Box-shaped molding

Abstract

To provide a box-shaped molding which holds chemical resistance equivalent to a PPS resin even when a strongly attacking chemical is used, and can achieve both high gas barrier property and strength without generating a burr in molding.SOLUTION: A box-shaped molding has a box shape composed of four surfaces, and has a liquid contact part therein, wherein the liquid contact part is formed of a resin composition containing (a) a crystalline resin, (b) an amorphous resin and (c) a filler, and in morphology analysis by SEM of the resin composition, a phase containing (a) the crystalline resin forms a sea and a phase containing (b) the amorphous resin forms an island, a number average particle diameter of the island is 0.2-1.3 μm, and 60-degree incident angle surface glossiness of the liquid contact surface of the liquid contact part is 85 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a box-shaped molded body. [Background technology]

[0002] Traditionally, metals have been used for containers used to store or transport highly hydrophobic organic solvents. However, as plastics have gained attention for their lightweight characteristics, various resin materials have been developed in recent years, and non-metallic containers with high liquid resistance are now being used. In particular, metals are at risk of corrosion when storing strongly acidic or strongly basic aqueous solutions, so the value of engineering plastics, which are resistant to both hydrophilic and hydrophobic liquids, is increasing. Crystalline resins are an example of such resin materials that are resistant to both hydrophilic and hydrophobic liquids. Taking advantage of their crystalline properties and their high gas barrier properties, they are used in containers for various purposes to store or transport liquids. Among these, polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) is preferably used.

[0003] However, when a crystalline resin is used for a container, the shrinkage rate during molding is large, and if the molded product is precise, the dimensional accuracy may become a problem.

[0004] Furthermore, when PPS is used as a crystalline resin, its high fluidity can cause burrs, a phenomenon in which resin leaks out from small gaps in the gas-releasing parts of the mold during resin molding, and this can worsen moldability.

[0005] One known solution to this problem is to use PPS / PPE resin, which is an alloy of the crystalline resin PPS and the amorphous resin polyphenylene ether (PPE) (Patent Documents 1 to 4). Compared to PPS resin alone, PPS / PPE resin takes advantage of the amorphous nature of PPE to suppress flash and reduce shrinkage, but because it has lower fluidity than PPS, it has sometimes been impossible to mold thin-walled molded products. To solve this problem, a thin-walled component has been proposed that combines strength and high chemical resistance by using PPS / PPE resin filled with a specific filler (Patent Document 5). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-291054 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-316245 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-264124 [Patent Document 4] Japanese Patent Application Publication No. 2019-14776 [Patent Document 5] Japanese Patent Publication No. 2020-180192 Summary of the Invention [Problem to be solved by the invention]

[0007] However, even when such PPS / PPE resins are used, chemical resistance may be insufficient depending on the organic solvent used, particularly when highly hydrophobic chemicals are used. One possible method for improving chemical resistance is to control the dispersion diameter of PPS / PPE, which has a phase separation structure, and reduce the dispersion diameter of PPE resin, which has relatively low chemical resistance. However, when exposed to highly aggressive chemicals, simply reducing the dispersion diameter appropriately may not be enough to prevent container deformation due to the chemicals.

[0008] Therefore, an object of the present invention is to provide a box-shaped molded body that maintains chemical resistance equivalent to that of PPS resin even when using highly aggressive chemicals, does not produce burrs during molding, and is capable of achieving both high gas barrier properties and strength. [Means for solving the problem]

[0009] As a result of extensive research into solving the above problems, the inventors discovered that it is possible to provide a box-shaped molded product that does not deform the container even when aggressive chemicals are used, that retains chemical resistance equivalent to that of PPS resin, that does not produce burrs during molding, and that is capable of achieving both high gas barrier properties and strength, and thus completed the present invention.

[0010] That is, the present invention is as follows. [1] A box-shaped molded body having a box-like shape consisting of four or more sides and having a liquid-contacting part inside, the liquid-contacting part is made of a resin composition containing (a) a crystalline resin, (b) an amorphous resin, and (c) a filler; In a morphology analysis of the resin composition by SEM, the phase containing the (a) crystalline resin forms a sea, and the phase containing the (b) amorphous resin forms islands; the number average particle size of the islands is 0.2 to 1.3 μm, The box-shaped molded body has a liquid-contacting surface of the liquid-contacting part that has a surface glossiness at a 60-degree incident angle of 85 or more. [2] The box-shaped molded body according to [1], which is used to fill with a liquid or to block the filled liquid. [3] The box-shaped molded body according to [1] or [2], wherein the liquid-contacting portion is a flow path for transporting a liquid. [4] The liquid contact area is heated to a temperature of 12.7 (cal / cm) 0.5The box-shaped molded body according to any one of [1] to [3], wherein after being immersed in a glass container filled with the hydrophobic solvent and left to stand in an oven at 60°C for 30 days, the rate of change in brightness of the liquid-contacting surface of the liquid-contacting part from before immersion is less than 10%. [5] The box-shaped molded body according to any one of [1] to [4], wherein the liquid-contacting portion has a portion with a thickness of 1 mm or less. [6] The water vapor permeability of the part less than 1 mm thick is 0.4 g (m 2 The box-shaped molded body according to [5], wherein the temperature is 100°C (days) or less. [7] The box-shaped molded body according to any one of [1] to [6], wherein the (a) crystalline resin contains polyphenylene sulfide. [8] The box-shaped molded body according to any one of [1] to [7], wherein the (b) amorphous resin contains polyphenylene ether. [9] The box-shaped molded product according to any one of [1] to [8], which is a liquid transfer container. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a box-shaped molded body that does not deform even when a highly aggressive chemical is used, and that is capable of achieving both gas barrier properties and strength. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and the present invention is not limited to the following embodiment. Furthermore, the present invention can be carried out by appropriately modifying it within the scope of its gist.

[0013] [Box-shaped molded body] The molded body of this embodiment is a box-shaped molded body having a box-like shape consisting of four or more sides and having a liquid-contacting portion inside it, wherein the liquid-contacting portion is made of a resin composition containing (a) a crystalline resin, (b) an amorphous resin, and (c) a filler, and in morphological analysis of the resin composition by SEM, the phase containing the (a) crystalline resin forms a sea and the phase containing the (b) amorphous resin forms islands, the number average particle diameter of the islands is 0.2 to 1.3 μm, and the 60-degree incident angle surface gloss of the liquid-contacting surface of the liquid-contacting portion is 85 or more.

[0014] [Resin composition] As described above, the box-shaped molded product of this embodiment has a liquid-contacting portion, and the liquid-contacting portion is made of a resin composition containing (a) a crystalline resin, (b) an amorphous resin, and (c) a filler. Each component of the resin composition will be described in detail below.

[0015] <(a) Crystalline Resin> The resin composition of the present embodiment contains (a) a crystalline resin, and by containing (a) a crystalline resin, the chemical resistance of the polymer alloy containing an amorphous resin can be improved. The crystalline resin (a) used in this embodiment is not particularly limited, but examples thereof include polyphenylene sulfide, polyethylene, polypropylene, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, syndioctatic polystyrene, etc. Among these, polyphenylene sulfide is preferred from the viewpoint of further improving chemical resistance.

[0016] [Polyphenylene sulfide] Depending on the production method, polyphenylene sulfide is divided into linear polyphenylene sulfide resin (hereinafter sometimes abbreviated as linear PPS) and crosslinked polyphenylene sulfide resin (hereinafter sometimes abbreviated as crosslinked PPS). The former linear PPS is a polymer containing arylene sulfide repeating units represented by the following general formula (Formula 1) in an amount of usually 50 mol % or more, preferably 70 mol % or more, and more preferably 90 mol % or more. [-Ar-S-] (1) (Here, Ar represents an arylene group, and examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group), a p,p'-diphenylenesulfone group, a p,p'-biphenylene group, a p,p'-diphenylenecarbonyl group, and a naphthylene group.) Linear PPS may be a homopolymer containing one type of arylene group as a structural unit, or a copolymer obtained by mixing two or more different arylene groups from the viewpoints of processability and heat resistance. Among these, linear polyphenylene sulfide resins having p-phenylene sulfide repeating units as the main structural unit are preferred because of their excellent processability and heat resistance and ease of industrial availability.

