Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
• • 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
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
  • B29C49/06—Injection blow-moulding
• • 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
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
  • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
  • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
  • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
  • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
  • B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
• • 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
• • 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
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
  • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/40—Closed containers
  • B32B2439/60—Bottles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to an injection blow molded container.
• Polyamide resin is an engineering plastic with excellent mechanical strength such as impact resistance and wear resistance, and excellent heat resistance, such as automotive parts, electronic / electric equipment parts, OA equipment parts, building materials and housing equipment-related parts.
• Patent Document 1 describes a multi-layer container using polymetaxylylene adipamide as a gas barrier resin.
• Patent Document 1 a structural unit derived from xylylenediamine represented by polymetaxylylene adipamide, a structural unit derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid, and Polyamide resins having the above have been used as gas barrier resins for forming a gas barrier layer, but containers having better moldability, impact resistance and solvent resistance have been demanded.
• An object of this invention is to provide the injection blow container excellent in the moldability and impact resistance, and also excellent in solvent resistance.
• the present invention has been made in view of such circumstances, and as a result of intensive studies to achieve the above object, the present inventors have found that 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine.
• 70 mol% or more of the structural units derived from dicarboxylic acid are structural units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and 30 mol% or less is derived from isophthalic acid.
• the polyamide resin (A), which is a constituent unit, and a polyamide resin (B) that does not contain a constituent unit derived from xylylenediamine and has an alkylene group having 5 to 12 carbon atoms are contained in a specific range.
• a container obtained by injection blow molding was excellent in moldability and impact resistance, and also excellent in solvent resistance, and the present invention was completed. It was. That is, the present invention relates to the following ⁇ 1> to ⁇ 14>.
• the polyamide resin (A) includes a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more of the structural unit derived from diamine is derived from xylylenediamine. 70 mol% or more of the structural unit derived from the dicarboxylic acid is a structural unit derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and 30 mol% or less is isophthalic acid.
• a structural unit derived from an acid wherein the polyamide resin (B) does not contain a structural unit derived from xylylenediamine and has an alkylene group having 5 to 12 carbon atoms.
• Injection blow molded container which is a bromide resin.
• the container is a two-layer container having a layer containing 60 to 95 parts by mass of the polyamide resin (A), 5 to 40 parts by mass of the polyamide resin (B), and another layer. The container as described in ⁇ 1>.
• ⁇ 4> The container according to any one of ⁇ 1> to ⁇ 3>, wherein the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms contains adipic acid.
• ⁇ 5> The container according to any one of ⁇ 1> to ⁇ 4>, wherein the xylylenediamine contains metaxylylenediamine.
• the polyamide resin (B) includes at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 666, polyamide 11, polyamide 12, and polyamide 6I6T, ⁇ 1> to ⁇ 5> A container according to any one of the above.
• the polyamide resin (A) is contained in an amount of 80 to 95 parts by mass, ⁇ 1> to ⁇ 6> A container according to any one of the above. ⁇ 8> The container according to any one of ⁇ 1> to ⁇ 7>, wherein 1 mol% or more of the structural unit derived from dicarboxylic acid of the polyamide resin (A) is a structural unit derived from isophthalic acid.
• the injection blow molded container is obtained by a method in which an injection process and a blow process are performed in the same apparatus, and blow molding is performed using residual heat held by a preform at the time of the injection process.
• a liquid containing at least one organic compound selected from the group consisting of hydrocarbons, alcohols, esters, ketones, and ethers is accommodated. Any one of ⁇ 1> to ⁇ 11> Container as described.
• an injection blow container which is excellent in moldability and impact resistance and further excellent in solvent resistance.
• the injection blow molded container of the present invention (hereinafter also simply referred to as “container”) is a layer containing polyamide resin (A) 60 to 95 parts by mass and polyamide resin (B) 5 to 40 parts by mass (hereinafter referred to as “container”).
