JP2023012373A - Box-shaped molding - Google Patents

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

The present invention relates to a box-shaped molding.

Conventionally, metal has been used for containers for storing and pouring highly hydrophobic organic solvents. However, along with the lightness of plastics attracting attention, various resin materials have recently been developed, and non-metallic containers that are highly resistant to liquids are being used. In particular, metals are likely to corrode when stored in strongly acidic or strongly basic aqueous solutions, so engineering plastics that are resistant to both hydrophilic and hydrophobic liquids are becoming increasingly useful. Examples of such resin materials that are resistant to both hydrophilic and hydrophobic liquids include crystalline resins. It is used for containers in various applications. Among them, polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) is preferably used.

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.

In addition, when PPS is used as a crystalline resin, its high fluidity causes burrs, which is a phenomenon in which resin leaks from a small gap in the gas release part of the mold during resin molding. It can make your sexuality worse.

As a means for solving this phenomenon, it is known to use a PPS/PPE resin in which a polyphenylene ether (hereinafter PPE) resin, which is an amorphous resin, is alloyed with a crystalline resin, PPS (Patent Document 1-4). Compared to PPS resin alone, PPS/PPE resin has the effect of suppressing burrs and reducing shrinkage by taking advantage of the characteristics of PPE being an amorphous resin. Sometimes it was not possible to mold the molded product. As a means of solving such problems, a thin member having both strength and high chemical resistance has been proposed by using PPS/PPE resin filled with filler under specific conditions. (Patent Document 5).

JP 2006-291054 A JP 2006-316245 A JP 2005-264124 A JP 2019-14776 A Japanese Patent Application Laid-Open No. 2020-180192

However, even when such a PPS/PPE resin is used, the chemical resistance may be insufficient depending on the organic solvent used, especially when highly hydrophobic chemicals are used. As a method of improving chemical resistance, it is conceivable to control the dispersion diameter of PPS/PPE, which has a phase separation structure, and to reduce the dispersion diameter of PPE resin, which has relatively low chemical resistance. In the case of contact with the chemical, deformation of the container due to the chemical could not be prevented simply by appropriately reducing the dispersion diameter.

Therefore, in the present invention, it is possible to maintain chemical resistance equivalent to that of PPS resin even when chemicals with strong attack properties are used, prevent the generation of burrs during molding, and achieve both high gas barrier properties and strength. , to provide a box-shaped molding.

As a result of intensive studies to solve the above problems, the present inventors have found that even when highly aggressive chemicals are used, the containers do not deform, chemical resistance equivalent to that of PPS resin is maintained, and burrs occur during molding. The present inventors have found that it is possible to provide a box-shaped molded article that can achieve both high gas barrier properties and strength without generating a high gas barrier property and strength, and have completed the present invention.

That is, the present invention is as follows.
[1]
A box-shaped molded body having a box-shaped shape with four or more sides and a liquid-contacting part inside thereof,
The wetted part is made of a resin composition containing (a) a crystalline resin, (b) an amorphous resin, and (c) a filler,
Morphology analysis of the resin composition by SEM shows that the (a) phase containing the crystalline resin forms the sea and the (b) phase containing the amorphous resin forms islands,
The islands have a number average particle size of 0.2 to 1.3 μm,
A box-shaped molded article, wherein the liquid-contacting surface of the liquid-contacting portion has a surface glossiness of 85 or more at an incident angle of 60 degrees.
[2]
The box-shaped molded article according to [1], which is used for filling a liquid or for blocking a filled liquid.
[3]
The box-shaped molded article according to [1] or [2], wherein the liquid-contacting portion is a flow path for liquid transfer.
[4]
The wetted part is immersed in a glass container filled with a hydrophobic solvent having an SP value of 12.7 (cal/cm) ^0.5 ), left to stand in an oven at 60 ° C. for 30 days, and then The box-shaped molded article according to any one of [1] to [3], wherein the change in brightness of the wetted surface of the part from before immersion is less than 10%.
[5]
The box-shaped molded article according to any one of [1] to [4], wherein the wetted portion has a portion with a thickness of 1 mm or less.
[6]
The box-shaped molded article according to [5], wherein the water vapor permeability of the portion having a thickness of 1 mm or less is 0.4 g·(m ² ·day) or less.
[7]
The box-shaped molded article according to any one of [1] to [6], wherein the (a) crystalline resin contains polyphenylene sulfide.
[8]
The box-shaped molded article according to any one of [1] to [7], wherein the (b) amorphous resin contains polyphenylene ether.
[9]
The box-shaped molded article according to any one of [1] to [8], which is a liquid transfer container.

According to the present invention, it is possible to provide a box-shaped molded article that does not deform even when a highly aggressive chemical is used, and that can achieve both gas barrier properties and strength.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. Moreover, the present invention can be modified and implemented as appropriate within the scope of the gist thereof.

[Box shaped compact]
The molded body of the present embodiment has a box-shaped shape consisting of four or more sides, and is a box-shaped molded body having a liquid-contacting portion therein, wherein the liquid-contacting portion comprises (a) a crystalline resin, ( b) an amorphous resin, and (c) a resin composition containing a filler, and in morphology analysis by SEM of the resin composition, the phase containing the (a) crystalline resin is the sea, and the phase containing the (b) non-crystalline resin is A phase containing a crystalline resin forms islands, and the islands have a number average particle diameter of 0.2 to 1.3 μm, and the liquid contact surface of the liquid contact portion has a 60-degree incident angle surface glossiness of 85 or more, it is a box-shaped molding.

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

<(a) Crystalline resin>
The resin composition of the present embodiment contains (a) a crystalline resin, and by containing (a) the crystalline resin, the chemical resistance of the polymer alloy containing the amorphous resin can be improved.
The (a) crystalline resin used in the present embodiment is not particularly limited, but includes polyphenylene sulfide, polyethylene, polypropylene, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, syndiotactic polystyrene, and the like. be done. Among them, polyphenylene sulfide is preferable from the viewpoint of further improving chemical resistance.

[[Polyphenylene sulfide]]
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) depending on the production method.
The former linear PPS is a polymer containing usually 50 mol % or more, preferably 70 mol % or more, more preferably 90 mol % or more of arylene sulfide repeating units represented by the following general formula (Formula 1).
[-Ar-S-] (1)
(Here, Ar represents an arylene group, and examples of the arylene group include a p-phenylene group, an m-phenylene group, and a substituted phenylene group (preferably an alkyl group having 1 to 10 carbon atoms and a phenyl group as the substituent), p,p'-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylenecarbonyl group, naphthylene group, and the like.)
The linear PPS may be a homopolymer having one arylene group as a structural unit, or a copolymer obtained by mixing two or more different arylene groups from the viewpoint of workability and heat resistance. good too. Among them, a linear polyphenylene sulfide resin having a repeating unit of p-phenylene sulfide as a main component is preferable because it is excellent in workability and heat resistance and is easily available industrially.