[0017] Typical methods for producing linear PPS include polymerizing a halogen-substituted aromatic compound, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate; polymerizing sodium sulfide or sodium hydrogen sulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, in a polar solvent; and self-condensation of p-chlorothiophenol. Of these, the most suitable method is reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfone solvent such as sulfolane.

[0018] These manufacturing methods are well known, and linear PPS can be obtained by the methods described in, for example, U.S. Pat. No. 2,513,188, Japanese Patent Publication Nos. 44-27671, 45-3368, 52-12240, 61-225217, U.S. Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, and Japanese Patent Publication No. 5-222196, as well as by the prior art methods exemplified in these patents.

[0019] A preferred linear PPS is a linear polyphenylene sulfide resin having an extractable amount with methylene chloride of 0.7% by mass or less, preferably 0.5% by mass or less, and having a terminal -SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom) of 20 μmol / g or more, preferably 20 to 60 μmol / g.

[0020] The amount of methylene chloride extracted can be measured using the following method. 5 g of linear PPS powder is added to 80 ml of methylene chloride, and Soxhlet extraction is performed for 6 hours. The mixture is then cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. The container used for the extraction is then washed three times with a total of 60 ml of methylene chloride, and the washings are collected in the weighing bottle. The container is then heated to approximately 80°C to evaporate and remove the methylene chloride from the weighing bottle. The residue is then weighed, and the amount of methylene chloride extracted, i.e., the percentage of oligomers present in the linear PPS, can be determined from the amount of residue.

[0021] The -SX group content can be determined as follows. First, linear PPS powder is dried at 120°C for 4 hours, and then 20 g of the dried linear PPS powder is added to 150 g of N-methyl-2-pyrrolidone and vigorously stirred at room temperature for 30 minutes to dissolve any powder agglomerates. The resulting slurry is filtered and then washed seven times, each time with 1 L of warm water at approximately 80°C. The resulting filter cake is reslurried in 200 g of purified water, and the pH of the slurry is adjusted to 4.5 by adding 1 N hydrochloric acid.

[0022] The mixture is then stirred at 25°C for 30 minutes, filtered, and washed six times with 1 liter of warm water at about 80°C each time. The resulting filter cake is reslurried in 200g of pure water and then titrated with 1N sodium hydroxide. The amount of -SX groups present in the linear PPS can be determined from the amount of sodium hydroxide consumed.

[0023] A specific example of a method for producing a linear PPS that satisfies the requirements of an extractable amount with methylene chloride of 0.7% by mass or less and a terminal -SX group content of 20 μmol / g or more is the method described in Japanese Patent Laid-Open No. 8-253587, in which an alkali metal sulfide and a dihaloaromatic compound are reacted in an organic amide solvent, and during the reaction, the gas phase in the reactor is cooled to condense part of the gas phase inside the reactor, and this condense is then refluxed into the liquid layer above the reaction solution, thereby reducing the oligomer content. The crosslinked (including semi-crosslinked) polyphenylene sulfide resin is obtained by polymerizing the linear polyphenylene sulfide resin described above, and then further heat-treating the polymer in the presence of oxygen at a temperature equal to or lower than the melting point of the polyphenylene sulfide resin to promote oxidative crosslinking and appropriately increase the polymer molecular weight and viscosity.

[0024] Among these crosslinked PPS, the most preferred crosslinked PPS is a crosslinked polyphenylene sulfide resin with a volatile content of 1000 ppm or less when collected in a molten state at 320°C, from the viewpoints of preventing gas and tar generation when the resin composition obtained by the present invention is molded and of mold releasability. The amount of volatile content collected in a molten state at 320°C can be determined by the following method. Specifically, 0.5 g of crosslinked PPS powder was weighed into a sealed test tube with an airflow inlet and outlet, and immersed in a solder bath heated to 320°C for 30 minutes. Nitrogen gas was injected into the test tube through the airflow inlet at a flow rate of 100 cc / min. The gas, including volatiles derived from the crosslinked PPS, was purged through the airflow outlet. The purged gas was then bubbled through the airflow inlet of a sealed test tube containing acetone, dissolving the volatiles in the acetone. The volatiles from the crosslinked PPS dissolved in acetone were analyzed using a gas chromatograph mass spectrometer (GC-MS) at a temperature ramp from 50°C to 290°C. The total amount of detected components was then quantified, assuming the same sensitivity as monochlorobenzene, to determine the amount of volatiles in the crosslinked PPS.

[0025] To obtain a crosslinked PPS with a volatile content of 1000 ppm or less when melted at 320°C, it is usually possible to obtain a crosslinked PPS with the desired volatile content by adjusting the polymer concentration and solvent composition during the polymerization stage of linear PPS, by adjusting the washing method for recovering the polymer during the polymerization stage, or by changing the temperature and time of high-temperature treatment during the subsequent crosslinking stage.

[0026] Furthermore, these PPSs (linear PPS, crosslinked PPS) may be acid-modified PPSs. Acid-modified PPSs are those obtained by modifying the above-mentioned PPSs with an acid compound. Examples of such acid compounds include unsaturated carboxylic acids or their anhydrides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and maleic anhydride, as well as saturated aliphatic carboxylic acids and aromatic-substituted carboxylic acids. Furthermore, inorganic acid compounds, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, and carbonic acid, are also examples of such acid compounds.

[0027] The melt viscosity of the above-mentioned linear PPS and crosslinked PPS at 300° C. is preferably 1 to 10,000 Pa·s, more preferably 50 to 8,000 Pa·s, and even more preferably 100 to 5,000 Pa·s.

[0028] In the specification, the melt viscosity is a value measured using a flow tester (Model CFT-500 manufactured by Shimadzu Corporation) in accordance with JIS K-7210 as a reference test method, after preheating PPS to 300°C for 6 minutes, with a load of 196 N and a die length (L) / die diameter (D) ratio of 10 mm / 1 mm.

[0029] Here, the (a) crystalline resin is preferably contained in an amount of 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass, based on 100% by mass of the resin composition. By ensuring that the (a) crystalline resin content is 20% by mass or more, it is possible to ensure gas barrier properties in thin-walled portions. Furthermore, by ensuring that the (a) crystalline resin content is 80% by mass or less, it is possible to suppress flash and outgassing from the molded product.

[0030] The resin composition contains (a) crystalline resin and (b) amorphous resin (described later), and the ratio of the content of the (b) amorphous resin to the content of the (a) crystalline resin ((b):(a)) is preferably 5:5 to 2:8, more preferably 4:6 to 2.2:7.8, and even more preferably 3.5:6.5 to 2.4:7.6. By setting the ratio of the content of the (b) amorphous resin to the content of the (a) crystalline resin ((b):(a)) to 5:5 or less, the gas barrier properties of the liquid-contacting parts can be ensured, and by setting this ratio to 2:8 or more, flash can be suppressed and outgassing from the molded product can be suppressed.

[0031] <(b) Amorphous resin> The resin composition of the present embodiment contains (b) an amorphous resin, and by containing (b) an amorphous resin, it is possible to suppress burrs and suppress outgassing from a molded product.

[0032] Examples of the (b) amorphous resin that can be used in this embodiment include thermoplastic resins that do not assume a crystalline state or that have extremely low crystallinity even if they crystallize, and thermoplastic polymer alloys such as those exemplified below. "Not assuming a crystalline state or having extremely low crystallinity even if they crystallize" refers to a resin in which no exothermic peak associated with crystallization is observed (no crystalline region), or even if observed, the crystallinity is so low that the heat of fusion of the crystal is, for example, 10 J / g or less. The heat of fusion of the crystal can be measured using a differential scanning calorimeter.

