WO2019044882A1 - Résine polyamide et film formé à partir de celle-ci - Google Patents

Résine polyamide et film formé à partir de celle-ci Download PDF

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Publication number
WO2019044882A1
WO2019044882A1 PCT/JP2018/031896 JP2018031896W WO2019044882A1 WO 2019044882 A1 WO2019044882 A1 WO 2019044882A1 JP 2018031896 W JP2018031896 W JP 2018031896W WO 2019044882 A1 WO2019044882 A1 WO 2019044882A1
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Prior art keywords
polyamide resin
acid
unit
weight
aromatic ring
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PCT/JP2018/031896
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English (en)
Japanese (ja)
Inventor
知之 中川
康成 花岡
秀作 和田
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宇部興産株式会社
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Priority to JP2019539566A priority Critical patent/JP7180604B2/ja
Publication of WO2019044882A1 publication Critical patent/WO2019044882A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a polyamide resin and a film comprising the same.
  • Polyamide resins are used as food packaging materials for retort foods and the like because they are excellent in mechanical strength, thermal properties, chemical properties and gas barrier properties.
  • the required characteristics are diversified and advanced.
  • processed meat products such as ham and sausage, which are one of the food packaging applications, and in water food packaging applications, shrink the packaging material by heating while maintaining thin and practical mechanical strength and gas barrier properties.
  • a polyamide film having an excellent heat shrinkability that enables easy packing of the contents.
  • polyamide resin and the polyamide film which can improve the heat shrinkability of a polyamide film are indicated.
  • a polyamide resin whose heat shrinkability can be improved a polyamide copolymer comprising ⁇ -caprolactam, an aliphatic diamine such as hexamethylene diamine, and an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid is disclosed (for example, , Patent Document 1).
  • An object of the present invention is to provide a film excellent in heat shrinkability, pinhole resistance and the like, and a polyamide resin suitable therefor.
  • the inventors of the present invention have found that a specific polyamide resin having a unit derived from a diamine or dicarboxylic acid having an aromatic ring structure in a molecular chain is excellent in heat shrinkability, pinhole resistance and the like, and reached the present invention.
  • a polyamide resin containing three or more types of units (A) a unit derived from a lactam and / or an aminocarboxylic acid and (B) a unit derived from an equimolar salt of a diamine and a dicarboxylic acid,
  • the unit derived from the equimolar salt of (B) diamine and dicarboxylic acid is It is a polyamide resin for shrink film comprising (B-1) a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure.
  • the invention preferably comprises, in all units of the polyamide resin: 60 to 70% by weight of units derived from (A) lactam and / or amino carboxylic acid and 30 to 40% by weight of units derived from equimolar salts of (B) diamine and dicarboxylic acid, and B-1)
  • a polyamide resin for shrink film comprising 25 to 39% by weight of a unit not having an aromatic ring structure and 1 to 15% by weight of a unit having an aromatic ring structure (B-2).
  • the present invention it is possible to provide a polyamide resin excellent in heat shrinkability, pinhole resistance and the like, and a film comprising the same.
  • the film made of the polyamide resin of the present invention has good stretchability.
  • the stretched film made of the polyamide resin of the present invention has good heat shrinkability, and thus can be suitably used as a packaging material, particularly a shrink film as a food packaging material.
  • a numerical range indicated using “to” indicates a range including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition.
  • the polyamide resin of the present invention is a polyamide resin containing three or more types of units, (A) a unit derived from a lactam and / or an aminocarboxylic acid and (B) a unit derived from an equimolar salt of a diamine and a dicarboxylic acid,
  • the unit derived from the equimolar salt of (B) diamine and dicarboxylic acid is A polyamide resin comprising (B-1) a unit having no aromatic ring structure and (B-2) a unit having an aromatic ring structure.
  • a unit derived from (A) lactam and / or amino carboxylic acid The unit derived from (A) lactam and / or amino carboxylic acid contained in the polyamide resin can be introduced into the polyamide resin by subjecting the lactam and / or amino carboxylic acid to polymerization.