• layer (X) Also referred to as “layer (X)” (the total of the polyamide resin (A) and the polyamide resin (B) is 100 parts by mass), and the polyamide resin (A) is derived from a diamine.
• a unit hereinafter, “structural unit derived from diamine” is also simply referred to as “diamine unit” and a structural unit derived from dicarboxylic acid (hereinafter, “structural unit derived from dicarboxylic acid” is simply referred to as “dicarboxylic acid unit”).
• 70 mol% or more of the structural unit derived from the diamine is a structural unit derived from xylylenediamine
• 70 mol% or more of the structural unit derived from the dicarboxylic acid is carbon.
• the container of the present invention comprises 60 to 95 parts by mass of the polyamide resin (A), 5 to 40 parts by mass of the polyamide resin (B), and 100 parts by mass of the total of the polyamide resin (A) and the polyamide resin (B).
• a resin composition hereinafter also referred to as “polyamide resin composition”.
• the container is excellent in moldability and impact resistance, Furthermore, it discovered that it was excellent in solvent resistance, and came to complete this invention.
• the polyamide resin (A) has been conventionally known as a polyamide resin excellent in solvent resistance and the like, but a container using the polyamide resin (A) alone has sufficient impact resistance. It was not obtained.
• the polyamide resin (B) that does not contain the structural unit, and providing a layer containing the polyamide resin (A) and the polyamide resin (B) in a specific range a container having excellent impact resistance can be obtained. I found it.
• the resin composition needs to be a cylindrical parison, and it is necessary to extrude at a high resin temperature. For this reason, it is considered that the resin composition extruded in a cylindrical shape from the die generates a weld line at a portion where the resin merges. Also, from the viewpoint of manufacturing, both ends of the hollow parison extruded into a cylindrical shape are open, and in order to obtain the parison as a blow molded container, one end serves as a high-pressure air sealing port, and the other end Need to be a portion where a cylindrical parison is fused (hereinafter also referred to as “pinch-off portion”).
• the container of the present invention has at least one layer (X) containing a polyamide resin (A) and a polyamide resin (B) described later.
• the polyamide resin (A) used in the present invention contains a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 70 mol% or more (70 to 100 mol%) of the structural unit derived from diamine is A structural unit derived from range amine, wherein 70 mol% or more (70 to 100 mol%) of the structural unit derived from dicarboxylic acid is derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms. 30 mol% or less (0 to 30 mol%) is a structural unit derived from isophthalic acid (however, the total does not exceed 100 mol%).
• the structural unit derived from diamine contains 70 mol% or more of structural units derived from xylylenediamine, preferably 80 mol% or more, more preferably 90 mol% or more.
• the structural unit derived from xylylenediamine may be either a structural unit derived from metaxylylenediamine, a structural unit derived from paraxylylenediamine, or a structural unit derived from orthoxylylenediamine, or one kind alone. Two or more types may be used in combination.
• the structural unit derived from xylylenediamine preferably contains at least one of a structural unit derived from metaxylylenediamine and a structural unit derived from paraxylylenediamine, and is derived from metaxylylenediamine It is more preferable to contain only the structural unit which does, or to contain the structural unit derived from metaxylylene diamine and the structural unit derived from paraxylylene diamine.
• the structural unit derived from xylylenediamine is a structural unit derived from 0 to 70 mol% derived from paraxylylenediamine and from metaxylylenediamine when the structural unit derived from xylylenediamine is 100 mol%. It is preferable to contain 30 to 100 mol%, more preferably 0 to 50 mol% of structural units derived from paraxylylenediamine and 50 to 100 mol% of structural units derived from metaxylylenediamine.
• the polyamide resin (A) contains a structural unit derived from dicarboxylic acid (dicarboxylic acid unit), and 70 mol% or more of the structural unit derived from dicarboxylic acid is an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms. It is a structural unit derived from an acid, and 30 mol% or less is a structural unit derived from isophthalic acid (however, the total does not exceed 100 mol%).