[0033] Specifically, the (b) amorphous resin is not particularly limited as long as it is a resin having amorphous properties, and examples thereof include styrene-based resins such as polystyrene, rubber-reinforced polystyrene (high-impact polystyrene), and acrylonitrile-butadiene-styrene copolymer (hereinafter also referred to as "ABS"); polycarbonate-based resins such as polycarbonate, polycarbonate / ABS alloy, and polycarbonate / polybutylene terephthalate alloy; and polyphenylene ether-based resins such as polyphenylene ether, polyphenylene ether / polystyrene alloy, polyphenylene ether / high-impact polystyrene alloy, and polyphenylene ether / polystyrene / high-impact polystyrene alloy.

[0034] Furthermore, as the (b) amorphous resin, particularly from the viewpoints of heat resistance, dimensional accuracy, and flame retardancy, a resin that has a high glass transition temperature and is relatively easy to make flame retardant is desirable, and a polyphenylene ether-based resin is preferred, and polyphenylene ether, polyphenylene ether / polystyrene alloy, polyphenylene ether resin / high-impact polystyrene resin alloy, or polyphenylene ether resin / polystyrene resin / high-impact polystyrene resin alloy is more preferred.

[0035] The content of the (b) amorphous resin in the thin portion of this embodiment is not particularly limited, but is preferably 10 to 40 mass % relative to the resin composition, more preferably 12 to 30 mass %, and even more preferably 15 to 20 mass %. By setting the content to 10% by mass or more, flash can be suppressed and outgassing from the molded product can be suppressed, and by setting the content to 40% by mass or less, gas barrier properties and chemical resistance of the thin-walled part can be ensured.

[0036] [Polyphenylene ether resin] As described above, the polyphenylene ether resin may be polyphenylene ether, polyphenylene ether / polystyrene alloy, polyphenylene ether / high-impact polystyrene alloy, polyphenylene ether / polystyrene / high-impact polystyrene alloy, etc. Among these, polyphenylene ether is preferred from the viewpoint of the dimensional accuracy and chemical resistance of the molded article.

[0037] The structure of the polyphenylene ether (hereinafter sometimes abbreviated as PPE) of the polyphenylene ether-based resin is not particularly limited, but it is preferably a homopolymer and / or copolymer polyphenylene ether that is composed of a repeating unit represented by the following bond unit formula (2) and has an intrinsic viscosity measured in chloroform at 30°C using an Ubbelohde viscometer of preferably 0.16 to 0.36, more preferably 0.20 to 0.34. [ka] ···(2) (wherein R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group in which at least two carbon atoms separate the halogen atom from the oxygen atom, and may be the same or different from one another; and n is an integer of 1 or greater.)

[0038] By setting the intrinsic viscosity of the polyphenylene ether resin to 0.16 or higher, a good balance of mechanical properties, fluidity, and releasability can be achieved, and by setting it to 0.36 or lower, fluidity particularly in the high shear range (for example, SFD characteristics of 0.5 mm) and flame retardancy can be improved.

[0039] Specific examples of this 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), poly(2,6-dichloro-1,4-phenylene ether), etc., and further include polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol with other phenols (e.g., 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Among these, poly(2,6-dimethyl-1,4-phenylene ether) and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, with poly(2,6-dimethyl-1,4-phenylene ether) being more preferred.

[0040] There are no particular limitations on the method for producing such PPE. For example, PPE can be easily produced by oxidatively polymerizing, for example, 2,6-xylenol using a complex of cuprous salt and amine by Hay as a catalyst, as described in U.S. Pat. No. 3,306,874. PPE can also be easily produced by adjusting the intrinsic viscosity using methods described in U.S. Pat. Nos. 3,306,875, 3,257,357, and 3,257,358, Japanese Patent Publication No. 17880 / 1977, 51197 / 1975, and 152628 / 1988, etc.

[0041] As described above, the polyphenylene ether resin is preferably 100% by mass of PPE, but it can also be used as a polymer alloy, in which case the PPE content in 100% by mass of the polymer alloy can be 1 to 99% by mass.

[0042] Examples of polystyrene that can be used for polyphenylene ether resins include homopolymers of styrene compounds and copolymers of two or more styrene compounds, and examples of high-impact polystyrene include rubber-modified styrenes in which rubber-like polymer particles are dispersed in a matrix of styrene compound polymers. Examples of styrene compounds that produce these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, and p-tert-butylstyrene.

[0043] When polyphenylene ether resins are used as polymer alloys as described above, the resins contained in the PPE may be copolymers obtained by combining two or more styrene compounds or high-impact polystyrene, but polystyrene obtained by polymerizing styrene alone is preferred. Furthermore, polystyrene resins with stereoregular structures such as atactic polystyrene and syndiotactic polystyrene can be effectively used as polyphenylene ether resins.

[0044] By setting the intrinsic viscosity of polyphenylene ether resin to 0.16 or higher, a good balance of mechanical properties, fluidity, and releasability can be achieved, and by setting it to 0.36 or lower, fluidity particularly in the high shear range (for example, SFD characteristics of 0.5 mm) and flame retardancy can be improved.

[0045] When a polyphenylene ether resin is used as the (b) amorphous resin, the ratio of the content of the (b) amorphous resin to the content of the (a) crystalline resin ((b):(a)) is preferably 4:6 to 2:8, and more preferably 3.5:6.5 to 2.2:7.8. By setting the ratio of the content of the (b) amorphous resin to the content of the (a) crystalline resin as the polyphenylene ether resin ((b):(a)) to 4:6 or less, the gas barrier properties, fluidity, and flame retardancy of the thin-walled portion can be improved, and by setting this ratio to 2:8 or more, flash during molding of the resin composition can be suppressed and mold releasability can be improved.

[0046] <(c) Filler> (c) The filler is not particularly limited, but may be at least one selected from the group consisting of glass fiber, carbon fiber, carbon nanotube, cellulose fiber, silicon carbide fiber, ceramic fiber, aramid fiber, alumina fiber, gypsum fiber, metal fiber, calcium titanate whisker, calcium carbonate whisker, and wollastonite. These fibrous inorganic fillers may be further treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aliphatic metal salt, or may be treated with a resin such as a urethane resin or an epoxy resin as a binder. Among these, glass fiber is preferred from the viewpoints of heat resistance and adhesion to resin.

[0047] Furthermore, the average length of (c) filler is preferably 50 to 170 μm. By setting the average length to 50 μm or more, mechanical strength can be improved, and by setting the average length to 170 μm or less, gas barrier properties and surface smoothness can be ensured. It is presumed that the reason for improved gas barrier properties is that the use of a short filler prevents the filler from protruding onto the surface of the molded article, thereby preventing the boundary between the filler and the resin from appearing on the surface, ensuring gas barrier properties. The average length of (c) filler is preferably 80 to 165 μm, and more preferably 120 to 160 μm.

[0048] Here, the average length of the (c) filler in this embodiment can be determined as follows. First, the thin-walled portion in this embodiment is placed in, for example, an electric furnace, and the molded product containing it is incinerated. The (c) filler can be extracted from the residue (ash). When extracting the (c) filler from the residue, for example, if the molded product contains fillers other than the (c) filler, the residue derived from the (c) filler can be separated by dispersing all of the residue in water or another solvent and allowing it to settle. Furthermore, the method for measuring the average length of the (c) filler is not particularly limited as long as it is an image processing device that can observe the filler under a microscope and binarize the obtained image. The arithmetic mean of the obtained major axis and minor axis values ​​for any 300 particles of the (c) filler can be used to determine the average length of the (c) filler. More specifically, it can be measured using the method described in the Examples.