The production method of this linear PPS is usually a method of polymerizing a halogen-substituted aromatic compound such as p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent, or Examples include a method of polymerizing in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, self-condensation of p-chlorothiophenol, etc. Among them, amide solvents such as N-methylpyrrolidone and dimethylacetamide, and sulfolane. A method of reacting sodium sulfide and p-dichlorobenzene in a sulfone solvent is suitable.

These production methods are known, for example, US Pat. US Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Patent Application Laid-Open No. 5-222196, etc., and the prior art methods exemplified in these patents. A linear PPS can be obtained by the method.

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

Here, the extraction amount with methylene chloride can be measured by the following method. That is, 5 g of the linear PPS powder is added to 80 ml of methylene chloride and subjected to Soxhlet extraction for 6 hours, then cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Furthermore, the container used for the above extraction is washed with a total of 60 ml of methylene chloride in three portions, and the washings are collected in the weighing bottle. Next, it is heated to about 80° C. to evaporate and remove the methylene chloride in the weighing bottle, and the residue is weighed. You can ask for a percentage.

The quantification of the -SX group referred to here can be performed by the following method. That is, after drying the linear PPS powder at 120° C. for 4 hours, 20 g of the dried linear PPS powder was added to 150 g of N-methyl-2-pyrrolidone, and vigorously stirred and mixed at room temperature for 30 minutes so as to eliminate powder aggregates to form a slurry. to After filtering the slurry, washing is repeated seven times using 1 liter of hot water at about 80° C. each time. The filter cake obtained here is slurried again in 200 g of pure water, and then 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5.

Next, it is stirred at 25° C. for 30 minutes, filtered, and then washed six times with 1 liter of hot water at about 80° C. each time. The resulting filter cake is slurried again in 200 g of pure water, and then titrated with 1N sodium hydroxide to determine the amount of -SX groups present in the linear PPS from the amount of sodium hydroxide consumed.

Here, a specific example of a method for producing a linear PPS that satisfies an extraction amount of 0.7% by mass or less with methylene chloride and a terminal —SX group of 20 μmol/g or more is described in Japanese Patent Application Laid-Open No. 8-253587. A part of the gas phase in the reactor is removed by reacting an alkali metal sulfide and a dihaloaromatic compound in an organic amide solvent, and cooling the gas phase in the reactor during the reaction. A method of reducing the oligomer component by condensing and refluxing this to the upper liquid layer of the reaction solution can be mentioned.
Then, the crosslinked (including semi-crosslinked) polyphenylene sulfide resin is obtained by polymerizing the linear polyphenylene sulfide resin described above, and then heat-treating it at a temperature below the melting point of the polyphenylene sulfide resin in the presence of oxygen to promote oxidative cross-linking. It has moderately increased polymer molecular weight and viscosity.

Among these crosslinked PPS, the most preferable crosslinked PPS is the volatilization that is collected in the molten state at 320° C. from the viewpoint of gas and tar generation when molding the resin composition obtained in the present invention and from the viewpoint of releasability. It is a crosslinked polyphenylene sulfide resin with a content of 1000 ppm or less. The amount of volatile matter collected in the 320° C. molten state referred to here can be determined by the following method.
That is, 0.5 g of crosslinked PPS powder was weighed into a sealed test tube having an airflow inlet and an outlet, and immersed in a solder bath heated to 320° C. for 30 minutes while nitrogen gas was supplied from the airflow inlet of the test tube at 100 cc/min. The gas containing volatile matter derived from the cross-linked PPS generated in the test tube is purged from the airflow outlet of the test tube, and the purged gas is transferred to a sealed test tube having an airflow inlet and outlet containing acetone. Acetone in the test tube is bubbled from the air flow inlet of the test tube to dissolve the volatile components in the acetone. The volatile content of the crosslinked PPS dissolved in acetone was analyzed by a gas chromatograph-mass spectrometer (GC-MS) using a temperature-rising analysis from 50°C to 290°C. Hypothetically quantified, the volatile content in the crosslinked PPS can be known.

In order to obtain a crosslinked PPS with a volatile content of 1000 ppm or less collected in the molten state at 320° C., the polymer concentration and solvent composition are usually devised during the polymerization stage of the linear PPS, or the polymer is recovered during the polymerization stage. A crosslinked PPS having a desired volatile content can be obtained by devising a washing method or changing the temperature and time of the high temperature treatment in the subsequent crosslinking step.

Further, these PPS (linear PPS, crosslinked PPS) may be acid-modified PPS. Here, the acid-modified PPS is obtained by modifying the above PPS with an acid compound. Carboxylic acids or anhydrides thereof, saturated aliphatic carboxylic acids and aromatic substituted carboxylic acids can also be used. Inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, and carbonic acid can also be mentioned as the acid compounds.

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

In the specification, the melt viscosity refers to JIS K-7210 as a reference test method, using a flow tester (CFT-500 manufactured by Shimadzu Corporation), preheating PPS at 300 ° C. for 6 minutes, then applying a load It is a value measured at 196 N and die length (L)/die diameter (D)=10 mm/1 mm.

Here, (a) the crystalline resin is preferably contained in an amount of 20 to 80% by mass, more preferably 25 to 75% by mass, and still more preferably 30 to 70% by mass in 100% by mass of the resin composition. is. (a) When the content of the crystalline resin is 20% by mass or more, the gas barrier properties of the thin portion can be ensured. Moreover, since the content of (a) the crystalline resin is 80% by mass or less, burrs can be suppressed and outgassing from the molded product can be suppressed.

In addition, the resin composition contains (a) a crystalline resin and (b) an amorphous resin described later, and the content of (b) the amorphous resin and the content of (a) the crystalline resin The ratio of amounts ((b):(a)) is preferably from 5:5 to 2:8, more preferably from 4:6 to 2.2:7.8, even more preferably 3.5 : 6.5 to 2.4: 7.6. (b) The ratio of the content of the amorphous resin to the content of the (a) crystalline resin ((b):(a)) is set to 5:5 or less to ensure the gas barrier properties of the wetted part. By setting the ratio to 2:8 or more, burrs can be suppressed and outgassing from the molded product can be suppressed.

<(b) amorphous resin>
The resin composition of the present embodiment contains (b) an amorphous resin, and by containing the (b) amorphous resin, burrs can be suppressed and outgassing from the molded product can be suppressed.

The (b) amorphous resin that can be used in the present embodiment includes a thermoplastic resin that does not take a crystalline state or has an extremely low degree of crystallinity even when crystallized, and thermoplastic resins such as those exemplified later. Polymer alloys may be mentioned. The term “no crystalline state” or “extremely low crystallinity even after crystallization” means that no exothermic peak associated with crystallization is observed (has no crystalline region), or even if observed, the heat of crystal fusion is, for example, 10 J. /g or less, the degree of crystallinity is extremely low. The heat of crystal fusion can be measured with a differential scanning calorimeter.

Specifically, the (b) amorphous resin is not particularly limited as long as it is a resin having amorphous properties. Examples include polystyrene, rubber-reinforced polystyrene (high impact polystyrene), acrylonitrile-butadiene-styrene. Styrene-based resins such as copolymers (hereinafter also referred to as "ABS"); Polycarbonate-based resins such as polycarbonate, polycarbonate/ABS alloy, polycarbonate/polybutylene terephthalate alloy; Polyphenylene ether resins such as impact polystyrene alloys, polyphenylene ether/polystyrene/high impact polystyrene alloys, and the like.