• the dicarboxylic acid unit constituting the polyamide resin (A) preferably contains 70 mol% or more of ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms from the viewpoint of improving moldability and solvent resistance.
• an upper limit is not specifically limited, It is 100 mol% or less, Preferably it is 99 mol% or less, More preferably, it is 97 mol% or less, More preferably, it is 96 mol% or less.
• the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms include suberic acid, adipic acid, azelaic acid, sebacic acid, and dodecanoic acid. From the viewpoint of moldability and solvent resistance, adipic acid And sebacic acid is preferred, and adipic acid is more preferred.
• the dicarboxylic acid unit constituting the polyamide resin (A) contains 30 mol% or less (0 to 30 mol%) of a structural unit derived from isophthalic acid from the viewpoint of improving moldability and impact resistance.
• the content of the structural unit derived from isophthalic acid is preferably 1 to 20 mol%, more preferably 3 to 10 mol%, still more preferably 4 to 8 mol% of the dicarboxylic acid unit.
• dicarboxylic acid unit other than ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms and isophthalic acid examples include alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, Aromatic dicarboxylic acids such as terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid and the like can be exemplified, but are not limited thereto.
• the total content of structural units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 12 carbon atoms and isophthalic acid is preferably 80 mol% or more of the total dicarboxylic acid unit, More preferably, it is 90 mol% or more, More preferably, it is 98 mol% or more, More preferably, it is 100 mol%.
• lactams such as ⁇ -caprolactam and laurolactam
• aminocaproic acid aminoundecanoic acid
• aminoundecanoic acid can be used as long as the effects of the present invention are not impaired.
• Aliphatic aminocarboxylic acids such as p-aminomethylbenzoic acid and the like can be used as copolymerized units.
• the polyamide resin (A) is produced by a melt polycondensation method (melt polymerization method). For example, there is a method in which a nylon salt composed of a diamine and a dicarboxylic acid is heated in the presence of water under pressure and polymerized in a molten state while removing added water and condensed water. It can also be produced by a method in which diamine is directly added to a molten dicarboxylic acid and polycondensed. In this case, in order to keep the reaction system in a uniform liquid state, diamine is continuously added to the dicarboxylic acid, while the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. The polycondensation proceeds.
• a melt polycondensation method melt polycondensation method
• a phosphorus atom-containing compound may be added in order to obtain an effect of promoting an amidation reaction and an effect of preventing coloration during polycondensation.
• Phosphorus atom-containing compounds include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphite, ethyl hypophosphite, phenyl Phosphonous acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate , Diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate, potassium ethylphosphonate,
• hypophosphorous acid metal salts such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, and calcium hypophosphite are particularly effective in accelerating the amidation reaction and are also effective in preventing coloring. Since it is excellent, it is preferably used, and sodium hypophosphite is particularly preferable, but the phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds.
• the amount of the phosphorus atom-containing compound added to the polycondensation system of the polyamide resin (A) is converted to the phosphorus atom concentration in the polyamide resin (A) from the viewpoint of preventing the polyamide resin (A) from being colored during the polycondensation. And preferably 1 to 500 ppm, more preferably 5 to 450 ppm, and still more preferably 10 to 400 ppm.
• the polycondensation system of the polyamide resin (A) it is preferable to add an alkali metal compound or an alkaline earth metal compound in combination with the phosphorus atom-containing compound.
• an alkali metal compound or an alkaline earth metal is required. It is preferable that the compound coexists.
• hydroxides of alkali metals / alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and lithium acetate
• sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate, and other alkali metal / alkaline earth metal acetates, etc. are not limited to these compounds.
• alkali metal hydroxides or alkali metal acetates are preferable.
• a value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound is preferably 0.5 to 2.0, more preferably 0.6 to 1.8, still more preferably 0.7 to 1.5.
• the polyamide resin (A) obtained by melt polycondensation is once taken out, pelletized, and dried before use. Further, in order to further increase the degree of polymerization, solid phase polymerization may be performed.
• a heating device used in drying or solid-phase polymerization a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum type heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer
• a conical heating apparatus provided with can be used suitably, a well-known method and apparatus can be used without being limited to these.
• the heating device of the rotating drum type in the above-mentioned apparatus can seal the inside of the system and facilitate polycondensation in a state where oxygen causing coloring is removed. Are preferably used.
• the relative viscosity of the polyamide resin (A) is preferably 1.5.
• the melting point of the polyamide resin (A) is preferably 180 to 280 ° C., more preferably 200 to 260 ° C., and further preferably 220 to 240 ° C. It is preferable for the melting point of the polyamide resin (A) to be in the above-mentioned range since the compatibility with the polyamide resin (B) is excellent, and as a result, impact resistance and solvent resistance are improved.
• the container of the present invention has at least one layer (X) containing the polyamide resin (A) and the polyamide resin (B) described above, and the polyamide resin (B) does not contain a structural unit derived from xylylenediamine. And a polyamide resin having an alkylene group having 5 to 12 carbon atoms. By containing the polyamide resin (B), the impact resistance is improved.
• the polyamide resin (B) include aliphatic polyamides and semi-aromatic polyamides.
• Aliphatic polyamides that do not contain structural units derived from metaxylylenediamine and have an alkylene group having 5 to 12 carbon atoms include polyamide 6 (also known as nylon 6), polyamide 66 (also known as nylon 66), and polyamide. 666 (a copolymer of polyamide 6 and polyamide 66, also known as nylon 666), polyamide 10 (also known as nylon 10), polyamide 11 (also known as nylon 11), polyamide 12 (also known as nylon 12), polyamide 46 (also known as: Nylon 46), polyamide 610 (alias: nylon 610), polyamide 612 (alias: nylon 612) are exemplified.
• Semi-aromatic polyamides that do not contain structural units derived from metaxylylenediamine and have an alkylene group of 5 to 12 carbon atoms include polyamide 6T (also known as nylon 6T, polyhexamethylene terephthalamide), polyamide Examples include 6I (alias: nylon 6I, polyhexamethylene isophthalamide), polyamide 6I6T (alias: nylon 6I6T, polyhexamethylene terephthalamide / polyhexamethylene isophthalamide), and the like.
• the use of the semi-aromatic polyamide as the polyamide resin (B) is preferable because a container having improved drop impact resistance can be obtained by imparting flexibility, and the container moldability can be improved by crystallization delay.
• polyamide resin (B) polyamide 6, polyamide 66, polyamide 666, polyamide 11, polyamide 12, and polyamide 6I6T are preferable from the viewpoint of improving impact resistance, and polyamide 6, polyamide 66, polyamide 666, and polyamide 12 are preferable.
• polyamide 6, polyamide 66 and polyamide 666 are further preferable, polyamide 6 and polyamide 666 are still more preferable, and polyamide 666 is particularly preferable.
• Tg (A) glass transition temperature of the polyamide resin (A)
• Tg (B) glass transition temperature of the polyamide resin (B) (° C.)
• Tg (A) -Tg (B) is more preferably 27 ° C. or higher, further preferably 30 ° C. or higher, and still more preferably 35 ° C. or higher.
• the upper limit is not particularly limited, but is preferably 100 ° C. or lower, more preferably 70 ° C.
• the polyamide resin (B) relieves stress generated in the polyamide resin (A) during and after molding, thereby providing a drop impact resistance. This is preferable because of improved properties.
• the glass transition temperature Tg (A) of the polyamide resin (A) is preferably 70 to 150 ° C., more preferably 75 to 130 ° C., and still more preferably 80 to 80 ° C. from the viewpoint of moldability and dimensional stability of the container. 110 ° C.
• the glass transition temperature Tg (B) of the polyamide resin (B) is preferably 20 to 120 ° C., more preferably 25 to 80 ° C., further preferably 30 to 60 ° C., from the viewpoint of impact resistance of the container. More preferably, it is 40 to 55 ° C.
• the polyamide-based resin composition used in the present invention has a polyamide resin (A) of 60 to 95 parts by mass, when the total of the polyamide resin (A) and the polyamide resin (B) is 100 parts by mass, and the polyamide resin (B) is contained in an amount of 5 to 40 parts by mass.
• the content of the polyamide resin (A) is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, still more preferably 85 parts by mass or more, and preferably 92 parts by mass or less.
• the content of the polyamide resin (B) is preferably 8 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.
• the polyamide resin composition used in the present invention may contain other resin components in addition to the polyamide resin (A) and the polyamide resin (B), but the content of the other resin components is as follows.
• the total resin component is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and still more preferably not contained.
• resin components include polyamide resin (A) and polyamide resin other than polyamide resin (B), polyphenylene ether resin, styrene resin, polycarbonate resin, acrylic resin, polyester resin, polyphenylene sulfide resin, liquid crystal polyester resin, polyacetal resin, Examples thereof include modified or unmodified elastomers such as styrene-ethylene-butylene-styrene copolymer (SEBS) and styrene-ethylene-propylene-styrene copolymer (SEPS).
• SEBS styrene-ethylene-butylene-styrene copolymer
• SEPS styrene-ethylene-propylene-styrene copolymer
• you may contain thermosetting resins, such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin.
• the polyamide resin composition contains a lubricant, a crystallization nucleating agent, a matting agent, a heat stabilizer, a weather stabilizer, an ultraviolet ray.
• a lubricant a crystallization nucleating agent
• a matting agent a heat stabilizer
• a weather stabilizer an ultraviolet ray.
• Absorber plasticizer, mold release agent, flame retardant, antistatic agent, anti-coloring agent, antioxidant, elastomer, inorganic pigment, organic pigment, dispersant, inorganic pigment masterbatch, organic pigment masterbatch, recycling aid
• Additives such as terminal functional group reactants and thickeners can be added. These additives can be added as necessary within a range not impairing the effects of the present invention.
• the method for preparing the polyamide resin composition is not particularly limited.
• the polyamide resin (A) and the polyamide resin (B) can be melt-kneaded in an extruder to obtain a desired polyamide resin composition. it can.
• each component of the polyamide-based resin composition may be mixed and melt-kneaded at the same time, or in order to improve the kneading dispersibility of the component having a small content, a master batch is prepared in advance and melt-kneaded again to obtain a polyamide.
• -Based resin compositions may be produced.
• a master batch is prepared by melt-kneading the polyamide resin (A), the polyamide resin (B), and other components such as a terminal functional group reactant, a recycling aid, and a colorant as necessary. And the master batch and the polyamide resin (A) may be melt-kneaded. Further, the polyamide resin (A) and other components may be melt-kneaded to prepare a master batch, and the master batch, the polyamide resin (A), and the polyamide resin (B) may be melt-kneaded. Not.
• the masterbatch and the polyamide resin (A) may be dry blended, and the obtained dry blend product may be directly put into a molding machine such as an injection molding machine. Further, the master batch and the polyamide resin (A) may be measured by a feeder and then directly molded by a molding machine such as an injection molding machine. Moreover, after dry-blending a masterbatch and a polyamide resin (A), you may shape
• the set temperature of the cylinder at the time of melt kneading is preferably 210 to 280 ° C, more preferably 220 to 270 ° C, and further preferably 230 to 260 ° C.
• the time for melt kneading is not particularly limited, but is preferably 1 second to 5 minutes, more preferably 3 seconds to 4 minutes, and further preferably 5 seconds to 3 minutes.
• the apparatus used for melt kneading is not particularly limited, but an open type mixing roll, a non-open type Banbury mixer, a kneader, a continuous kneader (single screw kneader, twin screw kneader, multi screw kneader, etc.), etc. Can be mentioned.
• the container of this invention is obtained by carrying out injection blow molding using the said polyamide-type resin composition.
• the container of the present invention is preferably a hollow container.
• the container of the present invention has at least one layer (X) obtained by using the polyamide-based resin composition, but a two-layer container having the layer (X) and another layer, or the above A single-layer container consisting of only the layer (X) is preferred, a single-layer container consisting of only the layer (X) is more preferred, and a single-layer hollow container is even more preferred.
• the container of this invention is a two-layer container, although it does not specifically limit as another layer, For example, the layer which consists of polyolefin resin is mentioned.
• the capacity of the container of the present invention is preferably 2 mL to 3 L, more preferably 5 mL to 1 L, still more preferably 8 mL to 500 mL, and particularly preferably 10 mL to 100 mL.
• the average thickness of the body part of the container of the present invention is preferably 0.1 mm or more, more preferably 0.3 mm or more, further preferably 0.4 mm or more, and 0.5 mm or more. It is still more preferable that it is 0.8 mm or more. Moreover, it is preferable that it is 3 mm or less, it is more preferable that it is 2 mm or less, and it is still more preferable that it is 1.5 mm or less. It is preferable that the average thickness of the body portion of the container is in the above-mentioned range since a container having excellent impact resistance and solvent resistance and having a light weight can be obtained.
• the shape of the container of the present invention is not particularly limited, but is preferably a hollow container, and various shapes such as a bottle shape, a cup shape, a tray shape, and a tank shape can be adopted. Among these, a bottle shape or a tank shape is preferable, and a bottle shape is more preferable.
• a container produced by the direct blow method, particularly a bottle-shaped container, according to the present invention a container excellent in impact resistance and solvent resistance is provided.
• the container is particularly suitable as a bottle-shaped container.
• the container of the present invention preferably contains a liquid containing an organic compound, and is at least one organic selected from the group consisting of hydrocarbons, alcohols, esters, ketones, and ethers. It is more preferable to store a liquid containing a compound, and it is more preferable to store an organic solvent selected from the group consisting of hydrocarbons, alcohols, esters, ketones, and ethers.
• hydrocarbons examples include hexane, pentane, 2-ethylhexane, heptane, octane, decane, cyclohexane, methylcyclohexane, IP solvent 1016 (manufactured by Idemitsu Kosan Co., Ltd.), IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.), etc.
• Unsaturated hydrocarbon solvents such as hexene, heptene, cyclohexene, etc .; toluene, xylene, ethylbenzene, decalin, 1,2,3,4-tetrahydronaphthalene, ipzol 100 (manufactured by Idemitsu Kosan Co., Ltd.), ipzol Examples thereof include aromatic hydrocarbon solvents such as 150 (made by Idemitsu Kosan Co., Ltd.), and halogenated hydrocarbon solvents such as dichloromethane and chlorobenzene.
• Alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, methylcyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene Examples include glycol, tripropylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, hexylene glycol, and 2-methyl-2,4-pentanediol.
• esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate and the like.
• ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl cyclohexanone, and methyl-n-butyl ketone.
• ethers include dimethyl ether, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole and the like.
• the container of the present invention contains a liquid containing at least one organic compound selected from the group consisting of hexane, heptane, xylene, toluene, ethylbenzene, butyl acetate, ethyl acetate, isopropyl alcohol, and butyl alcohol.
• it contains a liquid containing at least one organic compound selected from the group consisting of xylene, toluene, and butyl acetate.
• the container of the present invention can be effectively used as a container having high storage stability because deformation of the container due to the organic compound to be contained is suppressed.
• the container of the present invention preferably has a rate of change in body size represented by the following formula (i) of less than 2%.
• Formula (i) (A represents the body dimensions of the container immediately after containing toluene, and B represents the body dimensions of the container after storing the container containing toluene in an atmosphere of 50 ° C. and 90% RH for 60 days.)
• drum dimension measures the outer dimension of the following 4 directions. Specifically, when the line connecting the two points on the parting line of the container blow mold is used as the reference line (direction 1), it passes through the center of the container body and turns clockwise by 45 degrees from the reference line. 3 lines (directions 2, 3, 4) can be drawn.
• the outer dimension in each direction was measured by measuring the distance between these four lines and each intersection of the container. Among the obtained outer dimensions, the smallest value was used as the body dimension of the container.
• the rate of change in body size is preferably less than 2%, more preferably 1.4% or less, and even more preferably 1.0% or less. When the rate of change of the body part size is within the above range, the solvent resistance is excellent and the deformation of the container is suppressed.
• the injection blow molded container of the present invention is manufactured by injection blow molding.
• a test tubular preform (parison) is first molded by injection molding, and then blown into a bottle shape, for example, using the residual heat of the preform at the time of injection.
• a temperature control zone such as a reheating heater pod or a temperature control pod may be provided as necessary.
• the preform heated to a certain degree it is fitted into the final shape mold (blow mold), air is blown from the mouth, the preform is inflated to adhere to the mold, and then cooled and solidified.
• a stretch rod may be used in combination depending on the shape and required physical properties of the container.
• a normal injection molding method can be applied to the parison molding.
• a polyamide resin composition containing the polyamide resin (A) and the polyamide resin (B) is passed from the injection cylinder through a mold hot runner using a molding machine equipped with an injection machine and an injection mold.
• a parison corresponding to the shape of the injection mold can be manufactured.
• the final shape mold mentioned above is heated, and at the time of blowing, the outer side of the wall of the molded body is brought into contact with the inner surface of the mold for a predetermined time.
• the injection blow molded container of the present invention is preferably obtained by a hot parison molding method.
• the hot parison molding method is a method in which the injection process and the blow process are performed in the same apparatus, and blow molding is performed using residual heat held by the preform at the time of the injection process.
• the cold parison molding method the molded preform is cooled to room temperature and reheated from room temperature to the same pre-blowing temperature.
• the preform was formed into a primary blow molded article having a size larger than that of the final blow molded article using a primary stretch blow mold, and then the primary blow molded article was heated and shrunk. Thereafter, two-stage blow molding may be employed in which a final blow molded article is formed by performing stretch blow molding using a secondary mold. According to this blow molded article manufacturing method, the bottom of the blow molded article is sufficiently stretched and thinned, deformation of the bottom during hot filling and heat sterilization is suppressed, and a blow molded article having excellent impact resistance is obtained. be able to.
• the container of the present invention may be coated with an inorganic or inorganic oxide vapor deposition film or an amorphous carbon film.
• the inorganic substance or inorganic oxide include aluminum, alumina, and silicon oxide.
• the vapor deposition film of an inorganic substance or an inorganic oxide can shield elution and permeation of organic compounds such as acetaldehyde and formaldehyde from the container of the present invention.
• the formation method of a vapor deposition film is not specifically limited, For example, physical vapor deposition methods, such as a vacuum evaporation method, sputtering method, and an ion plating method, Chemical vapor deposition methods, such as PECVD, etc. are mentioned.
• the thickness of the deposited film is preferably 5 to 500 nm, more preferably 5 to 200 nm, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.
• the amorphous carbon film is a diamond-like carbon film, and is a hard carbon film also called i-carbon film or hydrogenated amorphous carbon film.
• Examples of the method for forming the film include a method in which the inside of the hollow molded body is evacuated by evacuation, a carbon source gas is supplied thereto, and plasma generating energy is supplied by supplying plasma generating energy, Thereby, an amorphous carbon film can be formed on the inner surface of the container.
• the amorphous carbon film not only can remarkably reduce the permeability of low-molecular inorganic gases such as oxygen and carbon dioxide, but can also suppress the sorption of various low-molecular organic compounds having an odor.