[0049] The content of the (c) filler in the resin composition of this embodiment is not particularly limited, but is preferably 10 to 60 mass %, more preferably 15 to 40 mass %, and even more preferably 20 to 40 mass %, relative to 100 mass % of the resin composition. By setting the content to 10% by mass or more, it is possible to further improve the mechanical strength, and by setting the content to 60% by mass or less, it is possible to ensure higher gas barrier properties.

[0050] <Polyphenylene sulfide nucleating agent> The resin composition of the thin-walled portion of the molded product of this embodiment may contain a nucleating agent for polyphenylene sulfide. When the resin composition contains a nucleating agent for polyphenylene sulfide, the gas barrier properties can be further improved when polyphenylene sulfide is used as the crystalline resin, and the dimensional accuracy of the thin-walled portion can also be improved.

[0051] The polyphenylene sulfide crystal nucleating agent is not particularly limited as long as it is an additive that increases the rate of polyphenylene sulfide crystal nucleation. Examples include inorganic nucleating agents such as silica, kaolin, talc, hytron, and boron nitride; organic metal carboxylates such as calcium stearate, aluminum stearate, dipotassium succinate, calcium benzoate, disodium phthalate, trisodium trimellitate, and tetrapotassium pyromellitate; and polymers with higher melting points than polyphenylene sulfide, such as polyphenylene sulfide ketone and nylon 46. Among these, inorganic nucleating agents are preferred, with talc being more preferred. More specifically, talc can be used as a plate-like crystal with an average particle size of 1 to 50 μm and composed primarily of hydrous magnesium silicate (SiO: 58 to 64%, MgO: 28 to 32%, Al2O3: 0.5 to 5%, Fe2O3: 0.3 to 5%). The average particle size of the talc is more preferably 10 to 40 μm, and even more preferably 20 to 35 μm.

[0052] The shape of the polyphenylene sulfide crystal nucleating agent can be measured in the same manner as in the measurement of the average length of the filler (c) described above. The nucleating agent may be subjected to a surface treatment using a silane coupling agent, a titanate coupling agent, an aliphatic metal salt, or the like; it may be subjected to an organo-treatment using an ammonium salt or the like by an intercalation method; or it may be subjected to a binder treatment using a resin such as a urethane resin or an epoxy resin.

[0053] <Scale-like inorganic filler> The filler used in the resin composition of the molded article of this embodiment may be a scaly inorganic filler. The content of the scaly inorganic filler is preferably 10 to 40% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 40% by mass, relative to 100% by mass of the resin composition. By setting the content to 10% by mass or more, it is possible to further improve the mechanical strength, and by setting the content to 40% by mass or less, it is possible to ensure higher gas barrier properties.

[0054] Here, examples of the scaly inorganic filler include glass flakes and mica. The scaly inorganic filler is scaly, and has an average major axis of preferably 1000 μm or less, more preferably 1 to 500 μm, and even more preferably 1 to 200 μm, and an average minor axis of preferably 1000 μm or less, more preferably 1 to 500 μm, and even more preferably 1 to 200 μm.

[0055] The aspect ratio (L1 / L2) of the average major axis L1 to the average minor axis L2 of the scaly inorganic filler is 3 or less, preferably 2 or less, and more preferably 1.6 or less. The scaly inorganic filler preferably has an average aspect ratio (L1 / T) of the average major axis L1 to the average thickness T of more than 5, more preferably 10 or more, and even more preferably 30 or more. The average major axis, average minor axis, and aspect ratio of the scaly inorganic filler can be measured by the same method as for the average length of the filler (c) described above.

[0056] <Emulsifying dispersant, compatibilizer> Furthermore, in this embodiment, when mixing component (a) and amorphous resin (b), it is preferable to add an emulsifying dispersant or a compatibilizing solvent. From the viewpoint of finely dispersing the islands of the sea-island structure, it is more preferable to use an emulsifying dispersant.

[0057] [[Emulsifying dispersant]] Examples of emulsifying dispersants used as components include (1) epoxy resins, (2) silane coupling agents, and (3) compounds containing epoxy groups and / or copolymers containing oxazolyl groups. Among these, copolymers of unsaturated monomers having epoxy groups and / or oxazolyl groups and monomers containing styrene as the main component are more preferably used.

[0058] The monomer primarily composed of styrene referred to here does not pose any problem if it is 100% by mass of styrene. However, if other monomers copolymerizable with styrene are present, the copolymer chain must contain at least 65% by mass or more, more preferably 75 to 95% by mass, of styrene monomer in order to maintain miscibility with the polyphenylene ether resin (b). Specific examples of such monomers include copolymers of styrene monomers with unsaturated monomers having epoxy and / or oxazolyl groups, and copolymers of styrene / acrylonitrile (90 to 75% by mass / 10 to 25% by mass) with unsaturated monomers having epoxy and / or oxazolyl groups.

[0059] Examples of epoxy group-containing unsaturated monomers include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, glycidyl itaconate, etc., and among these, glycidyl methacrylate is preferred. Furthermore, as the oxazolyl group-containing unsaturated monomer, for example, 2-isopropenyl-2-oxazoline is industrially available and can be preferably used.

[0060] Other unsaturated monomers copolymerizable with these epoxy and / or oxazolyl-containing unsaturated monomers include vinyl cyanide monomers such as acrylonitrile, vinyl acetate, and (meth)acrylic acid esters, in addition to the essential vinyl aromatic compound such as styrene. In the present invention, it is essential that the copolymer contains at least 65% by mass of styrene monomer, excluding the epoxy and / or oxazolyl-containing unsaturated monomers. Furthermore, the epoxy and / or oxazolyl-containing unsaturated monomers must be present in the copolymer in an amount of 0.3 to 20% by mass, preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

[0061] The amount of unsaturated monomer having an epoxy group and / or an oxazolyl group in the copolymer of such an emulsifying dispersant component must be 0.3% by mass or more, and if it is 20% by mass or less, the miscibility between the polyphenylene sulfide resin of component (a) and the polyphenylene ether resin of component (b) will be good, and the occurrence of flash in molded products made from the resulting resin composition can be significantly suppressed, while also achieving an excellent balance between toughness (impact strength) and rigidity.

[0062] Examples of copolymers of emulsifying and dispersing agent components obtained by copolymerizing copolymerizable unsaturated monomers include styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene-glycidyl methacrylate-acrylonitrile copolymer, styrene-vinyloxazoline copolymer, and styrene-vinyloxazoline-acrylonitrile copolymer.

[0063] The amount of the emulsifying dispersant component admixture is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of the total of the above-mentioned components (a) and (b). If the amount of the emulsifying dispersant component is 1 part by mass or more, the effect of improving the miscibility between components (a) and (b) tends to be more pronounced, and if it is 20 parts by mass or less, the occurrence of flash in molded products molded using the resulting resin composition tends to be significantly suppressed, and a good balance between toughness (impact strength) and rigidity tends to be achieved.

[0064] [Compatibilizer] The compatibilizer used as a component includes hydrogenated styrene-based thermoplastic elastomer, and known ones can be used.

[0065] <Other materials constituting the resin composition> The resin composition of the present embodiment may optionally contain the following components.

[0066] [Flame retardant] The resin composition of this embodiment may contain a flame retardant. To improve flame retardancy, flame retardants that are typically added to thermoplastic resins may be used, but it is preferable to add an organophosphorus flame retardant that does not contain halogen. The organophosphorus flame retardants may be used alone or in combination of two or more.

[0067] Examples of organic phosphorus flame retardants include phosphate ester compounds, phosphazene compounds, etc. The phosphate ester compounds are added to improve flame retardancy, and any organic phosphate esters that are commonly used as flame retardants can be used.