In addition, as the amorphous resin (b), in particular, from the viewpoint of heat resistance, dimensional accuracy, and flame retardancy, a resin that has a high glass transition temperature and is relatively easy to be made flame retardant is desirable. and more preferably 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.

The content of the (b) amorphous resin in the thin portion of the present embodiment is not particularly limited, but is preferably 10 to 40% by mass, more preferably 10 to 40% by mass, based on the resin composition. It is 12 to 30% by mass, more preferably 15 to 20% by mass.
By setting the content to 10% by mass or more, burrs can be suppressed and outgassing from the molded article can be suppressed. Further, by setting the content to 40% by mass or less, gas barrier properties and chemical resistance of the thin portion can be ensured.

[[Polyphenylene ether resin]]
The polyphenylene ether-based resin can be polyphenylene ether, polyphenylene ether/polystyrene alloy, polyphenylene ether/high impact polystyrene alloy, polyphenylene ether/polystyrene/high impact polystyrene alloy, etc., as described above. Among these, polyphenylene ether is preferable from the viewpoint of dimensional accuracy and chemical resistance of molded articles.

・・・（２）
（ここで、Ｒ_１，Ｒ_２，Ｒ_３及びＲ_４はそれぞれ、水素、ハロゲン、炭素数１～７までの第一級または第二級低級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基または少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択されるものであり、互いに同一であっても異なっていてもよい。また、ｎは１以上の整数である。） The structure of polyphenylene ether (hereinafter sometimes abbreviated as PPE), which is a polyphenylene ether-based resin, is not particularly limited. A homopolymer and/or copolymer polyphenylene ether having an intrinsic viscosity of preferably 0.16 to 0.36, more preferably 0.20 to 0.34, as measured using an Ubbelohde viscosity tube. Preferably.

... (2)
(Here, R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, are selected from the group consisting of hydrocarbonoxy groups or halohydrocarbonoxy groups in which at least two carbon atoms separate the halogen and oxygen atoms, which may be the same or different; Also, n is an integer of 1 or more.)

By setting the intrinsic viscosity of the polyphenylene ether resin to 0.16 or more, a good balance of mechanical properties, fluidity, and releasability can be obtained, and by setting it to 0.36 or less, fluidity in a high shear region (for example, 0.36) can be improved. 5 mm SFD characteristics) and flame retardancy can be enhanced.

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) and the like, as well as 2,6-dimethylphenol and other phenols (eg, 2, Also included are polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol). Among them, poly(2,6-dimethyl-1,4-phenylene ether), copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1 , 4-phenylene ether) are preferred.

The method for producing such a PPE is not particularly limited. For example, the complex of cuprous salt and amine described by Hay described in US Pat. In addition, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. and the method described in JP-A-63-152628, etc., can be easily produced by adjusting the intrinsic viscosity.

The polyphenylene ether-based resin preferably has a PPE component of 100% by mass as described above, but can also be used as a polymer alloy. Some can also be used.

Polystyrene that can be used for polyphenylene ether-based resins includes homopolymers of styrene-based compounds and copolymers of two or more styrene-based compounds, and high-impact polystyrene includes polymers of styrene-based compounds. Examples thereof include rubber-modified styrene in which a rubber-like polymer is dispersed in the form of particles in a matrix. Styrenic compounds that produce these polymers include, for example, styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4- dimethylstyrene, monochlorostyrene, p-tert-butylstyrene and the like.

When a polyphenylene ether-based resin is used as a polymer alloy as described above, the resin to be contained in the PPE may be a copolymer obtained by combining two or more styrene-based compounds or a high-impact polystyrene. Polystyrene obtained by polymerizing using alone is preferred. Polystyrene resins having a stereoregular structure, such as atactic polystyrene and syndiotactic polystyrene, can be effectively used as polyphenylene ether resins.

By setting the intrinsic viscosity of the polyphenylene ether-based resin to 0.16 or more, a good balance between mechanical properties, fluidity, and releasability is achieved. .5 mm SFD characteristics) and flame retardancy can be enhanced.

When using a polyphenylene ether resin as the (b) amorphous resin, the ratio of the content of the (b) amorphous resin to the (a) crystalline resin ((b):(a)) is It is preferably 4:6 to 2:8, 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 ((b):(a)) as the polyphenylene ether-based resin to 4:6 or less, the thin portion Gas barrier properties, fluidity, and flame retardancy can be improved, and by setting the ratio to 2:8 or more, burrs during molding of the resin composition can be suppressed and mold releasability can be improved. can be done.

<(c) Filler>
(c) The filler is not particularly limited, but examples include glass fiber, carbon fiber, carbon nanotube, cellulose fiber, silicon carbide fiber, ceramic fiber, aramid fiber, alumina fiber, gypsum fiber, metal fiber, At least one selected from the group consisting of calcium titanate whiskers, calcium carbonate whiskers, and wollastonite can be used. These fibrous inorganic fillers are further treated with surface treatment agents such as silane coupling agents, titanate coupling agents, and aliphatic metal salts, or treated with resins such as urethane resins and epoxy resins as binders. Anything is fine. Among them, glass fiber is preferable from the viewpoint of heat resistance and adhesion to resin.

The (c) filler preferably has an average length of 50 to 170 μm. By setting the average length to 50 μm or more, the 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. The reason why the gas barrier properties are improved is that by using a short filler, the protrusion of the filler to the surface of the molded product is suppressed, so the boundary between the filler and the resin does not appear on the surface, so the gas barrier property is secured. presumed to be able to (c) The average length of the filler is preferably 80-165 μm, more preferably 120-160 μm.

Here, (c) the average length of the filler in this embodiment can be obtained as follows. First, the thin portion in the present embodiment is placed in, for example, an electric furnace, the contained compact is incinerated, and (c) the filler can be collected from the residue (ash). When collecting (c) filler from the residue, for example, if the molded product contains filler other than (c) filler, (c) residue derived from filler other than fibrous inorganic filler and ( c) In order to separate the residue derived from the filler, it can be separated by dispersing all the residue in water or another solvent and allowing it to settle. In addition, (c) the method for measuring the average length of the filler is not particularly limited as long as it is an image processing device that can observe the filler with a microscope and binarize the obtained image, and the obtained major axis value The average length of the (c) filler can be obtained by arithmetically averaging the average of the minor axis values of arbitrary 300 grains of the (c) filler. More specifically, it can be measured by the method described in Examples.

The content of the (c) filler in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 60% by mass with respect to 100% by mass of the resin composition, and more It is preferably 15 to 40% by mass, more preferably 20 to 40% by mass.
By setting the content to 10% by mass or more, the mechanical strength can be further improved, and by setting the content to 60% by mass or less, higher gas barrier properties can be ensured.

