WO2012001832A1 - Réservoir en plastique - Google Patents

Réservoir en plastique Download PDF

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Publication number
WO2012001832A1
WO2012001832A1 PCT/JP2010/071687 JP2010071687W WO2012001832A1 WO 2012001832 A1 WO2012001832 A1 WO 2012001832A1 JP 2010071687 W JP2010071687 W JP 2010071687W WO 2012001832 A1 WO2012001832 A1 WO 2012001832A1
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WO
WIPO (PCT)
Prior art keywords
resin
polyphenylene ether
weight
acid
tank
Prior art date
Application number
PCT/JP2010/071687
Other languages
English (en)
Japanese (ja)
Inventor
雅史 大神
祐明 秋葉
岩崎　正樹
徹 真野
正仁 松村
武司 清田
西岡　和道
田中　宏治
赤松　健一
星野　哲也
Original Assignee
株式会社ニシヤマ
みのる化成株式会社
三菱エンジニアリングプラスチックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2010148191A external-priority patent/JP4773575B2/ja
Application filed by 株式会社ニシヤマ, みのる化成株式会社, 三菱エンジニアリングプラスチックス株式会社 filed Critical 株式会社ニシヤマ
Priority to CN201080067549.2A priority Critical patent/CN102959341B/zh
Publication of WO2012001832A1 publication Critical patent/WO2012001832A1/fr

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    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B65D90/00—Component parts, details or accessories for large containers
    • B65D90/02—Wall construction
    • B65D90/022—Laminated structures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H1/00—Water heaters, e.g. boilers, continuous-flow heaters or water-storage heaters
    • F24H1/18—Water-storage heaters
    • F24H1/181—Construction of the tank
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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

Definitions

  • the present invention relates to a resin tank in which a tank wall surface portion is composed of a resin multilayer structure, and more particularly to a resin tank excellent in pressure resistance and heat resistance.
  • a hot water storage system that stores hot water boiled by a heat source using gas, electricity, solar heat, a fuel cell, or the like is known.
  • a metal tank is generally used as a hot water storage tank that is a pressure-resistant and heat-resistant container (see Patent Document 1).
  • the conventional hot water storage tank is composed of a metal material in order to satisfy the pressure resistance performance, and the resin material is partially used from the viewpoint of improving the heat insulation performance. It is only used.
  • metal tanks are relatively heavy and are subject to restrictions on the installation location or require reinforcement of the installation location.
  • the temperature of the hot water is easy to cool, it is necessary to provide a heat insulating material on the outer periphery of the metal tank, and the hot water storage tank becomes larger by adding the heat insulating material.
  • an object of the present invention is to provide a resin tank as a pressure-resistant and heat-resistant container, which is advantageous in terms of cost.
  • the present invention provides a tank wall surface comprising an inner layer made of a polyphenylene ether resin, an outer layer made of a polyamide resin and provided outside the inner layer, and a polyphenylene containing a polyphenylene ether resin and a polyamide resin.
  • It is a resin-made tank which consists of a multilayer structure which consists of an ether type resin composition, and has the intermediate
  • the tank wall portion is composed of a multilayer structure having an inner layer made of a polyphenylene ether resin and an outer layer made of a polyphenylene ether resin composition containing a polyphenylene ether resin and a polyamide resin and provided outside the inner layer.
  • This is a resin tank.
  • the resin tank of the present invention can be mass-produced and automated by applying a general resin molding technique such as blow molding from a general-purpose resin material. Moreover, it can be made lighter than a metal tank and has excellent heat insulation. Even when the heat insulating material is provided, since the resin material has a lower thermal conductivity than the metal material, the amount of heat insulating material used can be reduced or eliminated. In addition, by configuring the tank wall surface portion from a multilayer structure, sufficient pressure resistance and heat resistance can be provided. Accordingly, it is possible to provide a resin tank as a pressure-resistant and heat-resistant container that is advantageous in terms of cost.
  • a hot water storage tank 10 to which a resin tank of the present invention is applied is a pressure-resistant and heat-resistant container used for storing hot water boiled by a heat source using gas or the like in a hot water storage system.
  • the hot water storage tank 10 is installed through the legs 11.
  • a pipe 13 for introducing hot water boiled by a heat source (not shown) into the tank is connected to the inlet 12 at the bottom of the tank, and a pipe 15 for leading the stored hot water to a necessary place at the outlet 14 at the top of the tank. It is connected.
  • the inlet portion 12 and the outlet portion 14 are not limited to the positions in the illustrated example, and can be provided at appropriate positions such as a side wall of the tank.
  • the specification of the hot water storage tank 10 is not particularly limited, for example, the capacity is 100 liters, the pressure resistance is 1.77 MPa, and the operating temperature is about 95 ° C.
  • the tank wall surface portion 16 includes an inner layer 21 made of a polyphenylene ether resin, an outer layer 22 made of a polyamide resin and provided outside the inner layer 21, and a polyphenylene containing a polyphenylene ether resin and a polyamide resin. It consists of the multilayer structure 20 which consists of an ether-type resin composition, and has the intermediate
  • the polyphenylene ether resin is hard, if it is scratched or distorted when it is incorporated into other parts, it is relatively brittle and is prone to breakage and breakage. Therefore, in the hot water storage tank 10 of the first embodiment of the present invention, the outer layer 22 made of polyamide resin is provided outside the inner layer 21 in order to protect the inner layer 21.
  • the polyamide resin has excellent toughness and impact resistance, it is suitable to be applied to the outer layer 22 for protecting the inner layer 21. That is, even if scratches or cracks occur on the outer surface of the outer layer 22, the scratches or cracks do not progress, and the inner layer 21 can be protected from external impacts over a long period of time.
  • the adhesive strength between the inner layer 21 and the intermediate layer 23 and the adhesive strength between the outer layer 22 and the intermediate layer 23 are ensured, and the strength of the entire multilayer structure 20 is increased. be able to.
  • the thickness dimension of the inner layer and the outer layer can be reduced as compared with the case where no intermediate layer is provided, and the hot water storage tank can be further reduced in size and weight. .
  • the thickness dimension of the inner layer 21, the thickness dimension of the intermediate layer 23, and the thickness dimension of the outer layer 22 appropriate dimensions can be adopted according to required pressure resistance, satisfactory heat insulating performance or heat retention performance.
  • An appropriate dimension can be adopted as the thickness dimension of the intermediate layer 23 according to the required peel strength.
  • the pressure is 0.5 MPa
  • the tank thickness is 7 mm
  • the thickness ratio is 6: 1: 3
  • the pressure resistance at 87 ° C. is 1.0 MPa, and it is considered that a safety factor of 2 can be secured for 0.5 MPa (target general water pressure).