[0068] Specific examples of the phosphate ester compound include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bis[di(2,6-dimethylphenyl)phosphate], 2,2-bis{4-[bis(phenoxy)phosphoryloxy]phenyl}propane, 2,2-bis{4-[bis(methylphenoxy)phosphoryloxy]phenyl}propane, and the like, but are not limited to these. Further, examples of phosphorus-based flame retardants other than those mentioned above include phosphate ester-based flame retardants such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, and diisopropyl phenyl phosphate; diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, and diphenyl-4-hydroxy-3,5-dibromobenzyl phosphate; monophosphate ester compounds such as phenyldiphenyl phosphate, phenylnonylphenyl hydroquinonyl phosphate, phenyldinonylphenyl phosphate, and phenyldinonylphenyl phosphate; and aromatic condensed phosphate ester compounds. Among these, aromatic condensed phosphate ester compounds are preferably used because they generate less gas during processing and have excellent thermal stability.

[0069] The flame retardant that can be used in this embodiment is preferably a phosphate ester compound (condensed phosphate ester) represented by the following general formula (I) or (II). Particularly preferred is a phosphate ester compound (condensed phosphate ester) represented by the following general formula (I).

[0070] [ka]

[0071] [ka]

[0072] (In general formulas (I) and (II), Q1, Q2, Q3, and Q4 are each a substituent and each independently represent an alkyl group having 1 to 6 carbon atoms; R11 and R12 each represent a methyl group; R13 and R14 each independently represent a hydrogen atom or a methyl group; n is an integer of 1 or greater; n1 and n2 each independently represent an integer of 0 to 2; and m1, m2, m3, and m4 each independently represent an integer of 0 to 3.)

[0073] In the condensed phosphate esters represented by the above general formulas (I) and (II), n is an integer of 1 or more, preferably an integer of 1 to 3, in each molecule.

[0074] Among the condensed phosphate esters represented by the above general formulas (I) and (II), preferred are condensed phosphate esters in which m1, m2, m3, m4, n1, and n2 in formula (I) are zero and R13 and R14 are methyl groups, or condensed phosphate esters in formula (I) in which Q1, Q2, Q3, Q4, R13, and R14 are methyl groups, n1 and n2 are zero, and m1, m2, m3, and m4 are integers of 1 to 3, and it is preferred that the condensed phosphate ester contains 50 mass% or more of a phosphate ester in which n is an integer of 1 to 3, particularly 1.

[0075] These aromatic condensed phosphate ester compounds are generally commercially available, and known examples include CR741, CR733S, and PX200 from Daihachi Chemical Industry Co., Ltd., and FP600, FP700, and FP800 from ADEKA Corporation.

[0076] Particularly preferred among these aromatic condensed phosphate ester compounds are those having an acid value of 0.1 or less (a value obtained in accordance with JIS K2501) from the viewpoint of thermal stability.

[0077] Moreover, as the phosphazene compound, phenoxyphosphazene and its crosslinked product are preferred, and from the viewpoint of thermal stability, phenoxyphosphazene compounds having an acid value of 0.1 or less (value obtained in accordance with JIS K2501) are particularly preferred.

[0078] The content of the flame retardant varies depending on the required level of flame retardancy, but is preferably in the range of 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, per 100 parts by mass of the total of (a) crystalline resin and (b) amorphous resin. When the content of the flame retardant is 1 part by mass or more, the fluidity and flame retardancy of the resin composition are improved, when it is 30 parts by mass or less, the flame retardancy of the resin composition is sufficient, and when it is 30 parts by mass or less, the balance of fluidity, mold releasability, and burr suppression is improved.

[0079] [[Other additives]] In addition to the various materials described above, the resin composition of the present embodiment may also contain, as needed, various additives that are added to ordinary thermoplastic resins, such as stabilizers such as heat stabilizers, antioxidants, and ultraviolet absorbers, conductivity-imparting agents, antistatic agents, colorants such as pigments and dyes, and mold release agents.

[0080] [Method of producing resin composition] The resin composition of this embodiment can be produced using various melt kneaders, kneading extruders, etc. As the melt kneader or kneading extruder, a known kneader can be used, and examples thereof include extruders such as a single-screw extruder or a multi-screw extruder such as a twin-screw extruder; and heat melt kneaders such as a roll, a kneader, a Brabender plastograph, and a Banbury mixer. Among these, a twin-screw extruder is preferred. A preferred method is to use the above-mentioned components and melt-knead them using a twin-screw extruder having at least two vent ports and at least one side feed port set at 280° C. or higher. In one preferred specific embodiment of the method for producing the resin composition of this embodiment using a twin-screw extruder, components (a) and (b), and an optional emulsifying dispersant component are simultaneously fed into a first feed port of the twin-screw extruder and melt-kneaded; while the basic resin composition composed of these components is in a melt-kneaded state, the first vent port of the twin-screw extruder is suction-deaerated at an absolute vacuum pressure of 95 kPa or less; subsequently, if the optional additive (e.g., a flame retardant) is in liquid form, the additive is fed using a liquid addition pump; the optional component is fed through a Side 1 feed port of the twin-screw extruder provided downstream, and component (c) is fed through a Side 2 feed port further downstream; the respective components are melt-kneaded; and finally, the second vent port of the twin-screw extruder is suction-deaerated at an absolute vacuum pressure of 95 kPa or less.

[0081] [Characteristics of resin composition] -Morphology of resin compositions- When the resin composition of this embodiment is analyzed for morphology using an SEM, (a) a phase containing a crystalline resin forms a sea, and (b) a phase containing an amorphous resin forms islands, and the number average particle size of the islands falls within the range of 0.2 to 1.3 μm.

[0082] By staining with heavy metal using osmium tetroxide and using morphology contrast, it can be confirmed that the parts that form the sea are (a) a phase containing crystalline resin, and the parts that form the islands are (b) a phase containing amorphous resin, based on the shade of the stain.

[0083] More specifically, in a conventional component, in a portion that is made of a resin composition containing a crystalline resin and an amorphous resin, when the phase containing the crystalline resin forms islands and the phase containing the amorphous resin forms a sea, if a highly aggressive hydrophobic liquid is used, the hydrophobic liquid may penetrate into the resin, causing deformation of the container, a decrease in gas barrier properties, and a decrease in mechanical strength.

[0084] Therefore, to prevent container deformation, deterioration of gas barrier properties, and deterioration of mechanical strength, it is preferable to design a molded article so that the phase containing the crystalline resin forms a sea and the phase containing the amorphous resin forms islands. To achieve a sea-like structure containing the (a) crystalline resin and an island-like structure containing the (b) amorphous resin, the mass ratio of the two components is preferably (a) crystalline resin / (b) amorphous resin = 5 / 5 to 8 / 2, more preferably 4:6 to 2.2:7.8. Having a higher amount of (a) crystalline resin than a (a) crystalline resin / (b) amorphous resin ratio of 5 / 5 is preferable because it makes it easier for the (a) crystalline resin-containing phase to form a sea. However, because the sea-island structure is also affected by the type and amount of the emulsifying dispersant described above, the mass ratio of the (a) crystalline resin to the (b) amorphous resin is not limited to this composition ratio.

[0085] Furthermore, when (a) the crystalline resin-containing phase forms a sea and (b) the amorphous resin-containing phase forms islands, the number-average particle size of the islands is 0.2 to 1.3 μm, preferably 0.25 to 1.0 μm, more preferably 0.3 to 0.9 μm, and even more preferably 0.4 to 0.8 μm. Having a number-average particle size of 1.3 μm or less prevents penetration of highly aggressive hydrophobic liquids into the polyphenylene ether resin, thereby preventing deformation of the container, even when the liquid contacts the polyphenylene ether resin. Having a number-average particle size of 0.2 μm or more prevents excessive high fluidity of the crystalline resin, resulting in the formation of burrs at gas escape sites or mold clamping parting lines during molding, which reduces moldability.

[0086] The morphology and number average particle size of the islands can be measured by observing the cross section with an electron microscope, and more specifically, can be measured by the method described in the examples.