<Crystal Nucleating Agent for Polyphenylene Sulfide>
The resin composition for the thin portion of the molded article of the present embodiment may contain a polyphenylene sulfide crystal nucleating agent. By including the polyphenylene sulfide crystal nucleating agent in the resin composition, it is possible to further improve the gas barrier properties and improve the dimensional accuracy of the thin portion when polyphenylene sulfide is used as the crystalline resin.

The polyphenylene sulfide crystal nucleating agent is not particularly limited as long as it is an additive that increases the rate of formation of polyphenylene sulfide crystal nuclei. Inorganic nucleating agents such as silica, kaolin, talc, hytron, and boron nitride. , calcium stearate, aluminum stearate, dipotassium succinate, calcium benzoate, disodium phthalate, trisodium trimellitate, tetrapotassium pyromellitic acid and other organic carboxylic acid metal salts, polyphenylene sulfide ketone, polyphenylene such as nylon 46 Polymers with higher melting points than sulfides are included. Among these, inorganic nucleating agents are preferable, and talc is more preferable. More specifically, talc has an average particle size of 1 to 50 μm, and is composed of hydrous magnesium silicate (SiO: 58 to 64%, MgO: 28 to 32%, Al2O3: 0.5 to 5%, Fe2O3: 0 .3 to 5%) as a main component. The average particle size of talc is more preferably 10 to 40 μm, still more preferably 20 to 35 μm.

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) above, using a silane coupling agent, a titanate coupling agent, an aliphatic metal salt, etc. A surface treatment may be applied, an organic treatment may be applied using an ammonium salt or the like by an intercalation method, or a binder treatment may be applied using a resin such as a urethane resin or an epoxy resin.

<Scale-like inorganic filler>
The filler used in the resin composition of the molded article of the present embodiment may be a scaly inorganic filler. The content of the scale-like inorganic filler is preferably 10 to 40% by mass, more preferably 15 to 40% by mass, and still more preferably 20 to 40% by mass with respect to 100% by mass of the resin composition. %.
By setting the content to 10% by mass or more, the mechanical strength can be further improved, and by setting the content to 40% by mass or less, higher gas barrier properties can be ensured.

Examples of scale-like inorganic fillers include glass flakes and mica. The scaly inorganic filler is a scaly material having an average major axis of preferably 1000 μm or less, more preferably 1 to 500 μm, still more preferably 1 to 200 μm, and an average minor axis of preferably 1000 μm or less. , more preferably 1 to 500 μm, still more preferably 1 to 200 μm.

In addition, the scaly inorganic filler has an aspect ratio (L1/L2) between the average major axis L1 and the average minor axis L2 of 3 or less, preferably 2 or less, and more preferably 1.6 or less.
The scale-like inorganic filler preferably has an average aspect ratio (L1/T) of the average length L1 and 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 scale-like inorganic filler can be measured by the same method as the average length of the above-mentioned (c) filler.

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

[[Emulsifying dispersant]]
Emulsifying dispersants used as components include (1) epoxy resins, (2) silane coupling agents, (3) compounds containing epoxy groups and/or copolymers containing oxazolyl groups. And/or a copolymer of an unsaturated monomer having an oxazolyl group and a monomer containing styrene as a main component can be used more preferably.

As for the monomer having styrene as the main component, there is no problem when the styrene component is 100% by mass, but when other monomers copolymerizable with styrene are present, the copolymer chain ( In order to maintain miscibility with the polyphenylene ether resin of component b), it is necessary to contain at least 65% by mass or more, more preferably 75 to 95% by mass of styrene monomer. Specific examples of these include copolymers of unsaturated monomers having epoxy groups and/or oxazolyl groups and styrene monomers. A copolymer of an unsaturated monomer having an epoxy group and/or an oxazolyl group and styrene/acrylonitrile=90 to 75% by mass/10 to 25% by mass, and the like.

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, and the like. Glycidyl methacrylate is preferred. As the oxazolyl group-containing unsaturated monomer, for example, 2-isopropenyl-2-oxazoline is industrially available and can be preferably used.

Other unsaturated monomers to be copolymerized with these unsaturated monomers having an epoxy group and/or an oxazolyl group include vinyl aromatic compounds such as styrene as essential components, and vinyl cyanides such as acrylonitrile as copolymer components. Examples include monomers, vinyl acetate, (meth)acrylic acid esters, etc. In the present invention, it is essential that the components excluding unsaturated monomers having epoxy groups and/or oxazolyl groups contain at least 65% by mass or more of styrene monomers. is. In addition, the unsaturated monomer having an epoxy group and/or an oxazolyl group should be contained in the copolymer in an amount of 0.3 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 10% by weight. .

The amount of unsaturated monomers having an epoxy group and/or an oxazolyl group in the copolymer of the emulsifying dispersant component must be 0.3% by mass or more, and if it is 20% by mass or less, polyphenylene of component (a) The miscibility between the sulfide resin and the polyphenylene ether resin of the component (b) is improved, and the occurrence of burrs in molded articles molded using the resulting resin composition can be greatly suppressed. impact strength) and rigidity.

Examples of copolymers of emulsifying dispersant components obtained by copolymerizing copolymerizable unsaturated monomers include, for example, styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, and styrene-glycidyl. Methacrylate-acrylonitrile copolymers, styrene-vinyloxazoline copolymers, styrene-vinyloxazoline-acrylonitrile copolymers, and the like are included.

The amount of the admixture of the emulsifying dispersant component is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, with respect to a total of 100 parts by mass of the components (a) and (b). , more preferably 3 to 10 parts by mass. When the amount of the emulsifying dispersant component is 1 part by mass or more, the effect of improving the miscibility of components (a) and (b) tends to be obtained, and when the amount is 20 parts by mass or less, In addition to being able to greatly suppress the occurrence of burrs in a molded article molded using the obtained resin composition, it tends to have an excellent balance between toughness (impact strength) and rigidity.

[[Compatibilizer]]
Hydrogenated styrenic thermoplastic elastomers can be mentioned as compatibilizers used as components, and known ones can be used.

<Other materials constituting the resin composition>
The resin composition of this embodiment can optionally contain the following components.

〔〔Flame retardants〕〕
The resin composition of this embodiment can contain a flame retardant. As a flame retardant to improve flame retardancy, a flame retardant that is commonly added to thermoplastic resins can be used, but it is preferable to add a halogen-free organophosphorus flame retardant. The organophosphorus flame retardants may be used singly or in combination of two or more.

Examples of organic phosphorus flame retardants include phosphate ester compounds and phosphazene compounds. The phosphate ester compound is added to improve flame retardancy, and any organic phosphate ester generally used as a flame retardant can be used.

Specific examples of phosphoric acid ester compounds include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di(2,6-dimethylphenyl) phosphate], 2,2-bis Examples include {4-[bis(phenoxy)phosphoryloxy]phenyl}propane, 2,2-bis{4-[bis(methylphenoxy)phosphoryloxy]phenyl}propane, but are not limited thereto. In addition to the above, phosphorus-based flame retardants include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate, and the like. Phosphate flame retardants, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzylphosphonate, dimethyl-4-hydroxy-3,5-dibromobenzylphosphonate, diphenyl-4-hydroxy- 3,5-dibromobenzyl phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl) phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, tris( 2,3-dibromopropyl) phosphate, and bis(chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenyl nonylphenyl hydroquinonyl phosphate, phenyl dinonyl phenyl phosphate and other monophosphate ester compounds, and aromatic condensed phosphoric acid Examples include ester compounds.
Among these, aromatic condensed phosphate compounds are preferably used because they generate little gas during processing and are excellent in thermal stability.