  • the specific gravity of the multilayer structure 20 in the above thickness dimension is about 1.09.
  • the hot water storage tank 10 of the present embodiment can be reduced in weight to about 70% of the weight of the metal tank (reducing the weight of about 30%) under the same pressure resistance and heat insulation performance. Furthermore, since the same heat insulation performance can be obtained even if the weight is reduced, it can be said that the heat insulation can be improved.
  • the inner layer 21 is made of a polyphenylene ether resin.
  • the polyphenylene ether resin used for the inner layer 21 is preferably composed of 30 to 90% by weight of polyphenylene ether resin and 70 to 10% by weight of styrene resin, 40 to 90% by weight of polyphenylene ether resin and 60 to 10% by weight of styrene resin.
  • the polyphenylene ether resin is more preferably 60 to 90% by weight and the styrene resin 40 to 10% by weight. When the polyphenylene ether resin is less than 30% by weight, heat resistance and mechanical strength tend to be lowered.
  • the deflection temperature under load can be maintained at about 100 ° C., and if the polyphenylene ether resin is 60% by weight or more, the deflection temperature under load is maintained at 130 to 140 ° C. be able to.
  • the deflection temperature under load is a value measured under the condition of a load of 1.80 MPa in accordance with ISO75.
  • the outer layer 22 is made of a polyamide resin.
  • the intermediate layer 23 is a polyphenylene ether-based resin containing at least a polyphenylene ether-based resin and a polyamide resin in order to achieve both the adhesiveness between the inner layer 21 and the intermediate layer 23 and the adhesiveness between the outer layer 22 and the intermediate layer 23. It consists of a composition. Since the polyphenylene ether resin in the intermediate layer 23 also functions as a structure and improves strength, the intermediate layer 23 also functions as a layer that protects the inner layer 21.
  • the polyphenylene ether resin used for the intermediate layer is preferably composed of 20 to 95% by weight of polyphenylene ether resin and 80 to 5% by weight of styrene resin, 25 to 85% by weight of polyphenylene ether resin, and 75 to 15% by weight of styrene resin. Preferably it consists of.
  • the polyphenylene ether resin is less than 20% by weight, heat resistance and mechanical strength tend to be lowered.
  • the polyphenylene ether resin composition is preferably a resin mixture comprising 20 to 90% by weight of a polyphenylene ether resin and 80 to 10% by weight of a polyamide resin.
  • a polyamide resin When the content of the polyphenylene ether resin is less than the lower limit and the content of the polyamide resin exceeds the upper limit, the adhesiveness to the inner layer 21 tends to be inferior, and the content of the polyphenylene ether resin exceeds the upper limit, and the polyamide If the resin content is less than the above lower limit, the adhesion to the outer layer 23 tends to be poor.
  • the mixing ratio as described above, sufficient adhesive strength between the outer layer 22 and the intermediate layer 23 is ensured while ensuring sufficient adhesive strength between the inner layer 21 and the intermediate layer 23.
  • the polyphenylene ether resin and the polyamide resin are more preferably 45 to 90% by weight of the polyphenylene ether resin, 55 to 10% by weight of the polyamide resin, further preferably 50 to 90% by weight of the polyphenylene ether resin, and 50 to 10% by weight of the polyamide resin. %, Particularly preferably 60 to 90% by weight of polyphenylene ether resin and 40 to 10% by weight of polyamide resin.
  • the polyphenylene ether resin and the polyamide resin are used in the above ratio, if the ratio of the polyphenylene ether resin in the polyphenylene ether resin is small, the polyphenylene ether resin content in the polyphenylene ether resin composition of the present invention is reduced. In some cases, the heat resistance and pressure resistance are inferior. Therefore, 35 parts by weight of the polyphenylene ether resin is included in 100 parts by weight of the total of the polyphenylene ether resin (for example, a composite resin of the above-mentioned polyphenylene ether resin and styrene resin) and the polyamide resin contained in the polyphenylene ether resin composition. As mentioned above, it is preferable that 45 parts by weight or more is contained.
  • the polyphenylene ether type used for the intermediate layer 23 is used.
  • the resin composition preferably contains 0.05 to 5 parts by weight of a compatibilizer with respect to 100 parts by weight of a resin mixture comprising a polyphenylene ether resin and a polyamide resin.
  • the content of the compatibilizer is less than the above lower limit, the adhesiveness, heat resistance, pressure resistance and mechanical strength may be reduced, and if the upper limit is exceeded, during the melt kneading in the production and molding process of the resin composition or When the thermal stability during use is lowered in a high temperature atmosphere, the mechanical strength tends to be lowered.
  • the content of the compatibilizing agent is more preferably 0.05 to 3 parts by weight, and still more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the total of the polyphenylene ether resin and the polyamide resin.
  • the blending amount of the radical generator is preferably 0.01 to 3 parts by weight, particularly 0.01 to 1 part by weight, based on 100 parts by weight of the total of the polyphenylene ether resin and the polyamide resin. If the blending amount is too small, the compatibility between the polyphenylene ether-based resin and the polyamide resin tends to be insufficient and the mechanical strength tends to decrease, and if it is too large, the resin composition is produced and melt kneaded in the molding process. In some cases, the thermal stability during use may be reduced in a high-temperature atmosphere.
  • Polyphenylene ether resin has high heat resistance, excellent mechanical properties such as tensile strength, high impact resistance, low water absorption, excellent dimensional stability, low coefficient of linear expansion, low specific gravity, difficulty It has the advantage of being flammable.
  • the polyphenylene ether resin is preferably a composite resin composition obtained by blending a polyphenylene ether resin with a styrene resin in order to improve fluidity and impact resistance.
  • the polyphenylene ether resin used in the polyphenylene ether resin according to the present invention is a polymer having a structural unit represented by the following general formula (1) in the main chain, and is either a homopolymer or a copolymer. May be.
  • two R a s each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group.
  • Each of the two R b s independently represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group.
  • both R a are not hydrogen atoms.
  • R a and R b are preferably a hydrogen atom, a primary or secondary alkyl group, or an aryl group.
  • the primary alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2 -, 3- or 4-methylpentyl group or heptyl group may be mentioned.
  • Preferable examples of the secondary alkyl group include isopropyl group, sec-butyl group, and 1-ethylpropyl group.
  • R a is preferably a primary or secondary alkyl group having 1 to 4 carbon atoms or a phenyl group.
  • R b is preferably a hydrogen atom.