  • lactams include ⁇ -caprolactam, ⁇ -enantholactam, ⁇ -undecalactam, ⁇ -dodecalactam, 2-pyrrolidone and the like, and at least one selected from the group consisting of these is preferable.
  • aminocarboxylic acid examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. At least one selected is preferred.
  • lactams and aminocarboxylic acids may be used alone or in combination of two or more. When a lactam and an aminocarboxylic acid are used in combination, they can be used as a mixture in any ratio.
  • the content of units derived from (A) lactam and / or amino carboxylic acid contained in all units of the polyamide resin is, for example, 50 to 98% by weight, preferably 55 to 90% by weight, and more preferably It is 60 to 88% by weight, particularly preferably 60 to 70% by weight. If the content of units derived from lactam and / or aminocarboxylic acid is at least the above lower limit, mechanical strength tends to be further improved. There exists a tendency for extending
  • the polyamide resin contains (B-1) a unit not having an aromatic ring structure and (B-2) a unit having an aromatic ring structure as a unit derived from an equimolar salt of diamine and dicarboxylic acid.
  • a unit derived from an equimolar salt of diamine and dicarboxylic acid is a unit formed by polymerizing an equimolar salt or equimolar mixture of diamine and dicarboxylic acid, and one kind of diamine and one kind of dicarboxylic acid It is regarded as one type of unit by combination of.
  • the diamine and dicarboxylic acid constituting the unit may be directly condensed, or may be condensed through another unit or a diamine or dicarboxylic acid constituting another unit.
  • the unit having no aromatic ring structure included in the polyamide resin (B-1) is an aromatic ring derived from an equimolar salt or equimolar mixture of diamine and dicarboxylic acid
  • diamines other than diamines having an aromatic ring structure examples include linear aliphatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine and dodecamethylenediamine; 1-butyl-1, 2 -Ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4 -Butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentane Diamine, 2,2-dimethyl-1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4 Dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6
  • dicarboxylic acids other than dicarboxylic acids having an aromatic ring structure adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Linear aliphatic dicarboxylic acids such as hexadecanedioic acid, octadecanedioic acid, eicosandioic acid; dimethylmalonic acid, 3,3-dimethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, 3- Methyl adipic acid, trimethyl adipic acid, 2-butyl octadioic acid, 2,3-dibutyl butane dioic acid, 8-ethyl octadecane dio
  • the unit having an aromatic ring structure contained in the polyamide resin (B-2) is derived from an equimolar salt or an equimolar mixture of diamine and dicarboxylic acid, and the diamine and dicarboxylic acid An equimolar salt or equimolar mixture of a dicarboxylic acid and a diamine having an aromatic ring structure, or an equimolar salt or equimolar mixture of a diamine and a dicarboxylic acid having an aromatic ring structure. Formed by polymerizing.
  • diamine having an aromatic ring structure p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 1,4 -Diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylme
  • One type of diamine having an aromatic ring structure may be used, or two or more types may be used in combination as appropriate.
  • dicarboxylic acids having an aromatic ring structure examples include isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as 4'-biphenyldicarboxylic acid, diphenylmethane-2,4-dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid and diphenylmethane-4,4'-dicarboxylic acid An acid is mentioned, and isophthalic acid and terephthalic acid are more preferable.
  • the dicarboxylic acid having an aromatic ring structure may be used alone or in combination of two or more.
  • the total content of units derived from equimolar salts of (B) diamine and dicarboxylic acid contained in all units of the polyamide resin is, for example, 2 to 50% by weight, preferably 10 to 45% by weight, It is preferably 12 to 40% by weight, particularly preferably 30 to 40% by weight.
  • the stretchability and heat shrinkability tend to be further improved. If the content is less than the above upper limit, crystallinity and film physical properties tend to be further improved, and it tends to be easier to obtain an industrially advantageous stretched film.
  • the total content of (A) the content of units derived from lactam and / or amino carboxylic acid and the total content of units derived from equimolar salts of diamine and dicarboxylic acid in all units of the polyamide resin is practically From the viewpoint of physical properties, it is preferably 90 to 100% by weight, more preferably 95 to 100% by weight, and still more preferably 97 to 100% by weight.
  • the (B-2) units having an aromatic ring structure contained in all units of the polyamide resin The content is, for example, 0.1 to 49% by weight, preferably 0.5 to 49% by weight, more preferably 1 to 49% by weight, and still more preferably 1.5 to 20% by weight. .
  • the content of the unit having an aromatic ring structure is at least the above lower limit, the stretchability and the heat shrinkability tend to be further improved. If the content is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
  • the content of the unit having an aromatic ring structure (B-2) is determined as follows.
  • the proportion of the unit having an aromatic ring structure (B-2) is a dicarboxylic acid having no aromatic ring structure equivalent to the weight of the diamine unit. It is the sum (weight%) with the weight of the unit.
  • the proportion of the unit having an aromatic ring structure (B-2) is an aromatic ring structure having an equimolar amount with the weight of the dicarboxylic acid unit.
  • the weight (% by weight) with the weight of diamine units not having is both a diamine unit and a dicarboxylic acid unit
  • the ratio of the unit having an aromatic ring structure (B-2) is the weight of the diamine unit and the ratio of the dicarboxylic acid unit It is the sum (weight%) of the weight of the part which is equimolar to the weight.
  • a unit having an aromatic ring structure contained in the polyamide resin is both a diamine unit and a dicarboxylic acid unit, and when the diamine unit and the dicarboxylic acid unit are not equimolar, a unit having an aromatic ring structure (B-2)
  • the ratio of is the sum of the weight (part by weight) of both equimolar parts, the sum of the weight of the unit having the remaining aromatic ring structure and the weight of the unit having no equimolar aromatic ring structure % By weight).
  • (B-2) units having an aromatic ring structure contained in all units of the polyamide resin The content is, for example, 0.1 to 44% by weight, preferably 0.5 to 44% by weight, and more preferably 1 to 44% by weight.
  • the content of the unit having an aromatic ring structure is at least the above lower limit, the stretchability and the heat shrinkability tend to be further improved. If the content is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
  • the unit having an aromatic ring structure (B-2) contained in all units of the polyamide resin The content is, for example, 0.1 to 39% by weight, preferably 0.5 to 39% by weight, and more preferably 1 to 39% by weight.
  • the content of the unit having an aromatic ring structure is at least the above lower limit, the stretchability and the heat shrinkability tend to be further improved. If the content is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
  • the content ratio of units having an aromatic ring structure (B-2) to the total content of units derived from a lactam and / or an aminocarboxylic acid (A) and units not having an aromatic ring structure (B-1) B-2) / ⁇ (A) + (B-1) ⁇ ⁇ 100] is, for example, 0.1 to 97% by weight, preferably 0.5 to 97% by weight, and more preferably 1 to It is 97% by weight.
  • the percentage of units having an aromatic ring structure is equal to or more than the above lower limit, stretchability and heat shrinkage tend to be further improved. If the content is less than the above upper limit, practical physical properties such as mechanical strength tend to be further improved.
  • the aromatic ring structure contained in all units of the polyamide resin is included.
  • the content of the unit not contained is preferably 25 to 39% by weight, and the content of the unit having an aromatic ring structure (B-2) contained in all the units of the polyamide resin is preferably 1 to 15% by weight.
  • the polyamide resin of the present invention is particularly In all units of polyamide resin, (A) 60 to 70% by weight of a unit derived from lactam and / or amino carboxylic acid and 30 to 40% by weight of a unit derived from (B) equimolar salt of diamine and dicarboxylic acid, and (B-1 2.)
  • a polyamide resin comprising 25 to 39% by weight of a unit having no aromatic ring structure and 1 to 15% by weight of a unit having an aromatic ring structure (B-2) is preferable.
  • a polyamide resin having such a composition is particularly preferable because it can provide a film excellent in heat shrinkability, pinhole resistance and the like.
  • the unit derived from the (A) lactam and / or aminocarboxylic acid is preferably a unit derived from (A) ⁇ -caprolactam and / or 6-aminocaproic acid.
  • the unit having no (B-1) aromatic ring structure is preferably a unit derived from an equimolar salt of hexamethylenediamine and adipic acid.
  • the unit having an aromatic ring structure (B-2) is preferably a unit derived from hexamethylenediamine and an equimolar salt of isophthalic acid and / or terephthalic acid.
  • the production of the polyamide resin can be carried out batchwise or continuously, and a batch type reaction kettle, a single tank type or multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus, a single screw type kneading extruder, a twin screw type kneading extruder, etc.
  • a well-known polyamide manufacturing apparatus such as a kneading reaction extruder, can be used.
  • the polymerization method known methods such as melt polymerization, solution polymerization and solid phase polymerization can be used. These polymerization methods can be used alone or in combination as appropriate.
  • the polyamide resin can be produced, for example, by charging (A) a lactam and / or aminocarboxylic acid, (B) equimolar salts of diamine and dicarboxylic acid, and water in a pressure container and sealing at 200 to 350 ° C. In the temperature range, after polycondensation under pressure, the pressure is lowered, and the polycondensation reaction is continued in the temperature range of 200 to 350 ° C. under atmospheric pressure or under reduced pressure to obtain a target polyamide resin by increasing the molecular weight. It can be manufactured. In this case, equimolar salts of (B) diamine and dicarboxylic acid are dissolved by mixing approximately equimolar diamine and dicarboxylic acid with water, alcohol, etc.
  • nylon salt and the solution state as it is, concentration Alternatively, it may be charged as a solid nylon salt obtained by recrystallization.
  • approximately equimolar diamine and dicarboxylic acid may be charged as they are into the pressure container.
  • (B-1) diamine and dicarboxylic acid constituting a unit having no aromatic ring structure are charged as equimolar salts thereof
  • (B-2) diamine and a dicarboxylic acid constituting a unit having an aromatic ring structure The pressure vessel may be charged as it is.
  • the equimolar mixture of approximately equimolar diamine and dicarboxylic acid substantially corresponds to an equimolar salt.
  • water used in the method for producing a polyamide resin it is desirable to use ion-exchanged water from which oxygen has been removed, distilled water, etc.
  • the amount thereof used is, for example, 1 to 150 with respect to 100 parts by weight of the raw material constituting the polyamide resin. It is a weight part.
  • phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid and alkali metal salts thereof can be added to promote polymerization and prevent oxidation.
  • the amount of the phosphorus-based compound added is usually 50 to 3,000 ppm relative to the polyamide resin to be obtained.
  • the polyamide resin may be manufactured by adding at least one molecular weight modifier selected from the group consisting of adipic acid, isophthalic acid, and dicarboxylic acids such as terephthalic acid. These molecular weight modifiers may be added alone or in combination of two or more.
  • the amount used varies depending on the reactivity of the molecular weight modifier and the polymerization conditions, but the relative viscosity of the polyamide to be finally obtained is in the range of 1.5 to 5.0 It is decided as appropriate.
  • the molecular weight of the polyamide resin is such that the relative viscosity ( ⁇ r) measured by the method described in JIS K 6810 is in the range of 1.5 to 5.0, preferably 2.0 to 4.5. There are no particular restrictions on the type of end groups of the polyamide resin and the concentration and molecular weight distribution thereof.
  • the high molecular weight polyamide resin is usually extracted from the reaction vessel in a molten state, cooled with water or the like, and then processed into pellets.
  • the main component is a polyamide resin containing a large amount of non-reacted monomers such as nylon 6, it is preferable to further remove the non-reacted monomers and the like by hot water washing or the like and then use for film production.
  • Polyamide resins can be suitably used for film production.
  • the invention encompasses the use of polyamide resin in the production of films.
  • a method for producing a film from a polyamide resin a known method for producing a film, for example, a production method such as a T-die method using a melt extruder, an inflation method, a tubular method, a solvent casting method, or a heat pressing method is applied. be able to.
  • the melting temperature of the polyamide in the method using a melt extruder is, for example, not less than the melting point of the polyamide used and not more than 320 ° C.
  • the film made of a polyamide resin may be a stretched film.
  • the invention encompasses the use of polyamide resins in the manufacture of oriented films.
  • a stretched film can be produced, for example, by stretching the above-mentioned film.
  • the stretching may be at least uniaxial, and may be appropriately selected according to the use of the film, such as uniaxial stretching, simultaneous biaxial stretching, and sequential biaxial stretching.
  • a resin composition is obtained
  • the resin composition is melt-extruded with an extruder equipped with a T-die to form an unstretched film.
  • the unstretched film may be subsequently stretched in a continuous process, or may be wound once stretched.
  • Stretching is carried out at a temperature above the glass transition temperature (hereinafter referred to as Tg) of the polyamide resin used.
  • Tg glass transition temperature
  • the first stage of sequential biaxial stretching (primary stretching) is stretched in the temperature direction of Tg or more (Tg + 50) ° C. to a draw ratio of 2 to 5 times, preferably 2.5 to 4 times in the extrusion direction of the film
  • the second stage of drawing (secondary drawing) performed in the direction perpendicular to the extrusion direction of the film is carried out at the same temperature as the primary drawing or at a slightly higher temperature, with a draw ratio of 2 to 5 times, preferably 2.5 to 4 times It is drawn.
  • a sequentially biaxially stretched film is manufactured.
  • the stretched film made of the polyamide resin of the present invention preferably has a hot water shrinkage of 20 to 60%, more preferably 22 to 60%, still more preferably 25 to 60%.
  • the stretched film made of the polyamide resin of the present invention can be suitably used as a packaging material, particularly as a food packaging material, by taking advantage of the high hot water shrinkage rate.
  • the heat stabilizer With respect to the polyamide resin, the heat stabilizer, the ultraviolet light absorber, the light stabilizer, the antioxidant, the antistatic agent, the tackifier, the sealability improver, the antifogging agent, and the release within the range that the effect of the present invention is not inhibited.
  • Additives, impact modifiers, plasticizers, pigments, dyes, perfumes, reinforcements and the like can be added.
  • Oxygen Permeability According to ASTM D-3985-81, oxygen of 50 ⁇ m unstretched film under conditions of 23 ° C. and 0% RH, using MOCON-OX-TRAN 2/20 manufactured by Modern Control. The permeability coefficient was measured.
  • Example 1 910.01 g (70 wt%) of ⁇ -caprolactam in a 5-liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure relief port, pressure regulator and polymer outlet, hexamethylene Equimolar salt of diamine (HMD) and adipic acid (AA) 520.00 g of an aqueous solution of 50% (equimolar salt of HMD and AA: 20% by weight), 67.19 g of an aqueous HMD 80% solution, isophthalic acid (IPA: Tokyo Kasei Co., Ltd.) 76.51 g (manufactured by Kogyo Co., Ltd.) (the molar ratio of HMD to IPA is 1: 1) (10% by weight) and 0.065 g of sodium hypophosphite are charged, nitrogen pressurization and pressure release are repeated several times, and a pressure vessel The interior was purged with nitrogen and then heated gradually.
  • HMD hexamethylene Equi
  • the ⁇ r of the obtained polyamide was 3.5.
  • About 2 g of the obtained polyamide was used to prepare a 100 ⁇ m-thick unstretched film using a press molding machine at 260 ° C.
  • a reference wire 50 mm interval
  • the film was stretched 2.7 times in the machine direction at a deformation speed of 150 mm / minute under the same temperature.
  • the stretched film was left to stand in an atmosphere of 23 ° C. and 50% RH for a whole day and then left in hot water of 90 ° C. for 1 minute to measure a hot water shrinkage, which was 32%.
  • Table 1 The results are shown in Table 1.
  • Example 2 When a hot water shrinkage factor of a stretched film obtained in the same manner as in Example 1 was measured except that a sample was cut out from an unstretched film produced by a press molding machine, preheated and stretched at an atmosphere temperature of 120 ° C., It was 36%. The results are shown in Table 1.
  • Example 3 When a hot water shrinkage percentage of a stretched film obtained in the same manner as in Example 1 was measured except that a sample was cut out from an unstretched film produced by a press molding machine, preheated and stretched at an atmosphere temperature of 150 ° C., It was 39%. The results are shown in Table 1.
  • Example 4 In a 70-liter pressure-resistant container equipped with a stirrer, thermometer, pressure gauge, pressure controller, nitrogen gas inlet, outlet and polymer outlet, 16.10 kg (70 wt%) of ⁇ -caprolactam, HMD and AA Equimolar salt 50% aqueous solution 9.20 kg (equimolar salt of HMD and AA: 20% by weight), HMD 80% aqueous solution 1.183 kg, terephthalic acid (TPA: manufactured by Tokyo Chemical Industry Co., Ltd.) 1.353 kg (HMD and TA) The molar ratio of 1: 1) (10% by weight), 1.15 g of sodium hypophosphite was added, nitrogen pressurization and pressure release were repeated several times, and the inside of the pressure container was purged with nitrogen and then heated up to 240 ° C.
  • TPA terephthalic acid
  • the obtained polyamide was melt-extruded from a T die at a molding temperature of 260 ° C. in a ⁇ 40 mm T die casting apparatus made of PLABO, and cooled at a first roll temperature of 40 ° C. to produce an unstretched film with a film thickness of 100 ⁇ m. Puncture strength of the unstretched film obtained, Gelbo flex, oxygen permeability, respectively, 12.1 N, it was 24 /0.03m 2, 26.9cc / m 2 ⁇ day. It was 33% when the hot-water-shrinkage percentage of the stretched film obtained by extending
  • Example 5 An unstretched film was produced from the polyamide obtained in Example 4 using a press molding machine, and the cut-out sample was obtained in the same manner as in Example 1 except that it was preheated and stretched at an atmosphere temperature of 120 ° C. It was 37% when the hot water contraction rate of the oriented film was measured. The results are shown in Table 1.
  • Example 6 An unstretched film was produced from the polyamide obtained in Example 4 using a press molding machine, and the cut-out sample was obtained in the same manner as in Example 1 except that it was preheated and stretched at an atmosphere temperature of 150 ° C. It was 39% when the hot water contraction rate of the stretched film was measured. The results are shown in Table 1.
  • Example 7 The polyamide obtained in Example 4 was melt extruded from a T die at a molding temperature of 260 ° C. in a ⁇ 40 mm T die casting apparatus made of PLABO and cooled at a first roll temperature of 40 ° C. to prepare an unstretched film with a film thickness of 100 ⁇ m. .
  • the obtained unstretched film was simultaneously biaxially stretched to a stretching speed of 150 mm / sec, a stretching temperature of 80 ° C., and a stretch ratio of 3.0 ⁇ 3.0 times using a Iwate BIX 703 lab stretching machine, and then 120
  • the heat treatment was performed with heated air of 0 ° C. to prepare a 25 ⁇ m thick biaxially stretched film.
  • the stretched film was left to stand in an atmosphere of 23 ° C. and 50% RH for a whole day and then left in hot water of 90 ° C. for 1 minute to measure the hot water shrinkage, which was 49%.
  • Table 2 The results are shown in Table 2.
  • Example 8 A stretched film obtained in the same manner as in Example 7 except that the unstretched film obtained in Example 7 was simultaneously biaxially stretched at a stretching temperature of 100 ° C. and then heat-treated with heated air at 100 ° C. It was 50% when the hot water contraction rate of was measured. The results are shown in Table 2. Moreover, the puncture strength of the obtained stretched film was 15.4N.
  • Example 9 A stretched film obtained in the same manner as in Example 7 except that the unstretched film obtained in Example 7 was simultaneously biaxially stretched at a stretching temperature of 120 ° C. and then heat-treated with heated air at 120 ° C. It was 51% when the hot water contraction rate of was measured. The results are shown in Table 2.
  • Example 10 16.10 kg (70% by weight) of ⁇ -caprolactam, 11.50 kg of a 50% equimolar salt solution of HMD and AA (25% by weight of equimolar salt of HMD and AA), 0.592 kg of 80% HMD aqueous solution, terephthalic acid A polyamide was obtained in the same manner as in Example 4 except that (TPA: manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.677 kg (the molar ratio of HMD to TA was 1: 1) (5% by weight). The ⁇ r of this polyamide was 3.9.
  • Example 11 It was 50% when the hot water shrinkage rate of the stretched film obtained by carrying out similarly to Example 8 using the polyamide obtained in Example 10 was measured. The results are shown in Table 2. Moreover, the puncture strength of the obtained stretched film was 15.1N.
  • Example 12 13.80 kg (60% by weight) of ⁇ -caprolactam, 16.10 kg of a 50% equimolar salt solution of HMD and AA (35% by weight of equimolar salt of HMD and AA), 0.592 kg of 80% HMD aqueous solution, terephthalic acid
  • a polyamide was obtained in the same manner as in Example 4, except that (TA: manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.677 kg (the molar ratio of HMD to TA was 1: 1) (5% by weight).
  • the ⁇ r of this polyamide was 3.15.
  • the puncture strength and the gelvoflex of the unstretched film obtained from this polyamide in the same manner as in Example 7 were 9.4 N and 5 pieces / 0.03 m 2 , respectively. It was 40% when the stretched film obtained by carrying out similarly to Example 7 using the obtained unstretched film was left to stand in a 60 degreeC hot water for 1 minute, and a hot water contraction rate was measured. The results are shown in Table 2.
  • Example 13 13.80 kg (60% by weight) of ⁇ -caprolactam, 11.50 kg of a 50% equimolar salt solution of HMD and AA (25% by weight of equimolar salt of HMD and AA), 1.775 kg of 80% HMD solution, terephthalic acid
  • a polyamide was obtained in the same manner as in Example 4 except that (TA: manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 2.031 kg (the molar ratio of HMD to TA was 1: 1) (15% by weight).
  • the ⁇ r of this polyamide was 2.98.
  • the puncture strength and the gelboflex of the unstretched film obtained from this polyamide in the same manner as in Example 7 were 9.3 N and 17 pieces / 0.03 m 2 , respectively. It was 40% when the stretched film obtained by carrying out similarly to Example 7 using the obtained unstretched film was left to stand in a 60 degreeC hot water for 1 minute, and a hot water contraction rate was measured. The results are shown in Table 2.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne une résine polyamide pour emballage rétractable et un film de celle-ci, la résine polyamide contenant au moins trois types d'unités, comprenant une unité (A) dérivée d'un lactame et/ou d'un acide aminocarboxylique, et une unité (B) dérivée d'un sel équimolaire d'acide diamine-dicarboxylique, l'unité (B) dérivée d'un sel équimolaire d'acide diamine-dicarboxylique comprenant une unité (B-1) qui ne présente pas de structure cyclique aromatique et une unité (B-2) qui a une structure cyclique aromatique.
PCT/JP2018/031896 2017-08-31 2018-08-29 Résine polyamide et film formé à partir de celle-ci WO2019044882A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110256268A (zh) * 2019-07-02 2019-09-20 扬州中宝药业股份有限公司 一种氨基己酸的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54152098A (en) * 1978-05-22 1979-11-29 Unitika Ltd Copolyamide
JPS63268744A (ja) * 1987-04-28 1988-11-07 Mitsubishi Kasei Corp 熱収縮性ポリアミドフイルム
WO2013002069A1 (fr) * 2011-06-27 2013-01-03 三菱瓦斯化学株式会社 Film multi-couches et contenant d'emballage à base du film
JP2017505364A (ja) * 2014-01-28 2017-02-16 ラディシフィル エス．ピー．エー． 高い透明性および低いガス透過性を有する三成分コポリマーならびにその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54152098A (en) * 1978-05-22 1979-11-29 Unitika Ltd Copolyamide
JPS63268744A (ja) * 1987-04-28 1988-11-07 Mitsubishi Kasei Corp 熱収縮性ポリアミドフイルム
WO2013002069A1 (fr) * 2011-06-27 2013-01-03 三菱瓦斯化学株式会社 Film multi-couches et contenant d'emballage à base du film
JP2017505364A (ja) * 2014-01-28 2017-02-16 ラディシフィル エス．ピー．エー． 高い透明性および低いガス透過性を有する三成分コポリマーならびにその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110256268A (zh) * 2019-07-02 2019-09-20 扬州中宝药业股份有限公司 一种氨基己酸的制备方法

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