As a flame retardant that can be used in the present embodiment, a phosphoric acid ester compound (condensed phosphoric acid ester) represented by the following general formula (I) or general formula (II) is preferable. Particularly preferred are phosphoric acid ester compounds (condensed phosphoric acid esters) represented by the following general formula (I).

(In general formulas (I) and (II), Q1, Q2, Q3 and Q4 each represent a substituent and each independently represent an alkyl group having 1 to 6 carbon atoms, and 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 more, n1 and n2 each independently represent an integer of 0 to 2, m1, m2, m3 and m4 each independently indicates an integer from 0 to 3.)

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

Among the condensed phosphates represented by the general formulas (I) and (II), preferred condensed phosphates are those in which m1, m2, m3, m4, n1 and n2 in formula (I) are zero, R13 and a condensed phosphate ester wherein R14 is a methyl group, or Q1, Q2, Q3, Q4, R13 and R14 in formula (I) are methyl groups, n1 and n2 are zero and m1, m2, m3 and m4 are 1 A condensed phosphoric acid ester having an integer of from 1 to 3 and containing 50% by mass or more of a phosphoric acid ester in which n is an integer from 1 to 3, particularly 1 is preferred.

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.

Among these aromatic condensed phosphate compounds, particularly preferred are aromatic condensed phosphate compounds having an acid value of 0.1 or less (value obtained according to JIS K2501) from the viewpoint of thermal stability. be.

As the phosphazene compound, phenoxyphosphazene and a crosslinked product thereof are preferable, and phenoxyphosphazene having an acid value of 0.1 or less (value obtained according to JIS K2501) is particularly preferable from the viewpoint of thermal stability. is a compound.

The content of the flame retardant varies depending on the required level of flame retardancy, but is in the range of 1 to 30 parts by mass with respect to the total of 100 parts by mass of (a) the crystalline resin and (b) the amorphous resin. It is preferably in the range of 5 to 25 parts by mass. 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 the amount is not more than parts by mass, the balance among fluidity, releasability and burr suppression is improved.

[[Other additives]]
In the resin composition of the present embodiment, in addition to the various materials described above, various additives that are added to ordinary thermoplastic resins, such as heat stabilizers, antioxidants, and ultraviolet absorbers, may be added as necessary. Agents, conductivity-imparting agents, antistatic agents, colorants such as pigments and dyes, and releasing agents can also be added as appropriate.

[Method for producing resin composition]
Various melt kneaders, kneading extruders, and the like can be used for the resin composition of the present embodiment. As the melt kneader or kneading extruder, known kneaders can be used, for example, extruders such as single screw extruders, multi-screw extruders such as twin screw extruders; , a heating melt kneader such as a Banbury mixer; Among them, a twin-screw extruder is preferred.
A method of melt-kneading each of the components described above using a twin-screw extruder having at least two vent ports and at least one side feed port set at 280° C. or higher is preferred.
One of the specific manufacturing method aspects of the resin composition of the present embodiment by a more preferable twin-screw extruder is to mix (a) components, (b) components, and an optional emulsifying dispersant component in a twin-screw extruder. Simultaneously supplied to one supply port and melt-kneaded, and in a state where the basic resin composition composed of these components is melt-kneaded, the first vent port of the twin-screw extruder is sucked and degassed at an absolute vacuum pressure of 95 kPa or less. , Subsequently, if the optional component additive (for example, flame retardant) is liquid, the additive is supplied by a liquid addition pump, and the optional component is supplied from the side 1 supply port of the twin-screw extruder provided downstream. In this method, component (c) is supplied from the downstream side 2 supply port, each component is melt-kneaded, and finally the second vent port of the twin-screw extruder is sucked and degassed at an absolute vacuum pressure of 95 kPa or less.

[Characteristics of resin composition]
-Morphology of Resin Composition-
When the morphology of the resin composition of the present embodiment is analyzed by SEM, (a) the phase containing the crystalline resin forms the sea, and (b) the phase containing the amorphous resin forms the islands. The average particle size satisfies the range of 0.2 to 1.3 μm.

The part forming the sea was (a) a phase containing a crystalline resin, and the part forming the islands was (b) a phase containing an amorphous resin. Heavy metal dyeing using osmium tetroxide and by using morphological contrast, it can be confirmed by the intensity of staining.

More specifically, in the conventional member, the part that was composed of the resin composition containing the crystalline resin and the amorphous resin has a phase containing the crystalline resin as an island and a phase containing the amorphous resin. When a highly aggressive hydrophobic liquid is used to form the sea, conventionally, the hydrophobic liquid permeates the resin, causing deformation of the container, deterioration of gas barrier properties, and deterioration of mechanical strength. was there.

Therefore, in order to suppress the deformation of the container, the deterioration of the gas barrier property, and the deterioration of the mechanical strength, the phase containing the crystalline resin constitutes the sea and the phase containing the amorphous resin constitutes the island. It is preferable to design the compact so that In order for (a) the phase containing the crystalline resin to constitute the sea and (b) the phase containing the amorphous resin to constitute the islands, the content mass ratio of the two is (a) the crystalline resin/(b) the amorphous Resin ratio is preferably 5/5 to 8/2, more preferably 4:6 to 2.2:7.8. Since the amount of (a) crystalline resin is larger than (a) crystalline resin/(b) amorphous resin = 5/5, the phase containing (a) crystalline resin tends to form the sea. preferable. However, since the sea-island structure is also affected by the type and amount of the emulsifying dispersant described above, the mass ratio of (a) the crystalline resin and (b) the amorphous resin is not limited to this composition ratio. .

In addition, when (a) the phase containing the crystalline resin forms the sea and (b) the phase containing the amorphous resin forms islands, the number average particle diameter of the islands is 0.2 to 1.3 μm. It is preferably 25 to 1.0 μm, more preferably 0.3 to 0.9 μm, still more preferably 0.4 to 0.8 μm. When the number average particle diameter of the islands is 1.3 μm or less, even when a highly aggressive hydrophobic liquid comes into contact with the polyphenylene ether resin, it is possible to prevent penetration into the polyphenylene ether resin and prevent deformation of the container. can. In addition, when the number average particle size is 0.2 μm or more, the high fluidity of the crystalline resin is excessively manifested, and burrs are generated from the parting line of the mold clamping and gas vents during molding, resulting in deterioration of moldability. can prevent it from happening.

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

Methods for adjusting the number average particle size of the islands to fall within the above range include adjusting the mass ratio of the crystalline resin and the amorphous resin, adjusting the type and amount of the emulsifying dispersant, and adjusting the amount of the polymer. Examples include molecular chain modification technology and extrusion reaction technology. Specifically, the dispersion diameter can be reduced by increasing the mass ratio of the crystalline resin and increasing the amount of the emulsifying dispersant. Moreover, by using a polymer molecular chain modification technique and an extrusion reaction technique, the compatibility between the crystalline resin and the amorphous resin can be improved, and the dispersion diameter can be reduced.

