JP5158844B2 - Refrigerant storage container for heating element cooling system - Google Patents

Description

  The present invention relates to a resin container.

Polypropylene resins have moisture barrier properties, moldability, oil resistance, and acid / alkali resistance, but have the disadvantage of being inferior in copper damage resistance and weldability. A resin composition made of an alloy of polypropylene resin and polyphenylene ether resin is effective in improving solvent resistance, impact resistance, chemical resistance, and rigidity, but is not sufficient for improving copper damage resistance and weldability. Absent.
In recent years, a higher moisture barrier property may be required. For example, blow molded containers of olefin-based resins are known as resin containers for beverages, foods, and edible oils (for example, Patent Documents 1 to 4).

On the other hand, in Patent Document 5, in addition to a tackifier, a layered silicate compound and a propylene resin, for example, a polyphenylene ether resin is used in combination to obtain a molded body such as a film, sheet or container having excellent gas barrier properties. There is a description that.
However, the contents disclosed in these prior art documents determine the shape by film, sheet, or blow molding, and there is a restriction that only a simple design can be formed. In addition, although the content is preserved for a long time without deterioration or weight reduction, when used as a mechanism part, the required mechanical properties and dimensional accuracy are not satisfied.

On the other hand, filler-containing PPS resins are often used for resin containers with high heat resistance, but the specific gravity is large, there is a problem with dimensional accuracy, and when moldability and post-processing are required, There was also a problem in weldability.
As described above, resin containers satisfying a good balance of moisture barrier properties, mechanical properties, and dimensional accuracy are not known, and development of containers using new materials is awaited.

JP 2005-8255 A JP 2002-255231 A JP 2002-103428 A JP 2000-255579 A JP 2003-335959 A

  The problem to be solved by the present invention is to provide a resin container excellent in moisture barrier properties, mechanical properties, and dimensional accuracy in a resin container in contact with water, moisture or an aqueous solution.

As a result of intensive studies in view of such a current situation, the present inventors are composed of a resin composition in which an inorganic filler is blended with a resin composition comprising a polypropylene resin, a polyphenylene ether resin and a hydrogenated block copolymer. The resin container has been found to be excellent in moisture barrier properties, mechanical properties, and dimensional accuracy, and has led to the present invention.
That is, the present invention
(1) (c) vinyl with respect to a total of 100 parts by weight of (a) polypropylene resin 55 to 95 parts by weight, (b) polyphenylene ether resin 45 to 5 parts by weight, (a) component and (b) component Mainly composed of at least one polymer block A mainly composed of an aromatic compound and a conjugated diene compound in which the total amount of 1,2-vinyl bond and 3,4-vinyl bond of the conjugated diene compound is 45 to 90%. 5 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block B, and (d) as an inorganic filler , (a) component and (b) (E) 30 to 60 parts by weight of a plate-like inorganic filler having an average flake diameter of 10 to 400 μm and (f) a fibrous inorganic filler 30 to 30 having an average diameter of 3 to 20 μm with respect to 100 parts by weight of the total of the components. 60 parts by weight, the total amount of the component (e) and the component (f) is 60 to 100 parts by weight , and the water vapor transmission coefficient is 0.40 g · mm / m 2 · day in a 40 ° C. and 90% RH environment. A refrigerant storage container for a heating element cooling system, comprising the following thermoplastic resin :
(2) (a) The polypropylene-based resin is a modified polypropylene-based resin obtained by reacting with an α, β-unsaturated carboxylic acid or a derivative thereof, and the refrigerant storage container of the heating element cooling system according to (1) above ,
(3) (c) The polymer block A constituting the hydrogenated block copolymer is a styrene polymer block, the polymer block B is a butadiene polymer block, and 1,2-vinyl of the butadiene polymer block The total amount of the bond and 3,4-vinyl bond is 65 to 90%, and the refrigerant storage container for the heating element cooling system according to (1) or (2) above ,
( 4 ) (e) The plate-like inorganic filler is at least one inorganic filler selected from mica, glass flakes, talc and graphite, and (f) the fibrous inorganic filler is a glass fiber (1) A refrigerant storage container for the heating element cooling system according to any one of to (3) ,
(5) a thermoplastic resin injection-molded article, glass parts, the least is one lid selected from the group consisting of metallic parts, characterized in Tei Rukoto joined to the refrigerant storage container main body (1) to (4) The refrigerant storage container of the heating element cooling system according to any one of
( 6 ) The lid is an injection molded product of a thermoplastic resin, and the thermoplastic resin lid is joined to the refrigerant storage container body by at least one of ultrasonic welding, spin welding, and hot plate welding. refrigerant storage container of the heating element cooling system according to the above (5), characterized in Tei Rukoto is.