  • Suitable homopolymers of polyphenylene ether resins include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2, 2 such as 6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-methyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), etc. , 6-dialkylphenylene ether polymer.
  • copolymer examples include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, and 2,6-diethylphenol.
  • 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymer such as 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer
  • Polymer graft copolymer obtained by graft polymerization of styrene to poly (2,6-dimethyl-1,4-phenylene ether), styrene to 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer And a graft copolymer obtained by graft polymerization.
  • polyphenylene ether resin in the present invention poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer are particularly preferable.
  • polyphenylene ether resins that define the number of terminal groups and the copper content as described in JP-A-2005-344065 can be suitably used.
  • the molecular weight of the polyphenylene ether resin is preferably such that the intrinsic viscosity at 30 ° C. measured in chloroform is 0.2 to 0.8 dl / g, more preferably 0.3 to 0.6 dl / g.
  • the intrinsic viscosity is 0.2 dl / g or more, the mechanical strength of the resin composition tends to be improved, and when it is 0.8 dl / g or less, the fluidity is improved and the molding process is easy.
  • Two or more kinds of polyphenylene ether resins having different intrinsic viscosities may be used in combination to achieve this intrinsic viscosity range.
  • the method for producing the polyphenylene ether resin used in the present invention is not particularly limited.
  • a monomer such as 2,6-dimethylphenol is oxidatively polymerized in the presence of an amine copper catalyst according to a known method.
  • the intrinsic viscosity can be controlled within a desired range by selecting the reaction conditions. Control of intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.
  • the polyphenylene ether resin may be used alone or in combination of two or more.
  • styrene resin examples include a styrene monomer polymer, a copolymer of a styrene monomer and another copolymerizable monomer, and a styrene graft. A copolymer etc. are mentioned.
  • examples of the styrene resin used in the present invention include polystyrene, styrene / butadiene / styrene copolymer (SBS resin), hydrogenated styrene / butadiene / styrene copolymer (SEBS), and hydrogenated styrene.
  • SEPS high impact polystyrene
  • AS resin acrylonitrile / styrene copolymer
  • ABS resin acrylonitrile / butadiene / styrene copolymer
  • MABS resin methyl methacrylate / acrylonitrile / butadiene / styrene copolymer
  • MABS resin acrylonitrile / acrylic rubber / styrene copolymer
  • AAS resin acrylonitrile / ethylene propylene rubber / styrene copolymer
  • AE styrene ⁇ IPN type rubber copolymer resin, or mixtures thereof.
  • it may have stereoregularity such as syndiotactic polystyrene
  • the weight average molecular weight of the styrenic resin is usually 50,000 or more, preferably 100,000 or more, more preferably 150,000 or more, and the upper limit is usually 500,000 or less. , Preferably 400,000 or less, more preferably 300,000 or less.
  • Examples of a method for producing such a styrene resin include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.
  • one styrene resin may be used alone, or two or more styrene resins may be mixed and used.
  • the polyamide resin used in the present invention has a —CONH— bond in the main chain and can be melted by heating, and may be a homopolymer or a copolymer.
  • Specific examples include various polyamide resins such as lactam polycondensates, polycondensates of diamines and dicarboxylic acids, and polycondensates of ⁇ -aminocarboxylic acids, or copolymerized polyamide resins and blends thereof. .
  • lactam examples include ⁇ -caprolactam and ⁇ -laurolactam.
  • diamine examples include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2-methylpentamethylene diamine, (2,2,4- or 2,4,4).
  • dicarboxylic acid examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium.
  • Aliphatic, alicyclic and aromatic dicarboxylic acids such as sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.
  • ⁇ -aminocarboxylic acid examples include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like.
  • polyamide resins obtained by polycondensation from these raw materials include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 56, polyamide 66, polyamide 610, polyamide 612, and polyamide 6 ⁇ 66 co-weight.
  • Polymer polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyamide 6I ⁇ 6T copolymer, polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene dodecamide, polyamide 9T, polyamide 9MT, and the like.
  • These polyamide resins may be used alone or in combination of two or more.
  • Preferred polyamide resins are polyamide 6, polyamide 66, polyamide MXD6 and polyamide 6I ⁇ 6T, and these can be used in combination with an amorphous polyamide resin.
  • the polyamide resin used in the present invention preferably has a relative viscosity of 2 to 7.5, measured according to JIS K6810, more preferably 2.5 to 7, and further preferably 3 to 6. If the relative viscosity is less than 2, the mechanical strength tends to decrease, and if it exceeds 7.5, the molding process may be difficult.
  • the terminal amino group concentration of the polyamide resin is preferably 10 to 140 eq / ton, more preferably 30 to 100 eq / ton, from the viewpoint of the molecular weight of the polymer, thermal stability, and compatibility with the polyphenylene ether resin.
  • the terminal carboxyl group concentration of the polyamide resin is preferably 10 to 140 eq / ton, more preferably 30 to 100 eq / ton, from the viewpoint of the molecular weight of the polymer, thermal stability, and compatibility with the polyphenylene ether resin. .
  • compatibilizer Preferred examples of the compatibilizer for the polyphenylene ether resin and the polyamide resin used in the polyphenylene ether resin composition of the present invention include unsaturated acids, unsaturated acid anhydrides, and derivatives thereof.
  • the compatibilizer is preferably maleic acid, itaconic acid, chloromaleic acid, citraconic acid, butenyl succinic acid, tetrahydrophthalic acid, and anhydrides thereof, and these acid halides such as maleimide, monomethyl maleate, dimethyl maleate, Examples thereof include amides, imides, C1-20 alkyl or glycol esters, and maleic acid and maleic anhydride are preferred.
  • compatibilizers may be used alone or in combination of two or more.
  • radical generator In the adhesive resin composition of the present invention, a radical generator may be blended together with the compatibilizer as described above. Examples of the radical generator include organic peroxides and azo compounds.
  • organic peroxides include, for example, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxides such as hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide; for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t -Dialkyl peroxides such as butyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide; -T-butylperoxybutane, 2,2-bis-t-butylperoxy Peroxyketals such as octane, 1,1-bis-t-butylperoxycycl
  • azo compound examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane) and the like.
  • radical generators a radical generator having a half-life temperature of 120 ° C. or more in 10 hours is preferable from the viewpoint of impact resistance.
  • a radical generator may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the polyphenylene ether-based resin used for the inner layer 21 and the polyphenylene ether-based resin composition used for the intermediate layer 23 include the above-mentioned polyphenylene ether-based resin, polyamide resin, and compatibilizer (or compatibilizer and Various resin additives other than the radical generator may be contained.