[Characteristics of box-shaped compact]
-Surface condition of the wetted surface of the wetted part-
In the box-shaped molded article of the present embodiment, the 60-degree incident angle surface glossiness of the liquid-contacting surface of the liquid-contacting portion is 85 or more, preferably 90 or more, more preferably 92 or more, and 93 or more. is more preferable. When the 60-degree incident angle surface glossiness of the wetted surface is 85 or more, the resistance to highly aggressive hydrophobic liquids can be further improved.

Although the detailed mechanism by which the above effect is produced is unknown, the reason is presumed as follows. It is believed that the glossiness of 85 or more reduces minute irregularities on the surface of the wetted surface. That is, since there are few minute irregularities, the surface area of the molded product that is in contact with the chemical becomes small. As a result, the portion of the island portion of the amorphous resin having a phase-separated structure that is permeated by the chemical becomes relatively small, and even when a highly aggressive hydrophobic liquid comes into contact with the container, the deformation of the container does not occur. It is thought that the reduction in mechanical strength and gas barrier properties can be prevented.

The 60-degree incident angle surface glossiness of the wetted surface can be measured with a gloss meter, and more specifically, it can be measured by the method described in the Examples.

As a method of adjusting the 60-degree incident angle surface glossiness of the wetted surface within the above range, a material with a low coefficient of friction is used for the coating type of the mold used for molding in order to suppress sticking of the resin to the mold. and a method of adjusting the mold temperature and injection speed during molding (described later). Specifically, setting the mold temperature at the time of molding to a temperature higher than the glass transition temperature of the crystalline resin tends to increase the 60-degree incident angle surface glossiness. In addition, in the method of using a material with a low coefficient of friction for the coating of the mold used for molding, a 60° There is a tendency that the incident angle surface glossiness can be increased. In the method of adjusting the injection speed, it tends to be possible to increase the 60-degree incident angle surface glossiness by adjusting the injection speed in the range of 50 to 100 mm/sec, more preferably 80 to 90 mm/sec. Also, by making the morphology (described later) suitable, there is a tendency that the 60-degree incident angle surface glossiness can be increased.

-Brightness of the wetted surface of the wetted part-
The rate of change in brightness after the liquid contact surface of the liquid contact portion is in contact with the hydrophobic liquid at 60° C. for 30 days is preferably less than 10%, more preferably less than 8%. More preferably less than 6%. A brightness change rate of less than 10% indicates that the effect of chemical attack on the surface can be prevented, and deformation of the container, deformation of the container, and deterioration of mechanical strength are more suitably prevented. tend to be able.

The brightness and the rate of change in brightness can be measured with a brightness meter, more specifically, by the method described in Examples.

Although the hydrophobic liquid used for contacting the liquid is not particularly limited, for example, the solubility parameter (SP value, unit (cal/cm) ^0.5 ) serves as a reference for selection. In particular, in the present invention, it is preferable to use a hydrophobic liquid having a solubility parameter of 8 to 16, such as ε-caprolactone, n-methylpyrrolidone, methyl methacrylate, γ-butyrolactone, ε-caprolactam, 1,3- propylene carbonate, methanol, ethanol, ethylene carbonate, ethylene glycol, glycerin and the like. Any amount of these solutions may be mixed and used.

-Thickness and Gas Barrier Properties of Wetted Parts-
In the box-shaped molded body of the present embodiment, it is preferable that the thickness of the wetted part is thin, specifically, it has a thickness of 1 mm or less in order to effectively save resources, reduce weight, and increase the degree of freedom in design. is preferred.

If the wetted part has a thickness of 1 mm or less, gas from the atmosphere may be dissolved in the liquid filled in the container, which may cause problems with the liquid properties. For this reason, the gas barrier property is preferably such that the water vapor permeability is 0.4 g/(m ² ·day) or less, more preferably 0.3 g/(m ² ·day) or less at a thickness of 1 mm. , 0.2 g/(m ² ·day) or less. Having a water vapor transmission rate of 0.4 g/(m ² ·day) or less tends to prevent water vapor from penetrating into the filled container and dissolving in the liquid. As a result, if there is a change in temperature outside the container system, air bubbles will be generated and the properties of the liquid to be filled will be impaired. It tends to be possible to prevent short circuits and performance degradation of the circuit board in the parts that are covered.
The water vapor permeability can be measured using a water vapor permeability tester, and more specifically, it can be measured by the method described in Examples.

As for the gas barrier property, the oxygen permeability at a thickness of 1 mm is preferably 150 cm ³ /(m ² ·day · atm) or less, more preferably 50 cm ³ /(m ² ·day · atm) or less, It is more preferably 30 cm ³ /(m ² ·day·atm) or less.
By having a water vapor permeability of 50 cm ³ /(m ² ·day · atm) or less, oxygen permeates the container filled inside the molded product, and dissolution in the liquid causes deterioration such as oxidation of the contents. tend to be able to prevent the progression of
The oxygen permeability can be measured using an oxygen permeability tester, and more specifically, it can be measured by the method described in Examples.

If the wetted portion has a portion (thin portion) with a thickness of 1 mm or less, the thin portion may be a portion that defines the internal space of a container or the like in which the chemical solution or the like exists, such as a flow path that comes into contact with the chemical solution or the like. It can be located in the part to be formed, or in the part where the chemical liquid volatilizes and prevents it from leaking to the outside or to the inside. The thin portion in the present embodiment has a predetermined surface glossiness of the wetted surface, and is made of a predetermined resin composition, thereby improving not only gas barrier properties and strength but also surface smoothness. As a result, in the case where the thin portion is, for example, a flow path in contact with a chemical liquid or the like, it is possible to suppress the influence of turbulence in liquid transfer.

-Structure of box-shaped compact-
In addition, the box-shaped molded body of the present embodiment is not limited in shape as long as it has a box-shaped shape consisting of at least four sides and has a liquid-contacting part inside it. At least a portion of the portion is preferably tubular, and more preferably the thinned portion has a tubular portion.
Here, the tubular shape is not particularly limited as long as a closed area is formed by the contour of the inner surface in a cross-sectional view, and various shapes such as circular, elliptical, and polygonal can be employed. Further, when the thin portion has a tubular portion, the thin portion may have any shape other than the tubular portion. The box-shaped molded body of the present embodiment can be formed in various shapes, for example, by using the wetted part and other parts together to form a tubular shape. In order to secure the strength of the tubular portion itself, the opening area of the tubular portion is preferably 400 mm ² or less, more preferably 200 mm ² or less, and 100 mm ² or less. It is even more preferable to have

The box-shaped molded body of the present embodiment may have a structure including one bottom surface and three side surfaces, or may have a structure including one bottom surface and four side surfaces. Alternatively, the structure may have one bottom surface and five or more side surfaces, and each structure may have two or more bottom surfaces. The box-shaped molding of this embodiment usually has a structure comprising one bottom surface and four side surfaces perpendicular to the bottom surface.