  The resin container of the present invention has excellent moisture barrier properties, dimensional accuracy, and mechanical properties.

The resin container of the present invention comprises (a) polypropylene resin, (b) polyphenylene ether resin, (c) hydrogenated block copolymer, and (d) inorganic filler. Preferably, (c) vinyl aromatic compound is mainly used for (a) 55 to 95 parts by weight of polypropylene resin, (b) 45 to 5 parts by weight of polyphenylene ether resin and 100 parts by weight of both components. At least one polymer block A and at least one conjugated diene compound mainly comprising a conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of 45 to 90%. 5-30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising the polymer block B, and (d) 5-80 parts by weight of an inorganic filler.
The resin container preferably has a structure in which a polyphenylene ether resin is microdispersed in a polypropylene resin matrix. Although it is difficult to make such a structure by a normal method, it becomes possible by using a hydrogenated block copolymer having a specific structure.

The component (a) polypropylene resin includes a crystalline propylene homopolymer, a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene and / or at least one other in the second and subsequent steps of polymerization. And a crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerization of an α-olefin (for example, butene-1, hexene-1, etc.), and the above crystalline property. It may be a mixture of a propylene homopolymer and a crystalline propylene-ethylene block copolymer.

  Such a polypropylene resin is usually used in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of 3 to 3. It can be obtained by carrying out the polymerization in the range of 100 atm. At this time, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer. Further, either a batch type or a continuous type can be used as the polymerization method. Solution polymerization in a solvent such as butane, pentane, hexane, heptane, and octane, slurry polymerization, bulk polymerization in a monomer without solvent, and gas phase polymerization in a gaseous monomer can be applied.

  In addition to the polymerization catalyst described above, an electron donating compound can be used as an internal donor component or an external donor component as the third component in order to increase the isotacticity and polymerization activity of the resulting polypropylene. As these electron donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, methyl toluate, triphenyl phosphite, tributyl phosphite, etc. Phosphorous acid esters, phosphoric acid derivatives such as hexamethylphosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, Examples include various alcohols and / or various phenols.

  Polypropylene resins can be used alone, regardless of the crystallinity or melting point of the polypropylene resin described above, but the resulting resin composition receives a heat history as a heat resistant material and exhibits heat resistance. Is required, it is preferable to use a polypropylene resin in which two kinds of polypropylene resins having different properties are blended in a specific range.

The melting point of the propylene homopolymer partial crystal phase is a melting point value measured with a differential scanning calorimeter (DSC-2 type manufactured by Perkin Elmer Co., Ltd.) at a temperature rising rate of 20 ° C./min and a temperature decreasing rate of 20 ° C./min.
A resin composition obtained from polypropylene having a melting point of less than 155 ° C. is excellent in toughness (elongation) after thermal history, but tends to have low rigidity and heat resistance (DTUL). Moreover, although the resin composition obtained from a polypropylene whose melting | fusing point is 163 degreeC or more is excellent in the rigidity and heat resistance (DTUL) after heat history, it exists in the tendency for the toughness (elongation) after heat history to become small.

  The polypropylene resin usually has a melt flow rate (measured under a load of 230 ° C. and 2.16 kg in accordance with ASTM D1238) of 0.1 to 300 g / 10 minutes, preferably 0.1 to 100 g / 10. Min, more preferably in the range of 0.1-30 g / 10 min. Further, any melt flow rate within these ranges can be used alone or in combination.

The component (b) polyphenylene ether resin (hereinafter simply referred to as PPE) is essential for imparting heat resistance, dimensional accuracy, copper damage resistance, and weldability during post-processing to the resin composition of the present invention. It is a component.
PPE is a homopolymer and / or copolymer containing a repeating unit structure represented by the following formula. The reduced viscosity (0.5 g / dl, chloroform solution, measurement temperature 30 ° C.) is preferably in the range of 0.15 to 0.70, and preferably in the range of 0.20 to 0.60. More preferred.

(Wherein R1, R2, R3 and R4 may be the same or different and each represents hydrogen, halogen, a lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a halogenalkyl group, an aminoalkyl group or a hydrocarbonoxy group. Or at least two carbon atoms selected from the group consisting of halohydrocarbonoxy groups separating the halogen primitive and oxygen atoms.)

  Specific examples of PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6). -Phenyl-1,4-phenylene ether) and poly (2,6-dichloro-1,4-phenylene ether), and 2,6-dimethylphenol and other phenols (for example, 2,3,6). And polyphenylene ether copolymers such as copolymers with trimethylphenol and 2-methyl-6-butylphenol). In particular, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1, 4-phenylene ether) is more preferred.