  • various resin additives that can be contained include, for example, heat stabilizers, antioxidants, weather resistance improvers, nucleating agents, foaming agents, flame retardants, lubricants, plasticizers, fluidity improvers, ultraviolet absorbers, dyes, Examples include pigments, fillers, reinforcing agents, dispersants, conductive agents, impact resistance improvers, and the like.
  • hindered phenol is used for the purpose of improving the thermal stability at the time of melt kneading and use in the production and molding process of the composition. It is preferable to blend at least one thermal stabilizer selected from a system compound, a phosphite system compound, a phosphonite system compound, and zinc oxide.
  • hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 2 , 6-Di-tert-butyl-4-methylphenol, 3,9-bis [1,1-dimethyl-2- ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ Ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethyleneglycol-bis [3- (3-tert-butyl-5-methyl-4-hydro Cyphenyl) propionate
  • n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate
  • 1,6-hexanediol-bis [3- (3 ′, 5′- t-butyl-4′-hydroxyphenyl) propionate]
  • 2,6-di-t-butyl-4-methylphenol 3,9-bis [1,1-dimethyl-2- ⁇ - (3-t- Butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred.
  • These may be used alone or in combination of two or more.
  • phosphite compounds include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene- Bis- (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tert-butyl-phenyl) Butane, tris (mixed mono and di-nonylphenyl) phosphite
  • the phosphonite compound include, for example, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,5-di-t-butylphenyl) -4 , 4'-biphenylenediphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dimethyl-5-ethylphenyl) -4,4'- Biphenylene diphosphonite, tetrakis (2,6-di-t-butyl-5-ethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3,4-tributylphenyl) -4,4'- Biphenylene diphosphonite, tetrakis (2,4,6-tri-t-butylphenyl
  • zinc oxide for example, those having an average particle diameter of 0.02 to 1 ⁇ m are preferable, and those having an average particle diameter of 0.08 to 0.8 ⁇ m are more preferable.
  • the blending amount of one or more stabilizers selected from hindered phenol compounds, phosphite compounds, phosphonite compounds, and zinc oxide is 100 parts by weight in total of polyphenylene ether resin or polyphenylene ether resin and polyamide resin. On the other hand, it is usually 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight.
  • the blending amount of the stabilizer is less than 0.01 parts by weight, the effect of improving the thermal stability is small, and when it exceeds 5 parts by weight, the mechanical strength is lowered and the economic disadvantage is increased, which is not preferable.
  • a flame retardant can be used in the polyphenylene ether resin used for the inner layer 21 and the polyphenylene ether resin composition used for the intermediate layer 23 of the present invention in order to impart flame retardancy.
  • the flame retardant is not particularly limited as long as it improves the flame retardancy of the composition, but a phosphoric acid ester compound, an alkali metal organic sulfonic acid metal salt, and a silicone compound are preferable.
  • a phosphoric acid ester compound used by this invention what is represented, for example by following formula (2) is mentioned.
  • R 1 , R 2 , R 3 and R 4 are each independently an aryl group which may be substituted, and X is a divalent aromatic which may have another substituent. And n represents a number from 0 to 5.
  • examples of the aryl group represented by R 1 to R 4 include a phenyl group and a naphthyl group.
  • examples of the divalent aromatic group represented by X include a phenylene group, a naphthylene group, and a group derived from, for example, bisphenol. Examples of these substituents include an alkyl group, an alkoxy group, and a hydroxy group. When n is 0, it is a phosphate ester, and when n is greater than 0, it is a condensed phosphate ester (may be a mixture).
  • phosphoric acid ester compounds include bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, and substituted and condensates thereof.
  • condensed phosphate compounds that can be suitably used as such components include, for example, “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol A bis ( Diphenyl phosphate)) and ADEKA Co., Ltd. under the trade name “FP500” (resorcinol bis (dixylenyl phosphate)) and are readily available.
  • the content of the polyphenylene ether resin or the polyphenylene ether resin and the polyamide resin is The amount is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to the total of 100 parts by weight. If the content of the phosphate ester flame retardant is less than 1 part by weight, the effect of improving flame retardancy cannot be sufficiently obtained, and if it exceeds 50 parts by weight, the heat resistance is lowered, which is not preferable.
  • the alkali metal salt organic sulfonic acid metal salt used in the present invention include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts.
  • the metal constituting the organic sulfonic acid metal salt is preferably an alkali metal, alkaline earth metal, etc., and the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, Examples include magnesium, calcium, strontium and barium.
  • the organic sulfonic acid metal salt can also be used by mixing two or more kinds of salts.
  • the aliphatic sulfonate used in the present invention is preferably a fluoroalkane-sulfonic acid metal salt
  • the fluoroalkane-sulfonic acid metal salt is preferably an alkali metal salt of fluoroalkane-sulfonic acid or an alkaline earth salt.
  • An alkali metal salt of a fluoroalkanesulfonic acid having 4 to 8 carbon atoms or an alkaline earth metal salt is more preferable. More preferred is a perfluoroalkane-sulfonic acid metal salt.
  • fluoroalkane-sulfonate examples include sodium perfluorobutane-sulfonate, potassium perfluorobutane-sulfonate, sodium perfluoromethylbutane-sulfonate, potassium perfluoromethylbutane-sulfonate, perfluorooctane -Sodium sulfonate, perfluorooctane-potassium sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid.
  • the aromatic sulfonic acid metal salt is preferably an aromatic sulfonic acid alkali metal salt, an aromatic sulfonic acid alkaline earth metal salt, an aromatic sulfone sulfonic acid alkali metal salt, an aromatic sulfone sulfonic acid alkaline earth metal salt, or the like.
  • the aromatic sulfonesulfonic acid alkali metal salt and the aromatic sulfonesulfonic acid alkaline earth metal salt may be a polymer.
  • aromatic sulfonic acid metal salt examples include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, and diphenylsulfone-3-sulfonic acid.
  • the amount of the organic sulfonic acid metal salt is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the total of polyphenylene ether resin or polyphenylene ether resin and polyamide resin. Particularly preferred is 0.03 to 2 parts by weight. If the amount of the organic sulfonic acid metal salt is less than 0.01 parts by weight, sufficient flame retardancy is difficult to obtain, and if it exceeds 5 parts by weight, the thermal stability tends to be lowered.
  • the silicone flame retardant used in the present invention is preferably a polyorganosiloxane having a linear or branched structure.
  • the organic group possessed by the polyorganosiloxane includes hydrocarbons such as alkyl groups and substituted alkyl groups having 1 to 20 carbon atoms, or vinyl and alkenyl groups, cycloalkyl groups, and aromatic hydrocarbon groups such as phenyl and benzyl. Chosen from.