The liquid-contacting portion provided in the box-shaped molded body of the present embodiment may exist inside the box-shaped molded body, specifically within the range of the internal space defined by the bottom and side surfaces of the box-shaped molded body. , more specifically, the bottom surface and the bottom side portion of each side surface.

In addition, in the box-shaped molded body of the present embodiment, portions other than the wetted portion are not particularly limited, and can be made of any material such as resin or metal. Also, the entire box-shaped molded body can be made of the same resin composition as the wetted portion.

[Manufacturing method of box-shaped compact]
The box-shaped molded article of the present embodiment can be produced by using the resin composition described above by a conventionally known method such as injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, film molding, heat molding, and molding. It can be molded by a known method such as press molding, rotational molding, lamination molding, or the like.

<Molding conditions>
When molding the resin composition of the present embodiment, it is generally preferable to set a resin temperature above the melting point of the crystalline resin and a mold temperature below the glass transition temperature of the crystalline resin. It should be adjusted appropriately depending on the construction of the aircraft.

Taking PPS/PPE as an example, generally known molding conditions for PPS/PPE require that the resin temperature is 320° C. or higher to suppress the generation of burrs while ensuring fluidity during injection molding. The mold temperature is set to 60° C. or less, but in this embodiment, it is preferable to set the resin temperature to 280 to 320° C., the mold temperature to 120 to 160° C., more preferably 290 to 310° C. °C, and the mold temperature is 135-145°C. When the resin temperature is 280°C or higher, fluidity is secured, and molding defects such as short shots and insufficient filling tend to be prevented. It tends to be possible to prevent burrs from which resin leaks out.

As for 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 increase the gloss to the extent specified in this embodiment. . In addition, if the mold temperature is not too high, for example, 160 ° C. or less, the resin is sufficiently cooled, and the resin sticks to the mold when the mold is opened, resulting in poor release and a fluffy appearance on the surface of the molded product. It tends to prevent defects from occurring.

[Use of box-shaped molding]
The box-shaped molded body of the present embodiment is not particularly limited, but for example, a container (liquid storage container) for storing a volatile chemical solution or solution (hereinafter these liquids are also referred to as a chemical solution, etc.), or a container for transporting (liquid transfer container).

When the box-shaped molded body of the present embodiment is used for the above applications, the liquid-contacting part is a member for partitioning (partitioning) the space inside the container in which the chemical solution or the like is present or filled, or such a container. and a device for using the drug solution, etc., as a member for dividing (partitioning) the space where the drug solution, etc. exists or is filled inside the connection member can be used. In addition, the wetted part may be used to form a flow path in contact with, for example, a chemical solution, or to block volatilization of the chemical solution from leaking to the outside, or to block leakage to the inside. It can also be used to

The box-shaped molded body of the present embodiment has the wetted part described above, and can be used without particular limitation as long as it is for storing or transporting a volatile chemical or solution. For example, a methanol container filled with methanol, especially a methanol container filled with methanol to be supplied to a direct methanol fuel cell (fuel cartridge, methanol container for fuel cells), or a driving engine using bioethanol fuel Ethanol tanks that supply fuel to , containers filled with electrolytes, especially containers that store solutions containing carbonate-based organic solvents such as propylene carbonate, ethylene carbonate, and dimethyl carbonate, which are electrolytes for lithium-ion secondary batteries. Also, in general organic solvent transfer equipment, a buffer tank, etc., is installed to suppress pressure fluctuations caused by changes in the amount of residual liquid when storing a container and transferring and filling another container. can be

Further, the thin portion can be used for the same purpose as the wetted portion, or can have the same shape. If the box-shaped molded body has the thin portion as the wetted portion, the shape and material thereof can be arbitrarily selected. can also Also, the entire box-shaped molded body can be made of the same resin composition as that of the thin-walled portion.

EXAMPLES 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.

First, the evaluation method of the test pieces of Examples and Comparative Examples and the components used to manufacture the test pieces are shown.

(1) (c) Measurement of average length of filler Using the pellets of the obtained resin composition, a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name: (“EC75SXII injection molding machine”), and a molded article having a thickness of 0.38 to 0.42 mm was produced under the conditions shown in Table 1 at the cylinder temperature (resin temperature) and mold temperature. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. A 10 mg sample was taken and the filler was taken out by TGA.
TGA conditions: The temperature was raised to 500°C at a heating rate of 5°C/min under an N2 gas atmosphere. After that, the temperature was maintained at 600° C. for 30 minutes in an air atmosphere, and the temperature was lowered to 25° C. at a rate of 2° C./min.
The removed filler was centrifuged to remove only the glass filler. Further, the glass filler was dispersed in ethanol by irradiating ultrasonic waves for 3 minutes, spread on a plate, dried, and then observed and measured with a microscope. WinRoof software is used for measurement, the major axis (μm) and minor axis (μm) of 300 fillers are measured, the average value of these is calculated, and the value obtained by arithmetically averaging 300 (c) filler The average length (μm) was used.

(2) Measurement of the morphology of the molded product Pellets of the obtained resin composition were placed in 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 under the cylinder temperature and mold temperature conditions shown in Table 1, a strip-shaped test piece having a width of 10 mm, a length of 80 mm, and a thickness of 4 mm was injection molded. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used.
Using a microtome (manufactured by Diatome) with a diamond knife, the resulting flat plate was cut into cross sections, and the resulting surface was observed with an electron microscope (manufactured by Hitachi High-Tech Fieldings) to confirm the sea-island structure. The particle size was measured at 100 points, and the average value was obtained as the number average particle size (μm).
In addition, osmium tetroxide was used to confirm that the portion forming the sea was (a) a phase containing a crystalline resin, and the portion forming the islands was (b) a phase containing an amorphous resin. Heavy metal staining was performed and morphological contrast was used to confirm the presence of a phase containing amorphous resin in the darkly stained areas.

(3) Gas barrier properties (water vapor)
The obtained pellets of the resin composition are supplied to 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 the cylinder temperature, metal A flat plate with a diameter of 10 mm and a thickness of 1 mm was molded under the mold temperature conditions shown in Table 1. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. Using this flat plate, a water vapor permeability tester PERMATRAN W3/31 (manufactured by Mocon Co., Ltd.) is used to set the permeation area to 50 cm ² in an atmosphere of temperature 40 ° C. and humidity 90% RH, and water vapor is measured in accordance with JIS K7129 B method. The permeability (g/(m ² ·day)) was measured.

(4) Gas barrier properties (oxygen)
The obtained pellets of the resin composition are supplied to 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 the cylinder temperature, metal A flat plate with a diameter of 10 mm and a thickness of 1 mm was molded under the mold temperature conditions shown in Table 1. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. Using this flat plate, an oxygen permeability tester MT-C3 (manufactured by Toyo Seiki Seisakusho) was used to set the permeation area to 38 cm ² in an atmosphere of 23 ° C. and 0% humidity, and according to JIS K7126-1 (pressure sensor method). The oxygen permeability (cm ³ /(m ² ·day · atm)) was measured according to the above.