  The method for producing PPE is not particularly limited. For example, PPE can be easily produced by oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 as a catalyst. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357, 3,257,358, JP-B 52-17880, JP-A 50-51197, It can be easily produced by the method described in JP-A-63-152628.

In addition to the PPE described above, the PPE can be obtained by combining the PPE with a styrenic monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof (for example, an ester compound or an acid anhydride compound) in the presence of a radical generator. Alternatively, it may be a known modified PPE obtained by reacting at a temperature of 80 to 350 ° C. in the melt, solution or slurry in the absence. In this case, the styrenic monomer and / or α, β-carboxylic acid or derivative thereof is preferably grafted or added to PPE at a ratio of 0.01 to 10% by weight. Furthermore, the mixture of the above-mentioned PPE and this modified PPE in any ratio may be sufficient.
Further, phosphorus compound-treated PPE obtained by adding 0.2 to 5 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene to 100 parts by weight of PPE and melt-kneading is also PPE excellent in color tone and fluidity. Can be used as

  In addition to the above-mentioned PPE, the PPE may be polystyrene, high impact polystyrene, syndiotactic polystyrene and / or rubber reinforced syndiotactic polystyrene in a range not exceeding 500 parts by weight, preferably 200 parts by weight or less. Those added in the above can also be suitably used.

The hydrogenated block copolymer that can be used as the component (c) acts as a dispersant for dispersing the polyphenylene ether resin in the above-described polypropylene resin matrix, and further has impact resistance on the resin composition. Is given.
This hydrogenated block copolymer is composed of a conjugated diene compound having a vinyl bond amount (that is, a total amount of 1,2-vinyl bond and 3,4-vinyl bond) of 30 to 95%, preferably 45 to 90%. A block copolymer consisting of at least one polymer block B mainly composed of at least one polymer block A mainly composed of a vinyl aromatic compound is hydrogenated by 50% or more.

  This hydrogenated block copolymer is, for example, AB type, ABAA type, BABA type, (AB-) nX type (where n is an integer of 1 or more). , X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound), ABABA type, etc. A hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure in which the block units are bonded, and the vinyl aromatic compound bonded in the block copolymer is 20 to 95% by weight, preferably 30%. Contains ~ 80 wt%.

  As the conjugated diene compound constituting the block copolymer B, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Of these, butadiene, isoprene and combinations thereof are preferred. The polymer block B mainly composed of the conjugated diene compound has a microstructure (bonded form of the conjugated diene compound) in the block. For example, in the polymer block B mainly composed of butadiene, the 1,2-vinyl bond is 30 to 30. In addition, in the polymer block B mainly composed of isoprene, the 3,4-vinyl structure is 30 to 95%. Moreover, about the vinyl bond amount of the polymer block B obtained by copolymerizing butadiene and isoprene, the total amount of 1,2-vinyl bond and 3,4-vinyl bond is 30 to 95%. The bonding form of these conjugated diene compounds can usually be known from an infrared spectrum, an NMR spectrum, or the like.

  Moreover, as a vinyl aromatic compound which comprises the polymer block A, 1 type (s) or 2 or more types are selected from styrene, (alpha) -methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene etc., for example. Among them, styrene is preferable.

  The number average molecular weight of the block copolymer having the above structure is preferably in the range of 5,000 to 1,000,000, more preferably 10,000 to 800,000, still more preferably 30,000 to 500. The molecular weight distribution (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography) is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

  A block copolymer having such a structure is obtained by hydrogenating an aliphatic double bond of a polymer block B contained therein, so that a hydrogenated block copolymer, that is, a vinyl aromatic compound-conjugated diene compound is obtained. Used as a hydrogenated block copolymer. The hydrogenation rate of such aliphatic double bonds is 50% or more, preferably 80% or more. This hydrogenation rate can usually be known from an infrared spectrum, NMR spectrum, or the like.

  The component (c) hydrogenated block copolymer has the structure of the hydrogenated block copolymer described above, but in producing a resin composition, the amount of vinyl bonds before hydrogenation is 30 to 55. Hydrogenated block copolymer obtained by hydrogenating at least one polymer block B mainly composed of a conjugated diene compound and at least one polymer block A mainly composed of a vinyl aromatic compound. Or at least one polymer block mainly composed of a conjugated diene compound having a vinyl bond content before hydrogenation of more than 55% and not more than 95%, preferably more than 55% and not more than 80%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly comprising B and a vinyl aromatic compound. It may be. Among the hydrogenated block copolymers classified into two types according to the different vinyl bond amounts of the conjugated diene compound before hydrogenation, the vinyl bond amount before hydrogenation is more than 5% and less than 30%, respectively. It has one polymer block B ′ mainly composed of a certain conjugated diene compound, and the ratio of these polymer blocks is B / B ′ = 99/1 to 50/50 (weight ratio). A hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least one polymer block A mainly composed of an aromatic compound is also included.