[0087] Methods for adjusting the number-average particle size of the islands within the above range include adjusting the mass ratio of the crystalline resin to the amorphous resin, adjusting the type and amount of emulsifying dispersant, and using polymer molecular chain modification and extrusion reaction techniques. Specifically, the dispersion size can be reduced by increasing the mass ratio of the crystalline resin and the amount of emulsifying dispersant. Furthermore, the compatibility between the crystalline resin and the amorphous resin can be improved by using polymer molecular chain modification and extrusion reaction techniques, thereby reducing the dispersion size.

[0088] [Characteristics of box-shaped molded body] -Surface condition of the wetted part- In the box-shaped molded product of this embodiment, the 60-degree incident angle surface gloss of the liquid contact surface of the liquid contact part is 85 or more, preferably 90 or more, more preferably 92 or more, and even more preferably 93 or more. By having the 60-degree incident angle surface gloss of the liquid contact surface be 85 or more, it is possible to further improve resistance to highly aggressive hydrophobic liquids.

[0089] Although the detailed mechanism by which this effect occurs is unknown, the following reason is presumed. A gloss level of 85 or higher is thought to reduce the amount of minute irregularities on the liquid-contacting surface. In other words, the reduced amount of minute irregularities reduces the surface area of ​​the molded product that comes into contact with chemicals. This reduces the area of ​​the island portions of the amorphous resin that have a phase-separated structure that is relatively permeable to chemicals, which is thought to prevent deformation of the container and a decrease in mechanical strength and gas barrier properties, even when a highly aggressive hydrophobic liquid comes into contact with the container.

[0090] The surface glossiness at an incident angle of 60 degrees of the liquid-contacting surface can be measured by a glossmeter, and more specifically, can be measured by the method described in the examples.

[0091] Methods for adjusting the 60-degree incident angle surface gloss of the liquid-contacting surface within the above range include using a material with a low coefficient of friction for the coating of the mold used for molding to prevent the resin from sticking to the mold, and adjusting the mold temperature and injection speed during molding (described below). Specifically, setting the mold temperature during molding higher than the glass transition temperature of the crystalline resin tends to increase the 60-degree incident angle surface gloss. Regarding the method of using a material with a low coefficient of friction for the coating of the mold used for molding, using a coating containing titanium nitride and chromium nitride components instead of a typical hard chrome material tends to increase the 60-degree incident angle surface gloss. Regarding the method of adjusting the injection speed, adjusting it to a range of 50 to 100 mm / sec, preferably 80 to 90 mm / sec, tends to increase the 60-degree incident angle surface gloss. Furthermore, favoring the morphology (described below) tends to increase the 60-degree incident angle surface gloss.

[0092] - Brightness of the wetted surface of the wetted part - The change in brightness of the liquid-contacting surface of the liquid-contacting part after contacting the hydrophobic liquid at 60°C for 30 days is preferably less than 10%, more preferably less than 8%, and even more preferably less than 6%. A change in brightness of less than 10% indicates that the surface is protected from the effects of chemical attack, and tends to more effectively prevent deformation of the container and a decrease in mechanical strength.

[0093] The brightness and the rate of change in brightness can be measured by a brightness meter, and more specifically, they are measured by the method described in the examples.

[0094] The hydrophobic liquid used in the above-mentioned contacting liquid is not particularly limited, but for example, the solubility parameter (SP value, unit (cal / cm)) 0.5) can be used as a guide for selection. In particular, in the present invention, it is preferable to use a hydrophobic liquid whose hydrophobicity indicated by the solubility parameter is 8 to 16, and examples thereof include ε-caprolactone, n-methylpyrrolidone, methyl methacrylate, γ-butyrolactone, ε-caprolactam, 1,3-propylene carbonate, methanol, ethanol, ethylene carbonate, ethylene glycol, and glycerin. These solutions may be mixed in any amount and used.

[0095] -Thickness of the liquid contact part and gas barrier properties- In the box-shaped molded body of this embodiment, for reasons of resource efficiency, weight reduction, and increased design freedom, it is preferable that the liquid-contacting portion be thin, and specifically, it is preferable that it have a portion that is 1 mm or less in thickness.

[0096] If the thickness of the liquid-contacting part is 1 mm or less, gases from the atmosphere may dissolve in the liquid filled in the container, causing problems with the liquid properties, compared to when the thickness is thicker. For this reason, the gas barrier properties are such that the water vapor permeability is 0.4 g / (m 2 ·day) or less, and 0.3g / (m 2 ·day) or less is more preferable, and 0.2g / (m 2 ·day) or less is more preferable. 2 By having a water vapor transmission rate of 1000 kJ / day or less, it tends to be possible to prevent water vapor from penetrating the filled container and dissolving into the liquid. This tends to prevent air bubbles from forming when temperature changes occur outside the container, which can impair the properties of the filled liquid, and also tends to prevent short circuits and reduced performance of circuit boards stored inside components that may be adversely affected by moisture, such as electronic circuits. The water vapor permeability can be measured using a water vapor permeability tester, and more specifically, can be measured by the method described in the examples.

[0097] Gas barrier properties: oxygen permeability is 150cm at a thickness of 1mm. 3 / (m 2·day·atm) or less, and 3 / (m 2 ·day·atm) or less is more preferable, and 3 / (m 2 It is more preferable that the temperature is 1000 K or less (1000 K / day atm). 50cm 3 / (m 2 By having a water vapor permeability of 1000 kJ / day atm or less, oxygen can penetrate the container filled inside the molded product and dissolve in the liquid, which tends to prevent the contents from oxidizing and other deterioration. The oxygen permeability can be measured using an oxygen permeability tester, and more specifically, can be measured by the method described in the examples.

[0098] When the liquid-contacting portion has a portion (thin portion) having a thickness of 1 mm or less, the thin portion can be positioned in a portion that partitions the internal space of a container or the like in which a chemical solution or the like is present, a portion that forms, for example, a flow path that comes into contact with the chemical solution or the like, or a portion that blocks leakage of the volatilized chemical solution or the like to the outside or inside. The thin portion in this embodiment has a predetermined surface glossiness on the liquid-contacting surface and is made of a predetermined resin composition, which can improve not only the gas barrier property and strength but also the surface smoothness, and thereby suppress the effects of turbulence in liquid transfer when the thin portion is, for example, a flow path that comes into contact with the chemical solution or the like.

[0099] -Box-shaped molded body structure- Furthermore, the box-shaped molded body of this embodiment has a box-shaped shape consisting of at least four sides, and its shape is not limited as long as it has a liquid-contacting part inside, but it is preferable that at least a portion of the liquid-contacting part is tubular, and it is more preferable that the thin-walled part has a tubular part. Here, the term "tubular" is not particularly limited as long as a closed area is formed by the outline of the inner surface in a cross-sectional view, and various shapes such as a circle, an ellipse, a polygon, etc. can be used. Furthermore, when the thin-walled portion has a tubular portion, the thin-walled portion can have any shape other than the tubular portion. The box-shaped molded body of this embodiment can have various shapes, for example, so that it becomes tubular by using the liquid-contacting portion together with other parts. Furthermore, the tubular portion has an opening area of ​​400 mm2 to ensure the strength of the tubular portion itself. 2 Preferably, the size is less than 200mm 2 Preferably, the size is less than 100mm. 2 It is more preferable that the size is:

[0100] The box-shaped molded body of this embodiment may have a structure with one bottom surface and three side surfaces, may have a structure with one bottom surface and four side surfaces, may have a structure with one bottom surface and five or more side surfaces, and in each of the above structures, the number of bottom surfaces may be two or more. The box-shaped molded body of this embodiment usually has a structure with one bottom surface and four side surfaces perpendicular to the bottom surface.

[0101] The liquid-contacting portion of the box-shaped molded body of this embodiment may be located inside the box-shaped molded body, specifically within the internal space defined by the bottom and side surfaces of the box-shaped molded body, and more specifically, may be the bottom side portions of the bottom surface and each side surface.