  • the polyorganosiloxane may not contain a functional group or may contain a functional group. When it contains a functional group, the functional group is preferably a methacryl group, an alkoxy group or an epoxy group.
  • a fluororesin can be included for the purpose of preventing dripping during combustion.
  • the fluororesin is a polymer or copolymer containing a fluoroethylene structure, for example, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene and fluorine. It is a copolymer with an ethylene monomer that does not contain.
  • Polytetrafluoroethylene (PTFE) is preferable, and the average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 10,000,000.
  • polytetrafluoroethylene having a fibril forming ability it is possible to impart a higher melt dripping prevention property.
  • PTFE polytetrafluoroethylene
  • Teflon registered trademark
  • 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.
  • Polyflon D-1 Polyflon F-103
  • Polyflon F201 produced by Daikin Industries, Ltd.
  • CD076 Asahi IC Fluoropolymers Co., Ltd.
  • Argoflon F5 manufactured by Montefluos Co., Ltd.
  • polyflon MPA manufactured by Montefluos Co., Ltd.
  • polyflon FA-100 manufactured by Daikin Industries, Ltd.
  • PTFE polytetrafluoroethylene
  • Polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is prepared by, for example, using tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 1 to 100 psi, at a temperature of 0 It can be obtained by polymerizing at ⁇ 200 ° C., preferably 20 ⁇ 100 ° C.
  • the content is 100 weights of the total of the polyphenylene ether resin or the polyphenylene ether resin and the polyamide resin.
  • the amount is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, and particularly preferably 0.1 to 1 part by weight with respect to parts.
  • a colorant may be blended.
  • the colorant include dyes, inorganic pigments, and organic pigments generally used for thermoplastic resins.
  • the dye examples include azo dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, diphenylmethane dyes, acridine dyes, cyanine dyes, nitro dyes, and nigrosine.
  • Inorganic pigments include oxide pigments such as titanium oxide, red pepper and cobalt blue, hydroxide pigments such as alumina white, sulfide pigments such as zinc sulfide and cadmium yellow, silicate pigments such as white carbon and talc, and carbon black. Etc.
  • organic pigments include nitro pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments.
  • the colorant may be used as a master batch with a polyamide resin or a polyphenylene ether-based resin for the purpose of improving the handleability during extrusion.
  • the blending amount of the colorant is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of polyphenylene ether resin or polyphenylene ether resin and polyamide resin.
  • titanium oxide is easy to prevent discoloration of the resin composition, and is effective in coloring a light color.
  • a release agent to the polyphenylene ether-based resin used for the inner layer 21 and the polyphenylene ether-based resin composition used for the intermediate layer 23 of the present invention for the purpose of improving the releasability at the time of molding.
  • the mold release agent include aliphatic carboxylic acid, aliphatic carboxylic acid ester, polyolefin wax, silicone oil and the like.
  • the aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid.
  • the aliphatic carboxylic acid also includes an alicyclic carboxylic acid.
  • preferred aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred.
  • aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.
  • the same aliphatic carboxylic acid as that described above can be used.
  • the alcohol component constituting the aliphatic carboxylic acid ester examples include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable.
  • the aliphatic alcohol also includes an alicyclic alcohol.
  • these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol.
  • Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds.
  • aliphatic carboxylic acid ester examples include beeswax (mixture based on myristyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin diester
  • examples thereof include stearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.
  • polyolefin waxes include olefin homopolymers and copolymers.
  • examples of the olefin homopolymer include polyethylene wax, polypropylene wax and the like, partial oxides thereof, and mixtures thereof.
  • examples of olefin copolymers include ethylene, propylene, 1-butene, 1-hexene, 1-decene, 2-methylbutene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, etc.
  • Copolymers such as ⁇ -olefins, monomers copolymerizable with these olefins, such as unsaturated carboxylic acids or acid anhydrides thereof (maleic anhydride, (meth) acrylic acid, etc.), (meth) acrylic acid esters Examples thereof include copolymers with polymerizable monomers such as (methyl (meth) acrylate, alkyl ester having 1 to 6 carbon atoms of (meth) acrylic acid such as ethyl (meth) acrylate), and the like. Further, these copolymers include random copolymers, block copolymers, or graft copolymers.
  • the olefin copolymer is usually a copolymer of ethylene and at least one monomer selected from other olefins and polymerizable monomers. Of these polyolefin waxes, polyethylene wax is most preferred.
  • the polyolefin wax may have a linear or branched structure.
  • silicone oils include those composed of polydimethylsiloxane, and some or all of the methyl groups of polydimethylsiloxane are substituted with phenyl groups, hydrogen atoms, alkyl groups having 2 or more carbon atoms, halogenated phenyl groups, and fluoroester groups. Silicone-modified oil, epoxy-modified silicone oil having an epoxy group, amino-modified silicone oil having an amino group, alcohol-modified silicone oil having an alcoholic hydroxyl group, polyether-modified silicone oil having a polyether structure, and the like. Two or more types may be used in combination.
  • the compounding amount of the release agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the total of polyphenylene ether resin or polyphenylene ether resin and polyamide resin. More preferably, it is 1 to 3 parts by weight.
  • the polyamide resin used for the outer layer 22 may contain various resin additives as long as the purpose is not impaired.
  • various resin additives that can be contained include, for example, heat stabilizers, antioxidants, weather resistance improvers, nucleating agents, foaming agents, flame retardants, lubricants, plasticizers, fluidity improvers, ultraviolet absorbers, dyes, Examples include pigments, fillers, reinforcing agents, dispersants, conductive agents, impact resistance improvers, and the like.
  • a heat stabilizer in order to improve heat resistance stability.
  • organic stabilizers such as phosphorus, hindered phenol, hindered amine, organic sulfur and oxalic anilide, and inorganic stabilizers such as copper compounds and halides are preferable.
  • a phosphorus stabilizer a phosphite compound and a phosphonite compound are preferable.
  • phosphite compound examples include distearyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t- Butyl-4-isopropylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-sec-) Butylphenyl) penta
  • Examples of the phosphonite compound include tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,5-di-t-butylphenyl) -4,4′-.
  • hindered phenol stabilizer examples include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1- Dimethyl-2- ⁇ - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol -Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydride Xylbenzylphosphonate-
  • hindered amine stabilizer examples include known hindered amine compounds having a 2,2,6,6-tetramethylpiperidine skeleton.
  • Specific examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenylacetoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2 , 6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2, 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-ethylcarba Yl
  • oxalic acid anilide-based stabilizer 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert Tributoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p-methoxy-disubstituted oxanilides Mixtures, o- and p-ethoxy-disubstituted oxanilide mixtures,
  • the sulfur-based antioxidant refers to an antioxidant having a sulfur atom.