These structures are, for example, B′-BA type, B′-ABA type, B′-ABA type, (B′-AB-) nX type. (Where n represents an integer of 1 or more, X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound) These are hydrogenated products of vinyl aromatic compound-conjugated diene compound block copolymers having a structure in which units are bonded, and the classification of hydrogenated block copolymers having these structures is conjugated diene compounds of the main polymer block B Belongs to one of the two types of vinyl bonds.
The number average molecular weight of the polymer block B or B ′ in the hydrogenated block copolymer is preferably 1000 or more, more preferably 5000 or more.

The inorganic filler used as the component (d) is an essential component for the resin composition comprising the above-described (a) to (c) to exhibit low moisture permeability. That is, by adding a PPE resin to the component (a), it becomes possible to remarkably improve the dimensional accuracy, heat resistance, copper damage resistance, and weldability at the time of post-processing. In addition, it has the disadvantage of impairing low moisture permeability. In order to compensate for this, it is necessary to add (d) an inorganic filler, and it is preferable to add (e) a plate-like inorganic filler as the inorganic filler of component (d). The plate-like inorganic filler has a high shielding property, and can maintain or improve the low moisture permeability required for the resin container as well as the polypropylene resin alone.

The average flake diameter of the plate-like inorganic filler as the component (e) is 10 to 400 μm, and preferably 50 to 300 μm. Examples of the plate-like inorganic filler include glass flakes and mica, but graphite, conductive metal flakes, talc, and sericite can also be used. Among these, it is preferable to use glass flakes and mica from the balance of cost, moldability, mechanical strength, and dimensional accuracy. As the shape of the glass flakes, it is scaly, the major axis after resin blending and in the molded product is 1000 μm or less, preferably in the range of 1 to 500 μm, and the aspect ratio (ratio of major axis to thickness) is 5 or more, The number is preferably 10 or more, more preferably 30 or more. The major axis of the glass flakes is preferably 1000 μm or less in consideration of the difficulty of uniform mixing with the resin component by classification at the time of blending and variations in physical properties of the molded product. On the other hand, the aspect ratio is preferably 5 or more considering the heat resistance, rigidity and impact resistance of the molded product.

  As the glass flakes, commercially available ones can be used as they are, but they may be appropriately pulverized when used in the resin. For the purpose of improving the affinity with the resin, the glass flakes treated with various coupling agents such as silane and titanate can be used. Moreover, about mica, it is a plate-shaped thing and a sozolite mica (trademark) can be used conveniently. A resin having a major axis of 1000 μm or less, preferably 500 μm or less after blending of the resin and in the molded product is suitable, and a weight average aspect ratio (average diameter / average thickness of mica) of 10 or more, preferably 30 or more is imparted with rigidity. It may be a point. In order to improve the affinity with the resin, mica surface-treated with a coupling agent can be used particularly well.

  The inorganic filler as the component (f) is a mechanical property, particularly an improvement in strength and rigidity, and the required properties of the resin container used for the resin composition comprising the components (a) to (e) described above. It is preferable to provide antistatic performance according to the above. As the inorganic filler of component (f), inorganic salts, glass fibers (long glass fibers, chopped strand glass fibers), glass beads, carbon fibers, whiskers, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite , Heat conductive materials (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, silicon dioxide, magnesium oxide, aluminum nitrate, barium sulfate, etc.), conductive metal fibers, carbon black showing conductivity, carbon showing conductivity Examples thereof include fibers and carbon nanotubes.

The average diameter of the fibrous inorganic filler is preferably 3 to 20 μm, and more preferably 5 to 15 μm.
When blending a fibrous inorganic filler, it is preferable to use glass fibers from the balance of cost, moldability and mechanical properties. From the viewpoint of ease of mixing with the resin, the fiber length of the glass fiber before blending is preferably 0.5 to 10 mm, more preferably 1 to 8 mm, and particularly preferably 2 to 7 mm. . Using a fibrous inorganic filler having a fiber length in this range, the average fiber length after blending the resin and in the molded product is preferably 20 to 1000 μm, more preferably 100 to 500 μm, and more preferably 200 to 400 μm. It is particularly preferable to do this. The fibrous inorganic filler is particularly preferably treated with a known coupling agent or sizing agent.