[0102] In the box-shaped molded body of this embodiment, the portions other than the liquid-contacting portion are not particularly limited and can be formed of any material such as resin or metal. Also, the entire box-shaped molded body can be formed of the same resin composition as the liquid-contacting portion.

[0103] [Manufacturing method of box-shaped molded body] The box-shaped molded body of this embodiment can be molded using the above-mentioned resin composition by a conventionally known method, such as injection molding, metal in-mold molding, outsert molding, blow molding, extrusion molding, sheet molding, film molding, heat press molding, rotational molding, or laminate molding.

[0104] <Molding conditions> When molding the resin composition of this embodiment, it is generally preferable to set the resin temperature to be equal to or higher than the melting point of the crystalline resin and the mold temperature to be equal to or lower than the glass transition temperature of the crystalline resin, and these are adjusted appropriately depending on the structure of the mold and injection molding machine.

[0105] Taking PPS / PPE as an example, commonly known molding conditions for PPS / PPE are to ensure fluidity during injection molding while suppressing the occurrence of flash, with the resin temperature set to 320°C or higher and the mold temperature set to 60°C or lower, but in this embodiment, the resin temperature is preferably set to 280-320°C and the mold temperature to 120-160°C, and more preferably to 290-310°C and 135-145°C. A resin temperature of 280°C or higher ensures fluidity and tends to prevent molding defects such as short shots and insufficient filling, while a resin temperature of 320°C or lower tends to appropriately control fluidity and tend to prevent flash caused by resin leaking from the parting line.

[0106] Regarding the mold temperature, molding at a temperature higher than the glass transition temperature of PPS, for example, 120°C or higher, tends to result in good mold transfer and enable the gloss to be increased to the level specified in this embodiment. Furthermore, by keeping the mold temperature not too high, for example, 160°C or lower, the resin is sufficiently cooled, which tends to prevent the resin from sticking to the mold when the mold is opened, resulting in mold release problems and poor appearance such as fuzz on the surface of the molded product.

[0107] [Applications of box-shaped molded products] The box-shaped molded body of this embodiment is not particularly limited, but can be, for example, a container (liquid storage container) for storing volatile chemical liquids or solutions (hereinafter these liquids will also be referred to as chemical liquids, etc.), or a container (liquid transfer container) for transporting them.

[0108] When the box-shaped molded product of this embodiment is used for the above-mentioned applications, the liquid-contacting part can be used as a member for partitioning (dividing) the space inside a container in which a chemical solution or the like exists or is filled, or as a member constituting a connecting member that connects such a container with equipment for using the chemical solution or the like, for partitioning (dividing) the space inside the connecting member in which a chemical solution or the like exists or is filled. Furthermore, the liquid-contacting part can be used, for example, to form a flow path that comes into contact with the chemical solution or the like, or to block leakage of the volatilized chemical solution or the like to the outside, and further to block leakage to the inside.

[0109] The box-shaped molded article of this embodiment can be used without any particular limitation as long as it has the above-mentioned liquid-contacting portion and is used to store or transport volatile chemicals or solutions. For example, it can be used as a methanol container filled with methanol, particularly a methanol container (fuel cartridge; fuel cell methanol container) filled with methanol to be supplied to a direct methanol fuel cell, an ethanol tank to supply fuel to a drive engine using bioethanol fuel, a container filled with electrolyte, particularly a container for storing a solution containing a carbonate-based organic solvent such as propylene carbonate, ethylene carbonate, or dimethyl carbonate, which is an electrolyte for a lithium-ion secondary battery, or a buffer tank provided in a device for delivering general organic solvents, for storing a container and delivering the liquid to another container for filling, to suppress pressure fluctuations that occur due to changes in the amount of residual liquid.

[0110] The thin-walled portion can be used for the same purpose as the liquid-contacting portion or can have the same shape. The box-shaped molded body can have any shape and material, as long as it has the thin-walled portion as the liquid-contacting portion. For example, it can be formed from a resin composition different from that of the thin-walled portion, or from a material such as metal. The entire box-shaped molded body can also be formed from the same resin composition as the thin-walled portion. [Example]

[0111] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0112] First, the evaluation methods for the test pieces of the examples and comparative examples and the components used to manufacture the test pieces will be described.

[0113] (1)(c) Measurement of the average length of the filler The resulting resin composition pellets were fed into a screw inline injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 330°C, and molded articles with thicknesses of 0.38 to 0.42 mm were produced under the conditions of cylinder temperature (resin temperature) and mold temperature listed in Table 1. The injection speed was 85 mm / sec, and a surface-treated mold containing titanium nitride was used. A 10 mg sample was taken and the filler was extracted using TGA. TGA conditions: The temperature was raised to 500°C at a rate of 5°C / min in a N2 gas atmosphere, then held at 600°C for 30 min in an air atmosphere, and then cooled to 25°C at a rate of 2°C / min. The extracted filler was centrifuged to extract only the glass filler. The glass filler was then dispersed in ethanol by ultrasonic irradiation for 3 minutes, spread on a plate, and dried before being observed and measured under a microscope. WinRoof software was used for the measurements, and the long and short diameters (μm) of 300 fillers were measured, and the average of these values ​​was calculated. The arithmetic mean of the 300 fillers was taken as (c) the average length (μm) of the filler.

[0114] (2) Morphology measurement of molded products The resulting resin composition pellets were fed into a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 330°C, and rectangular test pieces measuring 10 mm wide x 80 mm long x 4 mm thick were injection molded under the conditions of cylinder temperature and mold temperature shown in Table 1. When producing the molded products, an injection speed of 85 mm / sec was used, and a surface-treated mold containing titanium nitride was used. The cross section of the obtained plate was cut out using a diamond knife microtome (manufactured by Diatome Corporation), and the surface was observed using an electron microscope (manufactured by Hitachi High-Tech Fieldings Corporation) to confirm the sea-island structure. The particle size of the island portion was measured at 100 points, and the average value was calculated as the number average particle size (μm). Furthermore, by performing heavy metal staining using osmium tetroxide and using morphology contrast, it was confirmed that the areas that formed the sea were (a) a phase containing crystalline resin, and the areas that formed the islands were (b) a phase containing amorphous resin, and that the darkly stained areas were the phase containing amorphous resin.

[0115] (3) Gas barrier properties (water vapor) The resulting resin composition pellets were fed into a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 320°C, and molded into plates with a diameter of 10 mm and a thickness of 1 mm under the conditions of cylinder temperature and mold temperature shown in Table 1. The injection speed was 85 mm / sec, and a surface-treated mold containing titanium nitride was used to produce the molded product. Using this plate, a water vapor permeability test was performed in a PERMATRAN W3 / 31 (manufactured by Mocon) under an atmosphere of 40°C and 90% RH, with a permeation area of ​​50 cm. 2 The water vapor permeability (g / (m) was measured in accordance with JIS K7129 B method. 2 ·day)) was measured.

[0116] (4) Gas barrier properties (oxygen) The resulting resin composition pellets were fed into a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 330°C, and molded into a plate with a diameter of 10 mm and a thickness of 1 mm under the conditions of cylinder temperature and mold temperature shown in Table 1. The injection speed was 85 mm / sec, and a surface-treated mold containing titanium nitride was used to produce the molded product. Using this plate, oxygen permeability was measured in an MT-C3 oxygen permeability tester (manufactured by Toyo Seiki Seisakusho) in an atmosphere of 23°C and 0% humidity, with a permeation area of ​​38 cm. 2 and oxygen permeability (cm 3 / (m 2 ·day·atm) was measured.