  • thiobis N-phenyl- ⁇ -naphthylamine
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • tetramethylthiuram monosulfide tetramethylthiuram disulfide
  • nickel dibutyldithiocarbamate nickel isopropylxanthate
  • Examples include trilauryl trithiophosphite.
  • a thioether-based antioxidant having a thioether structure can be suitably used because it receives oxygen from an oxidized substance and reduces it.
  • the molecular weight of the sulfur-based antioxidant is usually 200 or more, preferably 500 or more, and the upper limit is usually 3,000.
  • the copper compound used as the inorganic stabilizer is a copper salt of various inorganic acids or organic acids, and may be either cuprous or cupric. Specific examples thereof include copper chloride and copper bromide. In addition to copper iodide, copper phosphate, and copper stearate, natural minerals such as hydrotalcite, stichite, pyrolite and the like can be mentioned.
  • halide used as the inorganic stabilizer examples include, for example, alkali metal or alkaline earth metal halides; ammonium halides and quaternary ammonium halides of organic compounds; alkyl halides, allyl halides. Specific examples thereof include ammonium iodide, stearyltriethylammonium bromide, benzyltriethylammonium iodide, and the like. Among these, alkali metal halide salts such as potassium chloride, sodium chloride, potassium bromide, potassium iodide, sodium iodide and the like are preferable.
  • a combined use of a copper compound and a halide is preferable because it exhibits excellent effects in terms of heat discoloration and weather resistance (light resistance).
  • a copper compound when used alone, the molded product may be colored reddish brown by copper, and this coloring is not preferable depending on the application. In this case, discoloration to reddish brown can be prevented by using a copper compound and a halide together.
  • copper salt-based, hindered amine-based or organic sulfur-based stabilizers are particularly preferable.
  • the amount of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1.2 parts by weight, and 0.01 to 0.8 parts by weight with respect to 100 parts by weight of the polyamide resin. Further preferred. If the blending amount is less than 0.01 parts by weight, the thermal discoloration improvement, weather resistance, and light resistance improvement effects may be insufficient, and if it exceeds 3 parts by weight, the mechanical strength tends to decrease.
  • the polyamide resin used for the outer layer 22 is preferably blended with a nucleating agent in order to increase the crystallization speed and improve the moldability.
  • the nucleating agent generally include inorganic crystal nucleating agents such as talc and boron nitride, but organic crystal nucleating agents may be added.
  • the compounding amount of the crystal nucleating agent is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight, and further preferably 0.2 to 0.6 parts by weight with respect to 100 parts by weight of the polyamide resin. If the blending amount is less than 0.05 parts by weight, the effect as a crystal nucleating agent may be insufficient, and if it exceeds 2 parts by weight, mechanical strength and impact resistance due to foreign matter effects tend to decrease.
  • a release agent with the polyamide resin used for the outer layer 22 in order to improve the releasability at the time of molding.
  • the mold release agent those which do not easily reduce the flame retardancy of the polyamide resin are preferable, and preferable examples include bisamide waxes such as carboxylic acid amide waxes and ethylene bisstearylamides, and long chain fatty acid metal salts.
  • the carboxylic acid amide wax is obtained by a dehydration reaction of a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid and a diamine.
  • the higher aliphatic monocarboxylic acid is preferably a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms and a hydroxycarboxylic acid, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, 12-hydroxystearic acid and the like. .
  • polybasic acids examples include dibasic or higher carboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, azelaic acid and other aliphatic dicarboxylic acids and phthalic acid, terephthalic acid And alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid and cyclohexyl succinic acid.
  • diamine examples include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.
  • the softening point of the carboxylic acid amide wax in the present invention can be arbitrarily adjusted by changing the mixing ratio of the polybasic acid to the higher aliphatic monocarboxylic acid used in the production thereof.
  • the mixing ratio of the polybasic acid is preferably in the range of 0.18 to 1 mol per 2 mol of the higher aliphatic monocarboxylic acid.
  • the amount of diamine used is preferably in the range of 1.5 to 2 moles per 2 moles of higher aliphatic monocarboxylic acid, and varies according to the amount of polybasic acid used.
  • bisamide waxes include diamine and fatty acid compounds such as N, N′-methylenebisstearic acid amide and N, N′-ethylene bisstearic acid amide, or N, N′-dioctadecyl terephthalic acid amide. And dioctadecyl dibasic acid amide.
  • the long chain fatty acid metal salt is a metal salt of a long chain fatty acid having 16 to 36 carbon atoms.
  • a metal salt of a long chain fatty acid having 16 to 36 carbon atoms For example, calcium stearate, calcium montanate, sodium montanate, zinc stearate, aluminum stearate, sodium stearate, lithium stearate Etc.
  • the compounding amount of the release agent is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 1.5 parts by weight, and further preferably 0.05 to 0.8 parts by weight with respect to 100 parts by weight of the polyamide resin. . If the blending amount is less than 0.001 part by weight, it may be difficult to exhibit a sufficient mold release effect and improve the moldability, and if it exceeds 2 parts by weight, the mechanical strength of the polyamide resin may be lowered.
  • the reactivity of the polyamide resin and the compatibilizer is such that the polyphenylene ether resin and the compatibilizer are Therefore, as a kneading procedure for producing a polyphenylene ether composition, kneading of a polyamide resin and a compatibilizing agent is performed prior to kneading of the polyphenylene ether resin and the compatibilizing agent.
  • the polyamide resin and the compatibilizing agent react early and the reaction activity of the compatibilizing agent is consumed in the reaction with the polyamide resin, so that the reaction between the polyphenylene ether resin and the compatibilizing agent does not proceed.
  • a kneading procedure in which a polyphenylene ether-based resin and a compatibilizing agent are melt-kneaded, and a polyamide resin is added and kneaded to the obtained mixture.
  • a polyphenylene ether-based resin composition used for the intermediate layer 23 using a kneading extruder, preferably, various polyphenylene ether-based resins, a compatibilizing agent, and various kinds of additives added as necessary.
  • the resin additive is mixed in advance and added to the upstream part of the kneading extruder and reacted in a molten state. Then, the polyamide resin is continuously added to the middle part of the kneading extruder and melt kneaded. Accordingly, it is preferable to adopt a method in which a flame retardant or the like is introduced from the downstream portion to obtain a resin composition pellet.
  • a polyphenylene ether-based resin, a compatibilizing agent, and various resin additives to be added as necessary are mixed in advance, and the mixture is put into a kneading extruder and reacted in a molten state.