When (e) the plate-like inorganic filler and (f) the fibrous inorganic filler are used in combination, the total amount of the (e) component and the (f) component is 100 parts by weight of the total of the (a) component and the (b) component. It is preferably 60 to 100 parts by weight, and more preferably 70 to 90 parts by weight. The content of the component (e) is preferably 30 to 60 parts by weight, and more preferably 35 to 55 parts by weight with respect to 100 parts by weight as a total of the components (a) and (b). In addition, the content of the component (f) is preferably 30 to 60 parts by weight, and more preferably 35 to 55 parts by weight with respect to 100 parts by weight of the total of the components (a) and (b). The weight ratio of the component (e) and the component (f) is preferably 70/30 to 30/70.

  In addition to the above components, other additional components such as antioxidants, metal deactivators, flame retardants (organophosphate compounds) as long as the characteristics and effects of the present invention are not impaired. , Ammonium polyphosphate flame retardants, aromatic halogen flame retardants, silicone flame retardants, etc.), fluorine polymers, elastomers for imparting impact resistance (including hydrogenated block copolymers), plasticizers ( Low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid ester, etc.), flame retardants such as antimony trioxide, weather resistance (light resistance) improver, polyolefin nucleating agent, slip agent, various colorants, mold release agent May be added.

The resin container of the present invention can be applied to any application that requires moisture barrier properties, mechanical properties, and dimensional accuracy, but as an example of a preferred application (i) an apparatus that requires cooling of a heating element, Specifically, there is a cooling storage container for OA equipment (for example, a personal computer). The OA equipment is assumed to have a maximum operating temperature range of -40 ° C to 100 ° C, and the cooling-mediated storage container also satisfies the mechanical properties and dimensional accuracy as a container in each application within this temperature range. However, in the moisture barrier property, a temperature range of 0 ° C. or lower is not a problem, and a temperature range of 0 ° C. to 60 ° C., which has many use opportunities and spends most of the product life, is important.
Although the environmental temperature constantly varies, the numerical value of the moisture barrier property in an environment of 40 ° C. can be applied as an index for quantifying the moisture barrier property in this temperature region as a required characteristic as a resin container. If the thermoplastic resin is 0.40 g · mm / m ² · day or less in a 40 ° C 90% RH environment using a method based on the JIS-Z0208 cup method test standard, the life of the product in terms of the function of the final product It is estimated that it will not cause any trouble.

  Another example of the preferred use of the resin container of the present invention is (ii) a storage container for water meter measuring mechanism parts of a water meter. The bottom of the container is provided with a bearing, a snap fit portion, and the like, and a meter is accommodated therein, so that a transparent lid is fitted so that the meter can be seen. Tap water flows outside the resin container and acts on the water amount measuring mechanism. However, if the resin container permeates moisture, the transparent lid becomes cloudy and the meter cannot be read. Since the resin container of the present invention has a low moisture permeability, it can be used without any problem for water meter applications.

  The lid is often the thermoplastic resin of the present invention obtained by injection molding, but an O-ring may be used to prevent liquid leakage, and any part or material having the same leakage prevention function may be used. Is possible. Moreover, it is also possible to install an instrument etc. inside a container in combination with glass, and it is also possible to join with metal parts. Further, ceramics, thermosetting resin, etc. can be used as separate parts.

For the method of joining the resin container and the lid, ultrasonic welding, spin welding, and hot plate welding are optimal when the thermoplastic resins of the present invention are used together, but fastening by snap fit is also possible, and other well-known methods This welding method is also possible. In the case of joining with an O-ring, a glass part, or a metal part, screw / bolt fastening, clamp fastening, and screw fastening are suitable, but various other known joining methods can also be used.
Injection molding is the most suitable method for producing the resin container of the present invention, but it can also be obtained by various known methods such as compression molding, extrusion molding, multilayer extrusion molding, profile extrusion molding, and hollow molding. It is.

In a preferred embodiment of the present invention, since the polyphenylene ether resin has a specific dispersion state and contains a plate-like filler, it has excellent moisture barrier properties and high dimensions comparable to metal containers even when joined to other parts. Shows precision and excellent mechanical properties. When a resin container is joined to a computer water-cooled pump, a certain amount of water flow can be circulated with little decrease during the duration of the computer. At this time, since there is almost no water evaporation under the assumed use environment, even if there are electronic parts or the like around, there is no adverse effect. Moreover, when it is set as the storage container of a water meter, it hardly fogs the glass of a meter indicator. In addition, because of excellent dimensional stability and excellent moisture barrier properties, it can be used as a part for cold water / hot water storage organs for homes where a maximum use temperature range of −40 ° C. to 100 ° C. is assumed. At this time, even when a transition metal (for example, copper) pipe is accommodated inside the container, almost no deterioration is observed.
<Example>

Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(1) Raw material

(A) Polypropylene resin (a-1) polypropylene propylene homopolymer of component (melting point = 167 ° C., MFR = 6)
(A-2) Polypropylene as component Maleic anhydride-modified polypropylene Melting point = 163 ° C., MFR = 100
(B) Component PPE
PPE having a reduced viscosity of 0.43 obtained by oxidative polymerization of 2,6-xylenol