[0117] (5) Flexural modulus and rate of change of flexural modulus The resulting resin composition pellets were fed into a screw inline injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240 to 330°C. Test specimens for measuring flexural modulus (10 mm wide x 80 mm long x 4 mm thick) were injection molded under the conditions of cylinder temperature and mold temperature shown in Table 1. The injection speed was 85 mm / sec, and a surface-treated mold containing titanium nitride was used. The flexural modulus (MPa) was measured in accordance with ISO 178. The test specimens were immersed in a glass container filled with a mixed solution of 30% by mass of γ-butyrolactone and 70% by mass of ethanol (SP value: 12.7) and allowed to stand in a 60°C oven for 30 days. The flexural modulus was then measured again using the same method. The percent change in flexural modulus (%) was calculated as follows: (flexural modulus before immersion - flexural modulus after immersion) / flexural modulus before immersion × 100.

[0118] (6) Glossiness The resulting resin composition pellets were fed into a screw inline injection molding machine (Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 330°C, and molded into 150mm square, 2mm thick flat plates and 120 x 80 x 100mm, 2mm thick box-shaped molded articles at the cylinder and mold temperatures listed in Table 1. The injection speed was 85mm / sec, and a surface-treated mold containing titanium nitride was used. The gloss of the bottom surfaces of the flat plates and box-shaped molded articles was measured using a gloss meter UGV-6P (Suga Test Instruments Co., Ltd.) at a temperature of 23°C, humidity of 50%, and an incident angle of 60°.

[0119] (7) Lightness and rate of change of lightness The resulting resin composition pellets were fed into a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 330°C, and a 150 mm square, 2 mm thick flat plate and a 120 x 80 x 100 mm, 2 mm thick box-shaped molded product were molded under the conditions of cylinder temperature and mold temperature shown in Table 1. The molded products were produced using an injection speed of 85 mm / sec and a surface-treated mold containing titanium nitride. The color difference of the bottom surfaces of the flat plate and box-shaped molded product was measured using a CC-iS light meter (manufactured by Suga Test Instruments Co., Ltd.) at an incident angle of 60 degrees in an atmosphere of 23°C and 50% humidity. The plate was then immersed in a glass container filled with a mixed solution of 30% by mass of γ-butyrolactone and 70% by mass of ethanol (SP value: 12.7) and left to stand in an oven at 60°C for 30 days, after which the brightness was measured in the same manner. The change in brightness (%) was calculated as follows: (brightness of plate before immersion - brightness of plate after immersion) / brightness of plate before immersion x 100. Furthermore, the box-shaped molded product was filled with a mixed solution of 30% by mass of gamma-butyrolactone and 70% by mass of ethanol (SP value: 12.7), the open section was covered with a PET film, and the product was left to stand in an oven at 60°C for 30 days, after which the lightness of the bottom surface was measured in the same manner. The lightness change rate (%) was calculated as follows: = (lightness of the bottom surface of the box-shaped molded product before immersion - lightness of the bottom surface of the box-shaped molded product after immersion) / lightness of the bottom surface of the box-shaped molded product before immersion × 100.

[0120] (8) Mass and mass change rate Test pieces for measuring the flexural modulus were molded using the same method as in (5), and after measuring their mass, they were immersed in a glass container filled with a mixed solution of 30% by mass of γ-butyrolactone and 70% by mass of ethanol (SP value: 12.7), and left to stand in an oven at 60°C for 30 days, after which their mass was measured in the same manner. The mass change rate (%) was calculated as follows: (test piece mass before immersion - test piece mass after immersion) / test piece mass before immersion × 100.

[0121] (9) Formability The resulting resin composition pellets were fed into a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set at 240°C to 330°C, and test pieces for measuring flexural modulus, 10 mm wide x 80 mm long x 4 mm thick, were injection molded under the conditions of cylinder temperature and mold temperature shown in Table 1. The molded articles were produced using an injection speed of 85 mm / sec and a surface-treated mold containing titanium nitride. At this time, the presence of burrs was visually inspected in the 50 μm gas vent area of ​​the mold.

[0122] [(a) Crystalline Resin] (a-1): A linear PPS containing p-phenylene sulfide repeating units with a melt viscosity (measured using a flow tester at 300°C, a load of 196 N, and an L / D ratio of 10 / 1 for 6 minutes) of 30 Pa s, an extractable amount with methylene chloride of 0.7 mass%, and an -SX group content of 32 μmol / g. (a-2): A mixture of polypropylene with an MFR of 0.41 g / 10 min and polypropylene with an MFR of 5.9 g / 10 min in a mass ratio of 4:1. The MFR was measured in accordance with ISO1133 under conditions of a temperature of 230°C and a load of 2.16 kg.

[0123] [(b) Amorphous resin] (b-1) Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol and having an intrinsic viscosity of 0.33 measured in chloroform at 30°C. (b-2) Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol and having an intrinsic viscosity of 0.46 measured in chloroform at 30°C. (b-3): A mixture of rubber-reinforced polystyrene (manufactured by Petrochemical Co., Ltd., product name "CT60") and homopolystyrene (manufactured by PS Japan Co., Ltd., product name "PSJ-Polystyrene 685") in a mass ratio of 1:1.4. The intrinsic viscosity was measured in chloroform at 30°C using an Ubbelohde viscometer.

[0124] [(c) Filler] Glass flakes (c-1) with an average particle size of 160 μm were used.

[0125] [(d) Emulsifying dispersant] Styrene-glycidyl methacrylate (d-1) was used.

[0126] [(e) Colorant] Carbon black (e-1) was used.

[0127] [Examples and Comparative Examples] (Preparation of Resin Composition Pellets) According to the formulation shown in Table 1 below, each component was melt-kneaded using a twin-screw extruder ("ZSK-40", manufactured by Werner & Pfleidere) set at a temperature of 290 to 320°C and a screw rotation speed of 500 rpm to obtain resin composition pellets.

[0128] [Evaluation criteria] A sample was deemed to have passed if the mass change rate was 10% or less, the flexural modulus change rate was 10% or less, and no burrs were observed. Table 1 below shows the evaluation results of the examples and comparative examples.

[0129] [Table 1] [Industrial Applicability]

[0130] The box-shaped molded body has industrial applicability as a fluid transfer container and a fluid storage container that has good chemical resistance to organic solvents, does not produce burrs during molding, and is capable of achieving both high gas barrier properties and strength.

Claims

1. A box-shaped molded body having a box-like shape with four or more sides and a liquid-contacting portion therein, the liquid-contacting part is made of a resin composition containing (a) a crystalline resin, (b) an amorphous resin, and (c) a filler; In a morphology analysis of the resin composition by SEM, the phase containing the (a) crystalline resin forms a sea, and the phase containing the (b) amorphous resin forms islands; the number average particle size of the islands is 0.2 to 1.3 μm; A box-shaped molded body, wherein the liquid contact surface of the liquid contact portion has a surface glossiness at a 60 degree incident angle of 85 or more.

2. The box-shaped molded product according to claim 1, which is used for filling with a liquid or for blocking filled liquid.

3. The box-shaped molded body according to claim 1 or 2, wherein the liquid-contacting portion is a flow path for transporting a liquid.

4. The liquid contact part is heated to a temperature of 12.7 (cal / cm) ０．５ 4. The box-shaped molded product according to claim 1, wherein, after immersion in a glass container filled with a hydrophobic solvent of 100 ppm or more and leaving the box-shaped molded product in an oven at 60°C for 30 days, a rate of change in lightness of the liquid-contacting surface of the liquid-contacting portion from before immersion is less than 10%.

5. The box-shaped molded body according to any one of claims 1 to 4, wherein the liquid-contacting portion has a portion with a thickness of 1 mm or less.

6. The water vapor permeability of the part having a thickness of 1 mm or less is 0.4 g / (m ２ 6. The box-shaped molded body according to claim 5, wherein the average temperature is 100°C or less.

7. The box-shaped molded body according to any one of claims 1 to 6, wherein the (a) crystalline resin contains polyphenylene sulfide.

8. The box-shaped molded body according to any one of claims 1 to 7, wherein the (b) amorphous resin contains polyphenylene ether.

9. The box-shaped molded body according to any one of claims 1 to 8, which is a liquid transfer container.

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