(5) Flexural modulus and rate of change in flexural modulus Pellets of the obtained resin composition were molded using a screw in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name “EC75SXII”) set at 240 ° C. to 330 ° C. Injection molding machine"), and the cylinder temperature and mold temperature were set to the conditions shown in Table 1, and a test piece for bending elastic modulus measurement of width 10 mm x length 80 mm x thickness 4 mm was injection molded. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. The bending elastic modulus (MPa) was measured according to ISO178. The test piece was immersed in a glass container filled with a mixed solution (SP value: 12.7) of 30% by mass of γ-butyrolactone and 70% by mass of ethanol, left to stand in an oven at 60°C for 30 days, and then the bending elastic modulus was measured again. was measured by the same method. Change rate (%) of flexural modulus=(flexural modulus before immersion−flexural modulus after immersion)/flexural modulus before immersion×100.

(6) Glossiness The pellets of the obtained resin composition were supplied to 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. A flat plate of 150 mm square and a thickness of 2 mm and a box-shaped molded product of 120×80×100 mm and a thickness of 2 mm were molded under the conditions shown in Table 1, , cylinder temperature, and mold temperature. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. Using this flat plate and the bottom surface of the box-shaped molded product, the glossiness was measured with a gloss meter ugv-6p (manufactured by Suga Test Instruments Co., Ltd.) at a temperature of 23 ° C., a humidity of 50%, and an incident angle of 60 °. It was measured.

(7) Brightness and rate of change in brightness Pellets of the obtained resin composition were molded using 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 flat plate of 150 mm square and a thickness of 2 mm and a box-shaped molded article of 120×80×100 mm and a thickness of 2 mm were molded under the conditions shown in Table 1 at the cylinder temperature and the mold temperature. was molded. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. Using this flat plate and the bottom surface of the box-shaped molded product, using a brightness meter CC-iS (manufactured by Suga Test Instruments Co., Ltd.), under the conditions of a temperature of 23 ° C., a humidity of 50%, and an incident angle of 60 ° Color difference was measured.
After that, the flat plate was 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), left to stand in an oven at 60°C for 30 days, and then similarly. Brightness was measured. Rate of change in brightness (%) = (brightness of flat plate before immersion - brightness of flat plate after immersion)/brightness of flat plate before immersion x 100.
In addition, for the box-shaped molded product, a mixed solution of γ-butyrolactone 30% by mass and ethanol 70% by mass (SP value: 12.7) was filled inside the box, and the opening was covered with a PET film and then heated to 60 ° C. After standing in the oven for 30 days, the brightness of the bottom surface was measured in the same manner. Rate of change in brightness (%) = (Brightness of bottom surface of box-shaped molded product before immersion - Brightness of bottom surface of box-shaped molded product after immersion)/Brightness of bottom surface of box-shaped molded product before immersion x 100 .

(8) Mass and mass change rate A test piece for measuring the flexural modulus was molded by the same method obtained in (5), and after measuring the mass, a mixed solution of 30% by mass of γ-butyrolactone and 70% by mass of ethanol ( SP value: 12.7) was filled in a glass container, left to stand in an oven at 60°C for 30 days, and then the mass was measured in the same manner. Mass change rate (%) = (mass of test piece before immersion - mass of test piece after immersion)/mass of test piece before immersion x 100.

(9) Moldability Pellets of the obtained resin composition were supplied to 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. , cylinder temperature, and mold temperature were set to the conditions shown in Table 1, and a test piece for measuring the bending elastic modulus of 10 mm width, 80 mm length, and 4 mm thickness was injection molded. When producing the molded product, the injection speed was 85 mm/sec, and a surface-treated mold containing a component of titanium nitride was used. At this time, it was visually determined whether or not burrs were generated in the 50 μm gas release portion provided in this mold.

[(a) crystalline resin]
(a-1): Melt viscosity (value measured after holding for 6 minutes at 300°C, load 196N, L/D = 10/1 using a flow tester) is 30 Pa s, and the extraction amount with methylene chloride is A linear PPS having a p-phenylene sulfide repeating unit of 0.7% by mass and a -SX group amount of 32 μmol/g.
(a-2): A mixture of polypropylene with MFR=0.41 g/10 min and polypropylene with MFR=5.9 g/10 min in a weight ratio of 4:1.
The MFR was measured under conditions of a temperature of 230° C. and a load of 2.16 kg according to ISO1133.

[(b) amorphous resin]
(b-1) A 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) A 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): Rubber-reinforced polystyrene (manufactured by Petrochemical, trade name “CT60”) and homopolystyrene (manufactured by PS Japan, trade name “PSJ-polystyrene 685”) at a mass ratio of 1:1.4 mixture.
The intrinsic viscosity was measured in chloroform at 30° C. using an Ubbelohde viscosity tube.

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

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

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

[Examples, Comparative Examples]
(Preparation of resin composition pellets)
According to the formulation shown in Table 1 below, each component is 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 a resin composition. A pellet was obtained.

〔Evaluation criteria〕
A case where the rate of change in mass was 10% or less, the rate of change in flexural modulus was 10% or less, and no burrs occurred was regarded as acceptable. Others were rejected.
Table 1 below shows the evaluation results of Examples and Comparative Examples.

The box-shaped molded body has good chemical resistance to organic solvents, does not generate burrs during molding, and is capable of achieving both high gas barrier properties and strength. It has industrial applicability as

Claims (9)

A box-shaped molded body having a box-shaped shape with four or more sides and a liquid-contacting part inside thereof,
The wetted part is made of a resin composition containing (a) a crystalline resin, (b) an amorphous resin, and (c) a filler,
Morphology analysis of the resin composition by SEM shows that the (a) phase containing the crystalline resin forms the sea and the (b) phase containing the amorphous resin forms islands,
The islands have a number average particle size of 0.2 to 1.3 μm,
A box-shaped molded article, wherein the liquid-contacting surface of the liquid-contacting portion has a surface glossiness of 85 or more at an incident angle of 60 degrees. 2. The box-shaped molding according to claim 1, which is used for filling a liquid or for blocking a filled liquid. 3. The box-shaped molded article according to claim 1, wherein said liquid contacting portion is a channel for transferring liquid. The wetted part is immersed in a glass container filled with a hydrophobic solvent having an SP value of 12.7 (cal/cm) ^0.5 ), left to stand in an oven at 60 ° C. for 30 days, and then 4. The box-shaped molded article according to any one of claims 1 to 3, wherein the wetted surface of the part has a rate of change in brightness from before immersion of less than 10%. The box-shaped molded article according to any one of claims 1 to 4, wherein the wetted portion has a portion with a thickness of 1 mm or less. 6. The box-shaped molded article according to claim 5, wherein the water vapor permeability of the portion having a thickness of 1 mm or less is 0.4 g/(m< ² >*day) or less. The box-shaped molded article according to any one of claims 1 to 6, wherein the (a) crystalline resin contains polyphenylene sulfide. The box-shaped molded article according to any one of claims 1 to 7, wherein the (b) amorphous resin contains polyphenylene ether. The box-shaped molded article according to any one of claims 1 to 8, which is a liquid transfer container.