(C) Component hydrogenated block copolymer Polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) structure, 43% bonded styrene, 95,000 number average molecular weight, polybutadiene before hydrogenation 80% of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds, polystyrene (1) number average molecular weight 30,000, polystyrene (2) number average molecular weight 10,000, polybutadiene part hydrogenation Hydrogenated product of styrene-butadiene block copolymer with a 99.9% rate

(E) Plate-like inorganic filler (e-1) Mica having an average flake diameter of 280 μm (e-2) Graphite having an average flake diameter of 130 μm (e-3) Glass flake having an average flake diameter of 130 μm (e-4) Average flake diameter of 5 μm Graphite (f) fibrous inorganic filler glass fiber having an average diameter of 13 μm and a chop length of 3.5 mm

(2) Pellet molding Using a twin-screw extruder ZSK-25 (manufactured by WERNER & PFLIDEERER), a first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, and a second raw material supply port is provided on the downstream side. Was provided with a vacuum vent. Moreover, the raw material supply method to a 2nd supply port is supplied using a forced side feeder from an extruder side release port. Using the extruder set as described above, (a) polypropylene, (b) polyphenylene ether, (c) hydrogenated block copolymer as an admixture, (e) plate-like inorganic filler, (f) fibrous inorganic The filler was blended with the composition shown in Table 1, and melt-kneaded under conditions of an extrusion temperature of 270 to 320 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 12 kg / hour to obtain pellets.

(3) Test piece Using the resin pellet obtained above, it is supplied to an in-line screw type injection molding machine set at 240 to 280 ° C, and the test piece for measuring the flexural modulus and the deflection temperature under load at a mold temperature of 60 ° C. A test piece for measurement was injection-molded and left in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment.

(3-1) Flexural modulus (ASTM D-790) and deflection temperature under load (ASTM D-648)
Next, the flexural modulus (ASTM D-790) and the deflection temperature under load (ASTM D-648) were measured using these test pieces.

(3-2) Moisture permeability coefficient (unit: g · mm / m ² · day)
The moisture permeation coefficient (unit: g · mm / m ² · day) at 40 ° C. was measured according to JIS Z0208 (moisture permeability test method (cup method) of moisture-proof packaging material). The moisture permeability coefficient was measured by cutting a 1 mm thick flat plate obtained by injection molding of the above pellets into an appropriate shape.

(3-3) Dimensional accuracy Dimensional accuracy was obtained by determining the ratio between the flow direction and the flow right-angle direction of the formed flat plate using a 150 mm square 2 mm thick flat plate mold used for injection moldability evaluation. When this ratio is 1, it is determined that the anisotropy is the smallest, and as the ratio is closer to 1, the anisotropy is smaller and it can be determined that the dimensional accuracy is better.

(3-4) Weldability Test pieces were welded as shown below, and the weldability between the resins was quantitatively measured. Weldability was performed using two types of ultrasonic welding and hot plate welding.
Ultrasonic welding is performed by using a Branson welding machine, cutting two ASTM dumbbell specimens from the center, superimposing them so that the welding area is 2.66 cm ² , and using a 30 mm diameter horn. Welding was performed under the conditions of a welding pressure of 200 MPa and an oscillation time of 0.37 sec. The sample after welding was left to stand in an environment of 23 ° C. and 50% RH for 24 hours and then subjected to a tensile test at a speed of 5 mm / min. The obtained results were divided by the strength obtained by a tensile test (ASTM D-638) using a normal ASTM dumbbell, and each material was compared as a retention rate.
The hot plate weldability uses a hot plate welder manufactured by Takagi Seiko, cuts the ASTM dumbbell test piece from the center part into two parts, and abuts the center part. Welding was performed under the conditions of a welding time of 30 seconds and a pressure bonding time of 30 seconds. The sample after welding was left to stand in an environment of 23 ° C. and 50% RH for 24 hours and then subjected to a tensile test at a speed of 5 mm / min. The obtained results were divided by the strength obtained by a tensile test (ASTM D-638) using a normal ASTM dumbbell, and each material was compared as a retention rate.

(3-5) Copper damage resistance Copper damage resistance is a test piece in which copper foil is in close contact and a test piece in which copper foil is not in close contact with a metal oven under a heat history (100 ° C. × 2000 hours) using a gear oven. The test piece after the heat history treatment was evaluated by applying a load corresponding to an atmospheric temperature of 65 ° C. and a stress of 150 kgf / cm ² , performing a heat-resistant creep test, and measuring the time until breakage. In order to quantify the effect of copper damage resistance, the ratio of the time until the break of the test piece with the copper foil in contact with the time until the break of the test piece without the copper foil attached is maintained. It calculated | required as a rate (%).