  • the pellet and the polyamide resin are put into a kneading extruder to be melt-reacted, and if necessary, additives such as a flame retardant and a reinforcing agent are blended from the downstream portion, and pellets of the resin composition It is preferable to employ a method of obtaining
  • the melt kneading temperature and time for producing the polyphenylene ether resin of the inner layer 21 and the polyphenylene ether resin composition of the intermediate layer 23 of the present invention are the polyphenylene ether resin, compatibilizing agent and polyamide resin constituting the resin composition.
  • the kneading temperature is 210 to 350 ° C., preferably 220 to 320 ° C., more preferably 220 to 290 ° C. If the kneading temperature is too high, thermal degradation of the resin composition becomes a problem, and mechanical strength may be lowered.
  • the hot water storage tank 10a according to the second embodiment is different from the first embodiment in which the multilayer structure 20 has a three-layer structure in that the multilayer structure 30 has a two-layer structure of an inner layer 31 and an outer layer 32. It is different.
  • the tank wall surface portion 16 of the second embodiment is composed of an inner layer 31 made of a polyphenylene ether resin and a polyphenylene ether resin composition containing a polyphenylene ether resin and a polyamide resin, and an outer layer 32 provided outside the inner layer 31. It is comprised from the multilayer structure 30 which has these.
  • the material of the inner layer 31 is the same as that of the inner layer 21 in the first embodiment.
  • the outer layer 32 of the second embodiment is made of a resin composition containing a polyphenylene ether resin and a polyamide resin, like the intermediate layer 23 of the first embodiment. Furthermore, it is preferable to contain a compatibilizing agent as in the intermediate layer 23 of the first embodiment. This is because the adhesive strength between the inner layer 31 and the outer layer 32 made of polyphenylene ether resin is ensured. Furthermore, since the polyamide resin has excellent toughness and impact resistance as described above, it can be suitably applied to the outer layer 32 for protecting the inner layer 31. That is, even if scratches or cracks occur on the outer surface of the outer layer 32, the scratches or cracks do not progress, and the inner layer 31 can be protected from external impacts over a long period of time.
  • the polyphenylene ether resin composition used for the outer layer 32 is preferably 20 to 60% by weight of polyphenylene ether resin and 80 to 40% by weight of polyamide resin, 30 to 50% by weight of polyphenylene ether resin and 70 to 50% of polyamide resin. Weight percent is more preferred.
  • the proportion of the polyamide resin is less than 40% by weight, the strength against external impact becomes weak and the inner layer 31 may not be sufficiently protected.
  • the proportion of the polyamide resin exceeds 80% by weight, the adhesive strength between the inner layer 31 and the outer layer 32 may be insufficient.
  • the ratio of the polyamide resin is 50 to 70% by weight because sufficient adhesive strength between the inner layer 31 and the outer layer 32 can be secured while the inner layer 31 is sufficiently protected.
  • the multilayer structures 20 and 30 according to the first and second embodiments of the present invention have the inner layer 21, the outer layer 22, and the intermediate layer 23 or the inner layer 31 as long as the effects of the present invention are not impaired.
  • another resin layer may be included.
  • the resin used for the other resin layer is not particularly limited, but from the viewpoint of molding processability, heat resistance, water resistance, pressure resistance, and mechanical strength, heat of polycarbonate resin, polyester resin, polyacetal resin, polyolefin resin, etc.
  • a plastic resin is preferred.
  • the hot water storage tank 10 and the hot water storage tank 10a having the above-described configuration can be manufactured by applying a general resin molding technique such as blow molding, and the welding work required for manufacturing a metal tank becomes unnecessary.
  • mass production and manufacturing can be automated easily, and the quality and stability of the hot water storage tank can be easily achieved.
  • the degree of freedom in selecting a tank shape is greater, the weight can be reduced, and the heat insulation is excellent.
  • a heat insulating material can be further provided. In that case, since the resin material has lower thermal conductivity than the metal material, the amount of heat insulating material used can be reduced.
  • the tank wall surface portion 16 is constituted by the multilayer structure 20 composed of three layers of the inner layer 21-intermediate layer 23-outer layer 22, or the multilayer structure 30 composed of two layers of the inner layer 31-outer layer 32, thereby providing sufficient pressure resistance. And heat resistance.
  • the hot water storage tank 10a since the inner layer 31 and the outer layer 32 are directly bonded without interposing the intermediate layer 23 in the first embodiment, it is possible to simplify the manufacturing apparatus and the manufacturing procedure. Have advantages. Therefore, it is possible to provide a hot water storage tank as a pressure-resistant and heat-resistant container, which is advantageous in terms of cost.
  • the polyphenylene ether resin that forms the inner layer 21 of the multilayer structure 20 and the inner layer 31 of the multilayer structure 30 includes a grade that satisfies the above-mentioned standard. Therefore, the hot water storage tanks 10 and 10a of the present embodiment can be suitably used as a tank for storing hot water applied also for drinking.
  • the polyphenylene ether resins forming the inner layers 21 and 31 of the multilayer structures 20 and 30 are “standards for food, additives, etc.” (Ministry of Health and Welfare Notification No. 370) or “standards for synthetic resin utensils or containers and packaging” ( Since there is a grade that conforms to the standard of the Ministry of Health, Labor and Welfare Notification No. 201), for example, it may be applied to a tank installed in a milk processing line or a food processing line.
  • the resin tank of the present invention is a material that does not corrode the inner layers 21 and 31 of the multilayer structures 20 and 30, it can be widely applied as a pressure- and heat-resistant container for storing these materials. Absent. Moreover, it is not restricted to storing a liquid, A gel-like material can also be stored. Further, the present invention is not limited to a resin tank having only a heat retaining function, and can also be applied to a resin tank having a built-in heater and having a heat retaining / heating function. Further, since the resin tank has a large degree of freedom in selecting the tank shape, the tank shape is not limited to the illustrated shape, and a desired shape can be selected.
  • FIGS. 4A, 4B and FIGS. 5A-5D are a front view and a top view of hot water storage tank 110, respectively.
  • FIG. 5A shows a multilayer blow molding machine 140 that is a hot water storage tank molding apparatus
  • FIG. 5B shows a state in which the mold 150 of the molding apparatus is opened
  • FIG. 5C shows a state in which the mold 150 is closed.
  • FIG. 5D has expanded and shown the D section of FIG. 5A.
  • the inner layer 121 uses the polyphenylene ether-based resin composition-1 described below, and the outer layer 122 includes the polyamide resin described below.
  • the intermediate layer 123 used was a polyphenylene ether-based resin composition-2 described below.
