using an oxygen barrier resin for the base polymer,
Since the amount of oxygen dissolved in the polymer is extremely small, it is presumed that the oxygen barrier property can be exerted as an oxygen-impermeable resin having the performance for a long time. Although the oxygen-impermeable resin of the present invention has the above-mentioned properties, the processability thereof is good in all cases, and the molding process such as extrusion, injection molding, and press working is stable. Is possible.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 53/00 C08L 53/00 67/00 67/00 69/00 69/00 77/00 77/00 ( 72) Inventor Hirotaka Takoshi 1-1-1 Onodai, Midori-ku, Chiba-shi, Chiba Showa Denko KK Research Institute (72) Inventor Tomohiko Miyauchi 1-13-9 Shiba-Daimon, Minato-ku, Tokyo Showa Denko K.K. (72) Inventor Kensuke Onishi 3-6-5 Iidabashi, Chiyoda-ku, Tokyo Showa Aluminum Can Co., Ltd. F-term (reference) 4J001 DA01 DB05 DC01 EA02 EA06 EA12 EB02 EB08 EB73 EC02 EC47 EC82 EE06F EE24F EE26F EE27F GA12 GE15 JA13 JB01 JB29 JB50 4J002 BP031 CL001 DD076 EE027 EG006 FD206 FD207 4J029 AA04 AA09 AC03 AC04 AD01 BA01 CA02 KH01 4J031 AA12 AA28 AA29 AA49 AA52 AA55 AB01 AC03 AC07 AD01 AF11

Claims (10)

[Claims] 1. A polycondensation polymer comprising a polyamide-based, polycarbonate-based or polyarylate-based polycondensation-based polymer segment constituting a major part and an olefin oligomer segment having a carbon-carbon unsaturated bond constituting a minor part. An oxygen-impermeable resin, wherein an olefin oligomer segment is bonded to a main chain in a block shape. 2. The olefin oligomer segment having a carbon-carbon unsaturated bond is a segment having a skeleton of a homopolymer of butadiene, norbornene, dicyclopentadiene or isoprene or a copolymer with olefin. Oxygen impermeable resin. 3. The polycondensation-based polymer is 0.5 to 15
The oxygen-impermeable resin according to claim 1, comprising a carbon-carbon unsaturated bond olefin oligomer segment having a molecular weight of 1,000 to 10,000 corresponding to a weight percent and a polycondensation polymer segment of 99.5 to 85 weight percent. 4. In the production of a polycondensation-based polymer, an olefin oligomer having a reactive functional group at both terminals and having a carbon-carbon unsaturated bond in the molecule is allowed to coexist and polycondensed simultaneously. A method for producing an oxygen-impermeable resin, wherein a polyolefin oligomer segment is bonded in a block shape inside a chain. 5. In the synthesis of polycarbonate or polyarylate, carbon-carbon having a molecular weight of 1,000 to 10,000 is used.
5. The production of an oxygen-impermeable resin according to claim 4, wherein an esterification reaction is carried out in the presence of a polyolefin oligomer having a carboxyl group or a hydroxyl group at both ends having a carbon unsaturated bond to bond the polyolefin oligomer segment inside the main chain. Method. 6. A polyamide having a carboxyl group, an amino group or a hydroxyl group at both terminals and a carbon-carbon unsaturated bond, and having a molecular weight of 1,000 to 1 in the synthesis of polyamide.
The method for producing an oxygen-impermeable resin according to claim 4, wherein an amidation reaction is performed in the presence of 0000 polyolefin oligomers to bond the polyolefin oligomer segments inside the main chain. 7. A polycondensation-based polymer having a molecular weight of 1,000 to 1 with respect to polycarbonate or polyarylate.
A method for producing an oxygen-impermeable resin in which a polyolefin oligomer having a carboxyl group or a hydroxyl group at both terminals having a carbon-carbon unsaturated bond of 0000 is reacted, a transesterification reaction is performed, and a polyolefin oligomer segment is bonded inside the main chain. 8. Polyamide oligomer having a carboxyl group, an amino group or a hydroxyl group at both terminals and a carbon-carbon unsaturated bond and having a molecular weight of 1,000 to 10,000 is used as the polyamide. A method for producing an oxygen-impermeable resin in which a polyolefin oligomer segment is bonded to the inside of a main chain by reacting and transamidating or transesterifying. 9. A polycondensation-based polymer comprising a polyamide-based, polycarbonate-based or polyarylate-based polycondensation-based polymer segment constituting a major part and an olefin oligomer segment having a carbon-carbon unsaturated bond constituting a minor part, Oxygen-impermeable resin in which olefin oligomer segments are bonded to the main chain in block form
An oxygen-impermeable resin composition containing 0 to 500 ppm of a transition metal compound. 10. The oxygen-barrier polymer comprises an oxygen-barrier polycondensation-based polymer segment constituting the major part of the polymer and a polyolefin oligomer segment constituting a minor part thereof, and further comprises a catalytic amount of a transition metal compound and a photooxidation promoter. An oxygen barrier resin composition which is a resin composition comprising: