WO2017150410A1 - ポリアミド樹脂及びそれからなるフィルム - Google Patents
ポリアミド樹脂及びそれからなるフィルム Download PDFInfo
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- WO2017150410A1 WO2017150410A1 PCT/JP2017/007345 JP2017007345W WO2017150410A1 WO 2017150410 A1 WO2017150410 A1 WO 2017150410A1 JP 2017007345 W JP2017007345 W JP 2017007345W WO 2017150410 A1 WO2017150410 A1 WO 2017150410A1
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- polyamide resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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 polyamide resin excellent in heat shrinkability and a film comprising the same.
- 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 alicyclic structure in a molecular chain is excellent in heat shrinkability, 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 including a unit having no (B-1) alicyclic structure and a unit having (B-2) an alicyclic structure.
- the present invention it is possible to provide a polyamide resin excellent in heat shrinkability 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 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 It is a polyamide resin including a unit having no (B-1) alicyclic structure and a unit having (B-2) an alicyclic 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. 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, as units derived from equimolar salts of (B) diamine and dicarboxylic acid, (B-1) a unit having no alicyclic structure and (B-2) a unit having an alicyclic structure .
- 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 alicyclic structure contained in the polyamide resin (B-1) has an alicyclic structure derived from an equimolar salt or equimolar mixture of diamine and dicarboxylic acid
- diamines other than diamines having an alicyclic 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- Methyl-1,6-hexanediamine, 3,3-di
- dicarboxylic acids other than dicarboxylic acids having an alicyclic structure include 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
- the unit having an alicyclic structure contained in the polyamide resin (B-2) is derived from an equimolar salt or 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 alicyclic structure, or an equimolar salt or equimolar mixture of a diamine and a dicarboxylic acid having an alicyclic structure. Formed by polymerizing.
- diamine having an alicyclic structure cyclopropanediamine, cyclopropyldiaminomethyl, cyclobutyldiaminomethyl, cyclopentyldiaminomethyl, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 1,2-cyclohexane
- Alicyclic diamines such as diamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane and the like; 1-amino-3-aminomethyl-3 5,5-trimethylcyclohexane (hereinafter, also referred to as “isophorone diamine”), 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexane Methylamine, (4-amino
- At least one selected from the group consisting of these is preferred, at least one selected from branched alicyclic diamines is more preferred, and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane is preferred. More preferable.
- 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane which is a branched alicyclic diamine, is a stereoisomer generally referred to as a cis form or a trans form according to the conformation.
- diamines having an alicyclic structure include cis-1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane and trans-1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane It is preferable to include at least one. These diamines may be used alone or in combination of two or more.
- dicarboxylic acids having an alicyclic structure examples include alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and dicyclohexylmethane-4,4'-dicarboxylic acid.
- An acid is mentioned, at least one is preferred, and 1,4-cyclohexanedicarboxylic acid is more preferred.
- 1,4-cyclohexanedicarboxylic acid which is an alicyclic dicarboxylic acid has a stereoisomer generally referred to as a cis form or a trans form depending on the conformation, but any may be present. Both may be mixed and used by an appropriate ratio. That is, the dicarboxylic acid having an alicyclic structure preferably contains at least one of cis-1,4-cyclohexanedicarboxylic acid and trans-1,4-cyclohexanedicarboxylic acid, and the cis / trans ratio is 100/0 to More preferably, it is 51/49. These dicarboxylic acids may be used alone or in combination of two or more.
- the cis / trans ratio which is the isomer ratio of diamine and dicarboxylic acid having an alicyclic structure used in the present invention, can be determined by nuclear magnetic resonance spectroscopy (NMR) or liquid chromatography.
- NMR nuclear magnetic resonance spectroscopy
- HPLC high performance liquid chromatography
- 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, Preferably, it is 12 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) unit having an alicyclic 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 alicyclic structure is at least the above lower limit, the stretchability and the 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 content of the unit having an alicyclic structure (B-2) can be determined as follows.
- the proportion of the unit having an alicyclic structure (B-2) is a dicarboxylic acid having no alicyclic 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 alicyclic structure (B-2) is an alicyclic 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 alicyclic 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 alicyclic 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 alicyclic structure (B-2)
- the ratio of is the sum of the weight of both equimolar parts (% by weight), the sum of the weight of the unit having the remaining alicyclic structure and the weight of the unit not having the same molar alicyclic structure ((% by weight) % By weight).
- (B) When the total content of units derived from equimolar salts of diamine and dicarboxylic acid is 10 to 45% by weight, it has no (B-1) alicyclic structure contained in all units of the polyamide resin
- the unit content is 1 to 44.9% by weight, preferably 1 to 44.5% by weight, and more preferably 1 to 44% by weight.
- practical physical properties such as mechanical strength tend to be further improved.
- stretchability and heat shrinkability to improve more as it is below the said upper limit.
- the unit having (B-2) alicyclic structure contained in all units of 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 alicyclic structure is at least the above lower limit, the stretchability and the 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 unit having (B-2) an alicyclic structure 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 alicyclic structure is at least the above lower limit, the stretchability and the 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.
- Content ratio of units having an alicyclic structure [(B-2) to total content of units derived from a lactam and / or an aminocarboxylic acid and a unit not having an alicyclic 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 alicyclic structure is at least 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 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 not having an alicyclic structure are charged as equimolar salts thereof, and (B-2) diamine and a dicarboxylic acid constituting a unit having an alicyclic 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. 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 ( ⁇ pair) measured by the method described in JIS K6810 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.
- Example 1 1064.01 g (82 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 Equimolar salt of diamine (HMD) and adipic acid (AA) 50% aqueous solution 416.50 g (equimolar salt of HMD and AA: 16% by weight), 10.46 g of HMD, 1,4-cyclohexanedicarboxylic acid (CHDA: Tokyo Chemical Industry Co., Ltd., 15.49 g (the molar ratio of HMD and CHDA is 1: 1) (2 wt%) of cis / trans ratio 77/23, and sodium hypophosphite 0.065 g are charged.
- HMD diamine
- AA adipic acid
- CHDA 1,4-cyclohexanedicarboxylic acid
- CHDA 1,4-cyclohexanedicarboxylic
- Nitrogen pressurization and depressurization were repeated several times, and the inside of the pressure vessel was purged with nitrogen and then heated gradually. Stirring was performed at a speed of 50 rpm. The temperature is raised from room temperature to 240 ° C. over 2 hours, polymerized at 240 ° C. for 2 hours, released to a gauge pressure of 0 MPa, and subsequently polymerized at 240 ° C. for 2.7 hours while flowing nitrogen gas at 260 ml / min. To obtain a polyamide. After completion of the polymerization, the stirring was stopped, and a colorless and transparent polyamide in a molten state was drawn out in a string from the polymer outlet, cooled with water, and pelletized to obtain pellets. The pellet was washed by stirring in hot water for 6 hours to remove unreacted monomer, and then vacuum dried at 110 ° C. for 72 hours. The ⁇ r of the obtained polyamide was 3.8.
- Example 2 106 6.00 g (82% by weight) of ⁇ -caprolactam, 416.05 g of an equimolar salt solution of HMD and AA in water (416.05 g of an equimolar salt of HMD and AA: 16% by weight), isophorone diamine (IPD: Huls Japan Ltd.)
- the product was manufactured under the trade name VESTAMIN IPD (12.93 g) and CHDA 13.06 g (the molar ratio of IPD to CHDA is 1: 1) (2% by weight).
- the procedure of Example 1 was repeated to obtain a polyamide.
- the ⁇ r of this polyamide was 4.1.
- An unstretched film and a stretched film were produced from this polyamide in the same manner as in Example 1, and the hot water shrinkage was measured to be 24%.
- Table 1 The results are shown in Table 1.
- Example 3 1065.99 g (82 wt%) of ⁇ -caprolactam, 208.13 g of a 50% equimolar salt solution of HMD and AA (equimolar salt of HMD and AA: 8 wt%), 64.68 g of IPD, 65.41 g of CHDA (IPD
- the molar ratio of 1 to CHDA was 1: 1) (10% by weight), and carried out in the same manner as in Example 1 to obtain a polyamide.
- the ⁇ r of this polyamide was 3.8.
- An unstretched film and a stretched film were produced from this polyamide by the same method as in Example 1, and the hot water shrinkage was measured to be 29%. The results are shown in Table 1.
- Example 4 975.00 g (75% by weight) of ⁇ -caprolactam, 597.95 g of an equimolar salt solution of HMD and AA (59.95 g of an equimolar salt of HMD and AA: 23% by weight), 10.48 g of HMD, 15.52 g of CHDA (HMD The molar ratio of 1 to CHDA was 1: 1) (2% by weight), and the procedure of Example 1 was repeated to obtain a polyamide.
- the ⁇ r of this polyamide was 4.1.
- An unstretched film and a stretched film were produced from this polyamide in the same manner as in Example 1, and the hot water shrinkage was measured to be 28%. The results are shown in Table 1.
- Example 5 99.0.03 g (75% by weight) of ⁇ -caprolactam, 607.22 g of a 50% equimolar salt solution of HMD and AA (23% by weight of equimolar salt of HMD and AA), 14.21 g of IPD, 12.19 g of AA (IPD
- the molar ratio of A to AA was 1: 1) (2% by weight), and carried out in the same manner as in Example 1 to obtain a polyamide.
- the ⁇ r of this polyamide was 4.3.
- An unstretched film and a stretched film were produced from this polyamide in the same manner as in Example 1, and the hot water shrinkage was measured to be 27%. The results are shown in Table 1.
- Example 6 101.50 g (75 wt%) of ⁇ -caprolactam, 624.68 g of a 50% equimolar salt solution of HMD and AA (23 wt% equimolar salt of HMD and AA), 13.51 g of IPD, 13.64 g of CHDA
- the molar ratio of 1 to CHDA was 1: 1) (2% by weight), and the procedure of Example 1 was repeated to obtain a polyamide.
- the ⁇ r of this polyamide was 3.9.
- An unstretched film and a stretched film were produced from this polyamide in the same manner as in Example 1, and the hot water shrinkage was measured to be 26%. The results are shown in Table 1.
- Example 7 ⁇ -caprolactam 912.80 g (70% by weight), equimolar salt of HMD and AA 50% aqueous solution 730.18 g (equimolar salt of HMD and AA: 28% by weight), IPD 12.97 g, CHDA 13.11 g (IPD The molar ratio of 1 to CHDA was 1: 1) (2% by weight), and the procedure of Example 1 was repeated to obtain a polyamide.
- the ⁇ r of this polyamide was 4.3. An unstretched film and a stretched film were produced from this polyamide in the same manner as in Example 1, and the hot water shrinkage was measured to be 36%. The results are shown in Table 1.
- Example 8 A 70-liter pressure-resistant container equipped with a stirrer, thermometer, pressure gauge, pressure controller, nitrogen gas inlet, outlet and polymer outlet: ⁇ -caprolactam 18859 g (82% by weight), equimolar between HMD and AA 3679 g of a 50% aqueous salt solution (equimolar salt of HMD and AA: 8% by weight), 1146 g of IPD, 1157 g of CHDA (1: 1 molar ratio of IPD to CHDA) (10% by weight), 1.2 g of sodium hypophosphite 2161 g of distilled water was charged, nitrogen pressurization and depressurization were repeated several times, and the inside of the pressure resistant container was purged with nitrogen and then heated up to 240 ° C.
- 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 unstretched films with a total film thickness of 50 ⁇ m and 100 ⁇ m.
- the 50 ⁇ m unstretched film was measured for the puncture strength as it was.
- For 100 ⁇ m using a BIX 703 laboratory stretching machine manufactured by Iwamoto Seisakusho, after performing simultaneous biaxial stretching to a stretching speed of 150 mm / sec, a stretching temperature of 80 ° C., and a stretching ratio of 2.7 ⁇ 2.7 times, heated air at 120 ° C. The heat treatment was performed 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 overnight, and the hot water shrinkage was measured to be 39%. The results are shown in Table 2.
- Example 9 1-5000 g (75% by weight) of ⁇ -caprolactam, 4000 g of a 50% equimolar salt solution of HMD and AA (equi-molar salt of HMD and AA: 10% by weight), 1615 g of IPD, 1385 g of AA (molar ratio of IPD to AA 1: 1) (15% by weight), 1.2 g of sodium hypophosphite and 2000 g of distilled water were charged, and carried out in the same manner as in Example 8 to obtain a polyamide.
- the ⁇ r of this polyamide was 3.7.
- An unstretched film and a stretched film were produced from this polyamide by the same method as in Example 8, and the hot water shrinkage was measured to be 46%.
- Table 2 The results are shown in Table 2.
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Abstract
Description
3種以上の単位を含むポリアミド樹脂であって、
(A)ラクタム及び/又はアミノカルボン酸に由来する単位並びに
(B)ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、
前記(B)ジアミン及びジカルボン酸の等モル塩に由来する単位は、
(B-1)脂環構造を有さない単位及び
(B-2)脂環構造を有する単位
を含むポリアミド樹脂である。
(A)ラクタム及び/又はアミノカルボン酸に由来する単位並びに
(B)ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、
前記(B)ジアミン及びジカルボン酸の等モル塩に由来する単位は、
(B-1)脂環構造を有さない単位及び
(B-2)脂環構造を有する単位
を含むポリアミド樹脂である。
ポリアミド樹脂に含まれる(A)ラクタム及び/又はアミノカルボン酸に由来する単位は、ラクタム及び/又はアミノカルボン酸を重合に供することでポリアミド樹脂中に導入することができる。
ラクタムとしては、ε-カプロラクタム、ω-エナントラクタム、ω-ウンデカラクタム、ω-ドデカラクタム、2-ピロリドンなどが挙げられ、これらからなる群から選択される少なくとも1種が好ましい。
アミノカルボン酸としては、6-アミノカプロン酸、7-アミノヘプタン酸、8-アミノオクタン酸、10-アミノカプリン酸、11-アミノウンデカン酸、12-アミノドデカン酸などが挙げられ、これらからなる群から選択される少なくとも1種が好ましい。
これらのラクタム及びアミノカルボン酸は単独で使用してもよく、2種類以上を適宜組み合わせて使用してもよい。ラクタムとアミノカルボン酸を併用する場合、任意の割合で混合して使用することができる。
ポリアミド樹脂は、(B)ジアミン及びジカルボン酸の等モル塩に由来する単位として、(B-1)脂環構造を有さない単位と、(B-2)脂環構造を有する単位とを含む。ここで、ジアミン及びジカルボン酸の等モル塩に由来する単位は、ジアミン及びジカルボン酸の等モル塩又は等モル混合物を重合して形成される単位であり、1種類のジアミン及び1種類のジカルボン酸の組合せで1種類の単位とみなす。なお、当該単位を構成するジアミン及びジカルボン酸は直接縮合していても、他の単位又は他の単位を構成するジアミン若しくはジカルボン酸を介して縮合していてもよい。
ポリアミド樹脂に含まれる(B-1)脂環構造を有さない単位は、ジアミン及びジカルボン酸の等モル塩又は等モル混合物に由来する脂環構造を有さない単位であり、脂環構造を有するジアミン以外のジアミンと、脂環構造を有するジカルボン酸以外のジカルボン酸とを重合することで形成される。
これらのジアミンは1種類で使用してもよいし、2種類以上を適宜組み合わせて使用してもよい。
これらのジカルボン酸は1種類で使用してもよいし、2種類以上を適宜組み合わせて使用してもよい。
ポリアミド樹脂に含まれる(B-2)脂環構造を有する単位は、ジアミン及びジカルボン酸の等モル塩又は等モル混合物に由来し、ジアミン及びジカルボン酸の少なくとも一方に脂環構造を有する単位であり、例えば、ジカルボン酸及び脂環構造を有するジアミンの等モル塩若しくは等モル混合物、又はジアミン及び脂環構造を有するジカルボン酸の等モル塩若しくは等モル混合物を重合することで形成される。
これらのジアミンは1種類で使用してもよいし、2種類以上を適宜組み合わせて使用してもよい。
ここで、脂環族ジカルボン酸である1,4-シクロヘキサンジカルボン酸は、立体配座によりシス体、トランス体と一般的に称される立体異性体が存在するが、いずれであってもよく、両者を適宜の比率で混合して使用してもよい。すなわち、脂環構造を有するジカルボン酸は、シス-1,4-シクロヘキサンジカルボン酸及びトランス-1,4-シクロヘキサンジカルボン酸の少なくとも一方を含むことが好ましく、シス体/トランス体比が100/0~51/49であることがより好ましい。
これらのジカルボン酸は1種類で使用してもよいし、2種類以上を適宜組み合わせて使用してもよい。
ポリアミド樹脂の全単位中における(A)ラクタム及び/又はアミノカルボン酸に由来する単位の含有率と(B)ジアミン及びジカルボン酸の等モル塩に由来する単位の総含有率との合計は、実用的な物性の観点から、90~100重量%となることが好ましく、95~100重量%となることがより好ましく、97~100重量%となることがさらに好ましい。
ポリアミド樹脂に含まれる脂環構造を有する単位がジアミン単位のみの場合、(B-2)脂環構造を有する単位の割合は、当該ジアミン単位の重量と等モルの脂環構造を有しないジカルボン酸単位の重量との和(重量%)である。同様に、ポリアミド樹脂に含まれる脂環構造を有する単位がジカルボン酸単位のみの場合、(B-2)脂環構造を有する単位の割合は、当該ジカルボン酸単位の重量と等モルの脂環構造を有しないジアミン単位の重量との和(重量%)である。ポリアミド樹脂に含まれる脂環構造を有する単位がジアミン単位とジカルボン酸単位の両方である場合、(B-2)脂環構造を有する単位の割合は、当該ジアミン単位の重量と当該ジカルボン酸単位の重量の等モルである部分の重量の和(重量%)である。ポリアミド樹脂に含まれる脂環構造を有する単位がジアミン単位とジカルボン酸単位の両方である場合で、当該ジアミン単位と当該ジカルボン酸単位が等モルでない場合、(B-2)脂環構造を有する単位の割合は、両方の等モルである部分の重量の和(重量%)に、残余の脂環構造を有する単位の重量とこれと等モルの脂環構造を有しない単位の重量との和(重量%)を加えたものである。
ポリアミド樹脂の製造方法で使用する水は、酸素を除去したイオン交換水、蒸留水等を使用することが望ましく、その使用量はポリアミド樹脂を構成する原料100重量部に対して、例えば1~150重量部である。
ポリアミド樹脂からのフィルムの製造方法には、公知のフィルム製造方法、例えば、溶融押出機を用いたTダイ法、インフレーション法、チューブラー法、溶剤キャスト法、熱プレス法などの製造方法を適用することができる。溶融押出機を用いた方法でのポリアミドの溶融温度は、例えば、使用するポリアミドの融点以上320℃以下である。
JIS K6810に準じ、96重量%の濃硫酸を溶媒として、1重量/容量%のポリアミド濃度で、ウベローデ粘度計を用い、25℃の温度で測定した。
フィルムに記した標線間距離(=L)を測定後、無緊張状態で90℃の熱水中に1分間放置し、標線間の縮み量(=ΔL)を測定し、収縮率(%)=ΔL/L×100として算出した。
試験片を23℃、50%RH条件下で24時間調湿し、同条件下で、TOYO BALDWIN社製テンシロンUTM-III-200を使用して、先端直径0.5mmの針が50mm/minの速度で試験片を突き抜けた時の最大荷重を測定し、試験片厚み(mm)で除した数値として算出した。
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、放圧口、圧力調整装置及びポリマー取り出し口を備えた5リットルの圧力容器にε-カプロラクタム1064.01g(82重量%)、ヘキサメチレンジアミン(HMD)とアジピン酸(AA)との等モル塩50%水溶液416.50g(HMDとAAとの等モル塩:16重量%)、HMD10.46g、1,4-シクロヘキサンジカルボン酸(CHDA:東京化成工業株式会社製、シス体/トランス体比が77/23)15.49g(HMDとCHDAのモル比が1:1)(2重量%)、次亜リン酸ナトリウム0.065gを仕込み、窒素加圧と放圧を数回繰り返し、圧力容器内を窒素置換してから徐々に加熱を行った。撹拌は速度50rpmで行った。2時間かけて室温から240℃まで昇温し、240℃で2時間重合させた後、ゲージ圧力0MPaまで放圧し、引き続き、窒素ガスを260ml/分で流しながら、240℃で2.7時間重合を行い、ポリアミドを得た。重合終了後、撹拌を停止し、ポリマー取り出し口から溶融状態の無色透明のポリアミドを紐状に抜き出し、水冷した後、ペレタイズしてペレットを得た。このペレットを熱水中、6時間撹拌洗浄し、未反応モノマーを除去した後、110℃で72時間真空乾燥した。得られたポリアミドのηrは3.8であった。
この未延伸フィルムから切り出した縦90mm、横10mmの試料に標線(50mm間隔)を引いて引張試験機(オリエンテック製テンシロンRTA-10KN)に取り付け、80℃の雰囲気温度(延伸時温度)で約1分間予熱した後、同温度下、変形速度150mm/分でフィルムの縦方向に2.7倍に延伸した。この延伸フィルムを23℃、50%RHの雰囲気中に一昼夜放置した後、熱水収縮率を測定したところ、23%であった。その結果を表1に示す。
ε-カプロラクタム1066.00g(82重量%)、HMDとAAとの等モル塩50%水溶液416.05g(HMDとAAとの等モル塩:16重量%)、イソホロンジアミン(IPD:ヒュルスジャパン社製、商品名VESTAMIN IPD)12.93g、CHDA13.06g(IPDとCHDAのモル比が1:1)(2重量%)を仕込み、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.1であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、24%であった。その結果を表1に示す。
ε-カプロラクタム1065.99g(82重量%)、HMDとAAとの等モル塩50%水溶液208.13g(HMDとAAとの等モル塩:8重量%)、IPD64.68g、CHDA65.41g(IPDとCHDAのモル比が1:1)(10重量%)を仕込み、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは3.8であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、29%であった。その結果を表1に示す。
ε-カプロラクタム975.00g(75重量%)、HMDとAAとの等モル塩50%水溶液597.95g(HMDとAAとの等モル塩:23重量%)、HMD10.48g、CHDA15.52g(HMDとCHDAのモル比が1:1)(2重量%)を仕込み、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.1であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、28%であった。その結果を表1に示す。
ε-カプロラクタム990.03g(75重量%)、HMDとAAとの等モル塩50%水溶液607.22g(HMDとAAとの等モル塩:23重量%)、IPD14.21g、AA12.19g(IPDとAAのモル比が1:1)(2重量%)を仕込み、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.3であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、27%であった。その結果を表1に示す。
ε-カプロラクタム1018.50g(75重量%)、HMDとAAとの等モル塩50%水溶液624.68g(HMDとAAとの等モル塩:23重量%)、IPD13.51g、CHDA13.64g(IPDとCHDAのモル比が1:1)(2重量%)を仕込み、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは3.9であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、26%であった。その結果を表1に示す。
ε-カプロラクタム912.80g(70重量%)、HMDとAAとの等モル塩50%水溶液730.18g(HMDとAAとの等モル塩:28重量%)、IPD12.97g、CHDA13.11g(IPDとCHDAのモル比が1:1)(2重量%)を仕込み、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.3であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、36%であった。その結果を表1に示す。
ε-カプロラクタム1066.00g(82重量%)、HMDとAAとの等モル塩50%水溶液468.00g(HMDとAAとの等モル塩:18重量%)を仕込み、脂環構造を有するジアミン及びジカルボン酸を使用しない以外は、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.0であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、19%であった。その結果を表1に示す。
ε-カプロラクタム975.00g(75重量%)、HMDとAAとの等モル塩50%水溶液650.00g(HMDとAAとの等モル塩:25重量%)を仕込み、脂環構造を有するジアミン及びジカルボン酸を使用しない以外は、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.4であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、22%であった。その結果を表1に示す。
ε-カプロラクタム910.00g(70重量%)、HMDとAAとの等モル塩50%水溶液780.00g(HMDとAAとの等モル塩:30重量%)を仕込み、脂環構造を有するジアミン及びジカルボン酸を使用しない以外は、実施例1と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.0であった。このポリアミドから実施例1と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、30%であった。その結果を表1に示す。
攪拌機、温度計、圧力計、圧力制御装置、窒素ガス導入口、放圧口及びポリマー取り出し口を備えた70リットルの耐圧容器にε-カプロラクタム18859g(82重量%)、HMDとAAとの等モル塩50%水溶液3679g(HMDとAAとの等モル塩:8重量%)、IPD1146g、CHDA1157g(IPDとCHDAのモル比が1:1)(10重量%)、次亜リン酸ナトリウム1.2g及び蒸留水2161gを仕込み、窒素加圧と放圧を数回繰り返し、耐圧容器内を窒素置換してから240℃まで昇温した。240℃で2時間重合させた後、ゲージ圧力0MPaまで放圧し、引き続き、窒素ガスを260L/hで流しながら、240℃で2.9時間重合を行い、ポリアミドを得た。重合終了後、撹拌を停止し、ポリマー取り出し口から溶融状態の無色透明のポリアミドを紐状に抜き出し、水冷した後、ペレタイズしてペレットを得た。このペレットを熱水流通下、12時間洗浄し、未反応モノマーを除去した後、110℃で12時間真空乾燥した。得られたポリアミドのηrは3.9であった。
ε-カプロラクタム15000g(75重量%)、HMDとAAとの等モル塩50%水溶液4000g(HMDとAAとの等モル塩:10重量%)、IPD1615g、AA1385g(IPDとAAのモル比が1:1)(15重量%)、次亜リン酸ナトリウム1.2g及び蒸留水2000gを仕込み、実施例8と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは3.7であった。このポリアミドから実施例8と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、46%であった。その結果を表2に示す。
ε-カプロラクタム18860g(82重量%)、HMDとAAとの等モル塩50%水溶液8280g(HMDとAAとの等モル塩:18重量%)を仕込み、脂環構造を有するジアミン及びジカルボン酸を使用しない以外は、実施例8と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.0であった。このポリアミドから実施例8と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、35%であった。その結果を表2に示す。
ε-カプロラクタム17250g(75重量%)、HMDとAAとの等モル塩50%水溶液11500g(HMDとAAとの等モル塩:25重量%)を仕込み、脂環構造を有するジアミン及びジカルボン酸を使用しない以外は、実施例8と同様の方法で実施し、ポリアミドを得た。このポリアミドのηrは4.4であった。このポリアミドから実施例8と同様の方法で未延伸フィルム、延伸フィルムを作製し熱水収縮率を測定したところ、41%であった。その結果を表2に示す。
Claims (14)
- 3種以上の単位を含むポリアミド樹脂であって、
(A)ラクタム及び/又はアミノカルボン酸に由来する単位並びに
(B)ジアミン及びジカルボン酸の等モル塩に由来する単位を含み、
前記(B)ジアミン及びジカルボン酸の等モル塩に由来する単位は、
(B-1)脂環構造を有さない単位及び
(B-2)脂環構造を有する単位
を含むポリアミド樹脂。 - ポリアミド樹脂の全単位中に、
前記(A)ラクタム及び/又はアミノカルボン酸に由来する単位を50~98重量%、
前記(B-2)脂環構造を有する単位を1~49重量%含む請求項1に記載のポリアミド樹脂。 - 前記(B-1)脂環構造を有さない単位が、ヘキサメチレンジアミン及びアジピン酸の等モル塩に由来する単位である請求項1又は2に記載のポリアミド樹脂。
- 前記(B-2)脂環構造を有する単位が、分岐状脂環族ジアミンに由来する部分構造を含む請求項1~3のいずれかに記載のポリアミド樹脂。
- 前記分岐状脂環族ジアミンが、シス-1-アミノ-3-アミノメチル-3,5,5-トリメチルシクロヘキサン及び/又はトランス-1-アミノ-3-アミノメチル-3,5,5-トリメチルシクロヘキサンを含む請求項4に記載のポリアミド樹脂。
- 前記(B-2)脂環構造を有する単位が、シス-1,4-シクロヘキサンジカルボン酸及び/又はトランス-1,4-シクロヘキサンジカルボン酸に由来する部分構造を含む請求項1~5のいずれかに記載のポリアミド樹脂。
- 請求項1~6のいずれかに記載のポリアミド樹脂からなるフィルム。
- 請求項7に記載のフィルムからなる熱収縮性に優れたフィルム。
- 請求項1~6のいずれかに記載のポリアミド樹脂からなる延伸フィルム。
- 請求項9に記載の延伸フィルムからなる熱収縮性に優れた延伸フィルム。
- 請求項7に記載のフィルムを延伸してなる延伸フィルム。
- 請求項11に記載の延伸フィルムからなる熱収縮性に優れた延伸フィルム。
- 熱水収縮率が20~60%である請求項11に記載の延伸フィルム。
- 請求項13に記載の延伸フィルムからなる包装用材料。
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