• the thickness of the amorphous carbon film is preferably 50 to 5,000 nm from the viewpoints of the effect of suppressing sorption of low molecular organic compounds, the effect of improving gas barrier properties, adhesion to plastic, durability, and transparency.
• the body size was measured by using a digital caliper (trade name: ABS Digimatic Caliper CD-AX / APX, manufactured by Mitutoyo Corporation) at an outer dimension at a height of 35 mm from the bottom of the container. More specifically, when a line connecting two points on the parting line of the blow mold of the container is used as a reference line (direction 1), it passes through the center of the body of the container and is 45 degrees to the right from the reference line. By rotating around, three lines (directions 2, 3, and 4) were drawn, the distances between these four lines and each intersection of the container were measured, and the outer dimensions in each direction were measured. Among the obtained outer dimensions, the smallest value was used as the body dimension of the container.
• the rate of change of the body size is represented by the following formula (i).
• Change rate of body size (AB) / A ⁇ 100
• A represents the body size of the container immediately after the toluene is accommodated
• B represents the body size of the container after storage.
• the evaluation criteria are as follows. The allowable range is up to evaluation C.
• C Change ratio of trunk part dimension exceeds 1.4% and less than 2%
• D Change rate of body size is 2% or more
• the obtained polymer was taken out from the nozzle at the bottom of the reaction can as a strand, cooled with water and then cut into pellets to obtain polyamide resin pellets having a molar ratio of adipic acid and isophthalic acid of 94: 6.
• the pellets were charged into a stainless steel drum-type heating device and rotated at 5 rpm.
• the atmosphere in the reaction system was raised from room temperature to 140 ° C. under a small amount of nitrogen stream. When the temperature in the reaction system reached 140 ° C., the pressure was reduced to 1 torr (133.322 Pa) or less, and the temperature in the system was further increased to 190 ° C. in 130 minutes.
• the solid state polymerization reaction was continued for 30 minutes at the same temperature. After completion of the reaction, the pressure reduction was completed, the temperature inside the system was lowered under a nitrogen stream, and the pellet was taken out when the temperature reached 60 ° C. to obtain a polyamide resin (A-2).
• the relative viscosity of the polyamide resin (A-2) was 2.68.
• the glass transition temperature was 92 ° C and the melting point was 229 ° C.
• Examples 1 to 24, Comparative Examples 1 to 17 Manufacture of containers
• the blended material is put into the hopper of an injection blow molding machine, and the required amount from the resin injection cylinder
• a single layer preform (10 g) was obtained by injecting the molten resin and filling the injection mold.
• the temperature of the obtained preform is adjusted to a predetermined temperature, as a secondary process, a single layer container (full length 95 mm, outer diameter 22 mm ⁇ , trunk average thickness 1.0 mm) is transferred to a blow mold and blow molded.
• Manufactured Manufactured.
• An injection blow integral molding machine comprising a preform injection molding zone having an injection cylinder and an injection mold, and a blow molding zone having a temperature control unit and a blow mold was used.
• Injection cylinder temperature 260 ° C
• Resin channel temperature in injection mold 265 ° C Parison surface temperature after injection molding: 130 ° C Parison temperature before blow: 125 ° C
• Blow mold cooling water temperature 35 °C
• Examples 1 to 24 that satisfy the requirements of the present invention have excellent blow moldability, excellent drop impact resistance of the container, and the dimensional change rate of the trunk portion even when toluene is contained. There were few containers excellent in solvent resistance. On the other hand, the hollow containers of Comparative Examples 1 to 17 were not sufficiently moldable and could not be stably obtained in the comparative examples having a high polyamide resin (B) content. On the other hand, in the comparative example with a small content of the polyamide resin (B), the drop impact resistance of the container was inferior.
• the container obtained by the present invention is excellent in moldability and impact resistance, and further excellent in solvent resistance, and can be used as a container for accommodating various organic compounds and compositions containing the same.

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• 2017
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• 2018
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