<Production of resin container>
Using the resin pellets obtained above, a resin container having a cylindrical shape with an outer diameter of 60 mm, an inner diameter of 56 mm, a height of 50 mm, and a wall thickness of 2 mm under the same molding temperature conditions as the test piece and having a bottom of 2 mm in thickness on one side Was molded. A hole with a diameter of 1 mm was provided at the bottom.
<Join of lid>
As shown in FIG. 2, a plate glass was clamped to the open end of the resin container via an O-ring.

<Moisture permeability coefficient of resin container>
The moisture permeability coefficient at 60 ° C. was measured as follows. A resin container was placed so that the clamped plate glass was on the lower side, and water was introduced from a 1 mm diameter hole provided in the bottom using a syringe. Thereafter, the hole was closed with a metal pin, and the protrusion was sealed by welding. The amount of water input was about 20 cc. Numerical value obtained by measuring the weight of this water-filled cup molded product, leaving it in an environment of 60 ° C., and determining the moisture permeability coefficient of JIS Z0208 (moisture-proof packaging material moisture permeability test method (cup method)) Was the moisture permeability coefficient.

<Gap between resin container and plate glass contact area>
Next, the clearance between the contact portions between the resin container and the plate glass was measured, and the adhesion accuracy between the container and the glass was evaluated as follows. That is, the transferable ink was applied to the entire circumference of the glass contact portion of the resin container, and the glass was gently placed to confirm the ink portion transferred to the glass surface and the portion where no transfer occurred. Next, using a three-dimensional measuring machine, 4 to 5 points of the container part where the transfer occurred on the glass were measured and used as a reference plane. Next, 10 points of container parts where no transfer occurred on the glass were measured uniformly, and the maximum value in the Z-axis direction among the measurements of the 10 points was defined as the glass contact part gap.

<Production of resin container>
As shown in the partially enlarged view of FIG. 1, the same shape as that of the resin container of Example 1 except that a protruding shape having the role of an energy director at the time of ultrasonic welding is provided on the circumference at the open end. A resin container made of a material was produced.

<Join of lid>
Using the same resin pellet as the resin container, a disk-shaped lid having an outer diameter of 70 mm and a wall thickness of 2 mm was produced. The disc-shaped lid was fitted into the open end of the resin container of Example 2 and welded under appropriate conditions using an ultrasonic welder manufactured by Branson (see FIG. 1).

<Moisture permeability coefficient of resin container>
Water was sealed in the same manner as in Example 1 and the hole was closed, and then the weight of the water-sealed container was measured and left in an environment of 60 ° C., and JIS Z0208 (moisture-proof packaging material moisture permeability test method (cup method)) The value obtained by using the method for determining the moisture permeability coefficient was taken as the moisture permeability coefficient.

<Strength of ultrasonic weld>
Ultrasonic welding of resin container and disk-shaped lid, container assembly filled with water is allowed to fall freely from a height of 1.5m to a concrete floor with various directions facing downward, cracks in the welded part, The leakage of the enclosed water was confirmed. Ten samples were each subjected to a drop test, and if any one of them was cracked, it was determined that there was a crack.
<Weld strength retention>
Based on the weldability test method described above, tests for ultrasonic weld strength and hot plate weld strength were performed to determine the weld strength retention rate.
The above results are also shown in Table 1.

The same evaluation was performed using the same resin composition as in Example 2 except that the resin container and the lid were joined using a spin welder manufactured by Branson.
The results are also shown in Table 1.

<Production of resin container>
As shown in the partially enlarged view of FIG. 3, the open end is provided with a protrusion having the role of a hot plate contact portion on the circumference, and is the same shape as the resin container of Example 1 and made of the same material. A container was prepared.
<Join of lid>
Using the same resin pellet as the resin container, a disk-shaped lid having an outer diameter of 70 mm and a wall thickness of 2 mm was produced. The disk-shaped lid was fitted into the open end of the resin container of Example 4 and welded under appropriate conditions using a hot plate welder manufactured by Shin-Kobe Prelatex (see FIG. 3).
The same evaluation was performed using the same resin composition as in Examples 2 and 3.
The results are also shown in Table 1.

A test piece was prepared in the same manner as in the above (1) raw material to (3) test piece except that the composition of the raw material was as shown in Table 1, and various characteristics were measured. Further, a resin container and a disk-shaped lid were prepared in the same manner as in Example 2, water was sealed in the container, and the moisture permeability coefficient and the strength of the ultrasonic welded portion of the resin container were measured.
Further, the welding strength retention was determined in the same manner as in Example 2.
The above results are also shown in Table 1.