  • Polyphenylene ether resin poly (2,6-dimethyl-1,4-phenylene) ether (“PX100L” manufactured by Polyxylenol Singapore, intrinsic viscosity 0.47 dl / g measured at 30 ° C.
  • Styrene resin-1 high impact polystyrene (“HT478” manufactured by Nippon Polystyrene Co., Ltd., weight average molecular weight (Mw) 200,000, MFR 3.2 g / 10 min (measured at 200 ° C., load 5 kg)
  • Styrenic resin-2 Styrene-ethylene / butylene-styrene block copolymer (hereinafter abbreviated as “SEBS”) (“Septon 8006” manufactured by Kuraray Co., Ltd., styrene content 33% by weight, number average molecular weight 200,000)
  • SEBS Styrene-ethylene / butylene-styrene block copolymer
  • Polyamide resin Polyamide 6 (“Amilan CM1056” manufactured by Toray Industries, Inc.)
  • Compatibilizer Maleic anhydride (“Crystalman AB” manufactured by NOF Corporation)
  • Stabilizer-1 Phosphonite heat stabilizer (“Sand Stub P-EPQ
  • the blending amount of each component is 0.3 parts by weight of stabilizer-1 with respect to 100 parts by weight in total of 60% by weight of polyphenylene ether resin, 35% by weight of styrene resin-1 and 5% by weight of styrene resin-2.
  • Stabilizer-2 0.3 parts by weight.
  • the blending amount of each component is 0.2 parts by weight of compatibilizer and 10 parts by weight of stabilizer for 100 parts by weight in total of 47% by weight of polyphenylene ether resin, 25% by weight of styrene resin-1 and 28% by weight of polyamide resin. 0.5 parts by weight and 0.5 parts by weight of stabilizer-2.
  • the blow molding method was applied to the production of the tank 110.
  • the tank 110 was molded using a molding apparatus including a dedicated multilayer blow molding machine 140 and a mold 150.
  • the molding machine 140 is provided with four screws 141, 142, 143, 144 for melting the resin pellets.
  • An accumulator and an extruding device for accumulating molten resin are provided in succession to the screws 141, 142, 143, and 144.
  • the accumulator is divided into five layers, and it is possible to extrude different types of materials in a configuration of four types and five layers.
  • the screw 141 was used for the inner layer 121
  • the screw 142 was used for the outer layer 122.
  • both are used for the intermediate layer 123.
  • ⁇ Molding conditions The polyphenylene ether resin composition-1 for the inner layer 121 was melted at 220 to 290 ° C. with a ⁇ 141 mm screw 141.
  • the polyamide resin for the outer layer 122 was melted at 200 to 270 ° C. by another ⁇ 90 mm screw 142.
  • the polyphenylene ether-based resin composition-2 for the intermediate layer 123 was melted at 220 to 270 ° C. using two screws: a ⁇ 143 mm screw 143 and a ⁇ 55 mm screw 144.
  • the molten resin of the polyphenylene ether resin composition-1 is placed in the accumulator for the inner layer, the molten resin of the polyamide resin is placed in the accumulator for the outer layer, and the molten resin of the polyphenylene ether resin composition-2 is placed in the accumulator for the intermediate layer.
  • the extruded resin had a cylindrical shape with an outer diameter of 120 to 250 mm, a length of about 2 m, and a weight of 7 to 17 kg.
  • ⁇ Heat and pressure resistance test> A screw shape was created by post-processing at each of the upper and lower nozzles of the tank 110, and a hole of ⁇ 10 to 15 was made in the center of the nozzle. A joint was connected to the created screw shape, and a hose for water injection and a hose for drainage were connected to each other.
  • the tank 110 was installed upright. Tap water heated to 80 to 95 ° C. was poured from a water supply hose while keeping the set temperature of the water heater constant, and the tank was filled with hot water. Thereafter, the joint on the drain side was closed, and the connection of the joint on the water injection side was switched to the hydraulic pump. Until the tank was damaged, pressure was gradually applied to the tank using a hydraulic pump, and a destructive test was conducted.
  • the resin-made three-layer hot water storage tank (1) subjected to the test was not damaged up to 87 ° C. and 0.6 MPa.
  • heat resistance and pressure resistance are further improved by increasing the thickness of the inner polyphenylene ether resin layer.
  • the pressure resistance is further improved by bonding the polyphenylene ether resin and the polyamide resin.
  • the tank thickness is 7 mm, the pressure resistance at 87 ° C. is 1.0 MPa, and it is considered that a safety factor of 2 can be secured for 0.5 MPa (target general water pressure).
  • Hot water storage tank (resin tank), 11 Leg part 12 Inlet part 14 Outlet part 16 Tank wall surface part, 20 multilayer structure, 21 Inner layer, 22 outer layer, 23 Middle layer, 30 multilayer structure, 31 Inner layer, 32 Outer layer, 111 Nozzle for water injection, 112 nozzle for drainage, 121 inner layer, 122 outer layer, 123 intermediate layer 140 multilayer blow molding machine, 141, 142, 143, 144 screw, 150 molds, 151 Parison.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un réservoir en plastique utilisé comme récipient résistant à la pression et à la chaleur qui est d'un coût avantageux. Un réservoir de stockage d'eau chaude (10) (réservoir en plastique) comporte une partie de surface de paroi de réservoir (16) constituée d'une structure multicouche (20) comprenant une couche intérieure (21) en résine de polyphénylène éther, une couche extérieure (22) en résine de polyamide et située à l'extérieur de la couche intérieure, et une couche intermédiaire (23) en résine de polyphénylène éther et en résine de polyamide et qui est placée entre la couche intérieure et la couche extérieure.
PCT/JP2010/071687 2010-06-29 2010-12-03 Réservoir en plastique WO2012001832A1 (fr)

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CN103749247A (zh) * 2014-01-16 2014-04-30 常熟市慧丰塑料制品有限公司 一种多功能喷水壶
CN110220105B (zh) * 2019-04-25 2021-01-29 山东鑫瑞安装工程有限公司 一种高强度的压力罐
CN111231431A (zh) * 2020-01-09 2020-06-05 吉林大学 弹性梯度材料及其制备方法
CN112433405B (zh) * 2020-11-24 2022-04-19 中国科学技术大学 一种液晶高分子基板及其加工方法
CN112477336B (zh) * 2020-11-24 2022-04-19 中国科学技术大学 一种液晶高分子膜及其制作方法

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JPH10253164A (ja) * 1997-03-14 1998-09-25 Nippon Dennetsu Co Ltd プラスチック製電気温水器
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