A test piece was prepared in the same manner as in the above (1) raw material to (3) test piece except that the composition of the raw material was as shown in Table 1, and various characteristics were measured. Further, a resin container and a disk-shaped lid were prepared in the same manner as in Example 2, water was sealed in the container, and the moisture permeability coefficient and the strength of the ultrasonic welded portion of the resin container were measured.
Further, the welding strength retention was determined in the same manner as in Example 2.
The above results are also shown in Table 1.

A test piece was prepared in the same manner as in the above (1) raw material to (3) test piece except that the composition of the raw material was as shown in Table 1, and various characteristics were measured. Further, a resin container and a disk-shaped lid were prepared in the same manner as in Example 2, water was sealed in the container, and the moisture permeability coefficient and the strength of the ultrasonic welded portion of the resin container were measured.
Further, the welding strength retention was determined in the same manner as in Example 2.
The above results are also shown in Table 1.

[Comparative Examples 1-3]
A test piece was prepared in the same manner as in the above (1) raw material to (3) test piece except that the composition of the raw material was as shown in Table 1, and various characteristics were measured. Further, a resin container and a disk-shaped lid were prepared in the same manner as in Example 2, water was sealed in the container, and the moisture permeability coefficient and the strength of the ultrasonic welded portion of the resin container were measured.
Further, the welding strength retention was determined in the same manner as in Example 2.
The above results are also shown in Table 1.

[Comparative Example 4]
The following resins used in container applications were obtained, molded, and evaluated using the same method as in the examples. The results are also shown in Table 1.
G703H; Asahi Kasei Chemicals PPE-HIPS Alloy / GF 30%

  In container applications that come into contact with water, moisture, or aqueous solutions, it is possible to provide a resin container that satisfies the required characteristics of moisture barrier properties, mechanical properties, dimensional accuracy, copper damage resistance, and balanced in each property, It is useful for refrigerant storage containers for heating element cooling systems, dry containers around building water meters, cold / hot water storage containers for houses, and the like.

It is a figure which shows the shape and structure of the resin-made containers used for the test in the Example. It is a figure which shows the shape and structure of the resin-made containers used for the test in the Example, and a lid | cover.

Claims (6)

(C) Vinyl aromatic compound with respect to a total of 100 parts by weight of (a) polypropylene resin 55 to 95 parts by weight, (b) 45 to 5 parts by weight of polyphenylene ether resin, (a) component and (b) component And at least one polymer block A mainly composed of conjugated diene compound whose total amount of 1,2-vinyl bond and 3,4-vinyl bond of the conjugated diene compound is 45 to 90%. 5 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of a single polymer block B, and (d) the sum of component (a) and component (b) as an inorganic filler (E) 30 to 60 parts by weight of a plate-like inorganic filler having an average flake diameter of 10 to 400 μm and (f) 30 to 60 parts of a fibrous inorganic filler having an average diameter of 3 to 20 μm with respect to 100 parts by weight. The total amount of the component (e) and the component (f) is 60 to 100 parts by weight , and the water vapor transmission coefficient is 0.40 g · mm / m 2 · day or less in a 40 ° C. and 90% RH environment. The refrigerant | coolant storage container of the heat generating body cooling system characterized by comprising the thermoplastic resin which is. The refrigerant storage container for a heating element cooling system according to claim 1, wherein (a) the polypropylene resin is a modified polypropylene resin obtained by reacting with an α, β-unsaturated carboxylic acid or a derivative thereof. (C) The polymer block A constituting the hydrogenated block copolymer is a styrene polymer block, the polymer block B is a butadiene polymer block, and the 1,2-vinyl bond of the butadiene polymer block and 3 3. The refrigerant storage container for a heating element cooling system according to claim 1, wherein the total amount of 1,4-vinyl bonds is 65 to 90%. (E) The plate-like inorganic filler is at least one inorganic filler selected from mica, glass flakes, talc and graphite, and (f) the fibrous inorganic filler is a glass fiber. The refrigerant | coolant storage container of the heat generating body cooling system in any one of 1-3 . The thermoplastic resin injection molded article, a glass component, claim 1-4 in which at least is one lid selected from the group consisting of metallic parts, characterized in Tei Rukoto joined to the refrigerant storage container main body The refrigerant | coolant storage container of the heat generating body cooling system of description. The lid is injection-molded article of the thermoplastic resin, the lid of the thermoplastic resin, ultrasonic welding, spin welding, hot plate welding, Tei Rukoto joined to the refrigerant storage container main body by at least one of The refrigerant | coolant storage container of the heat generating body cooling system of Claim 5 characterized by these.

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