JP7344013B2 - Protective housing material for mobile battery units - Google Patents

Description

The present invention relates to a protective housing member for a battery unit for a mobile object.

BACKGROUND ART In recent years, hybrid electric vehicles, electric vehicles, etc. have become more popular, and the batteries of mobile vehicles such as hybrid vehicles and electric vehicles are generally housed in a protective case that is different from the case that houses the batteries themselves. Protective casings that can be used in such moving objects must not only exhibit impact resistance and dimensional stability within the assembled battery module, but also be lightweight and compact in order to improve the environment inside the moving object. ing. Therefore, there is a demand for protection cases for battery modules that can be applied to complex shapes and have reduced weight. As a protective case for a battery unit for a mobile object, a polyphenylene ether resin composition can be used, for example, as disclosed in Patent Document 1, because it has high moldability, dimensional stability, and low specific gravity (hereinafter referred to as (Polyphenylene ether is sometimes simply referred to as "PPE").

Patent No. 6314215

By the way, since batteries for mobile objects can be exposed to vibrations for a long period of time, protective casings for battery units for mobile objects need to be applied to complex shapes and to reduce weight as described above. The problem is whether various devices such as battery cells inside the body can be reliably held, or whether the protective casing can be reliably connected and maintained with each structure. Specifically, the protective casing of a battery unit for a mobile object can be damaged by large vibrations that occur during operation of the mobile object, or even if the battery cell itself is damaged and leaks electrolyte. It is necessary that the protective casing of the battery unit is not damaged. Furthermore, the protective casing of a battery unit for a mobile object needs to be securely held and connected to various internal devices and external structures, but it is necessary to secure it to other parts using screws. In some cases, a large amount of stress remains in the screwed part. Therefore, the protective casing of a battery unit for a mobile object can be damaged due to a combination of various environmental loads such as cutting oil and various lubricating oils used when forming screw holes and fixing screws, or leaked electrolyte. However, even if such stress continues to remain, it is necessary that it does not break.
Furthermore, with increasing demands for safety, protective casings for battery units for mobile objects are also required to be flame retardant.

However, while conventional PPE-based resin compositions have high moldability, high dimensional stability, and low specific gravity, they also have sufficient resistance to cutting oil and electrolyte, and resistance to large vibrations that occur when driving a car. It did not have both resistance and flame retardancy.

Therefore, the present invention is capable of responding to the complexity of the shape and the reduction of weight of the molded body, has flame retardancy, securely holds various devices installed inside, or can be connected to each structure. It is an object of the present invention to provide a protective casing member for a battery unit for a moving body, which can reliably connect and maintain the battery unit.

［式中、Ｒ^１１及びＲ^１２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｍ^１は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａは、１～３の整数であり；ｍは、１～３の整数であり；ａ＝ｍである］、及び
下記式（２）で表されるジホスフィン酸塩

［式中、Ｒ^２１及びＲ^２２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｒ^２３は、直鎖状若しくは分岐状の炭素原子数１～１０のアルキレン基、炭素原子数６～１０のアリーレン基、炭素原子数６～１０のアルキルアリーレン基、又は炭素原子数６～１０のアリールアルキレン基であり；Ｍ^２は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂは、１～３の整数であり；ｎは、１～３の整数であり；ｊは、１又は２の整数であり；ｂ・ｊ＝２ｎである］
からなる群より選ばれる少なくとも１種のホスフィン酸塩類を含有する、［１］又は［２］に記載の移動体用電池ユニットの保護筐体部材。 [1]
(a) a polyphenylene ether resin; and (b) a block copolymer comprising at least one polymer block mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound. Molding a resin composition containing at least a partially hydrogenated hydrogenated block copolymer and/or a modified product of the hydrogenated block copolymer, and/or (c) an olefinic polymer consisting of an olefin. A protective casing member for a battery unit for a mobile object obtained by
The resin composition has a critical strain of 0.5% or more in chemical resistance evaluation, a flexural modulus of 2500 MPa or more measured according to ISO-178, and a combustion resistance measured based on the UL94 vertical combustion test. The level is V-0,
In the morphological image of the protective casing member of the mobile battery unit, the continuous phase contains the component (a) and the component (b) and/or the component (c) present in the continuous phase. A network phase structure having a linear dispersed phase is formed,
In the first processed image obtained by binarizing the morphological image, the area occupied per unit area of the first white portion that is white after the binarizing process is AW1 (μm 2 /μm 2 ⁾ , ^and the For the first non-small portions that are black after the binarization process and have an area of 15×10 ⁻⁴ μm ² or more, the total circumference of the total circumference of the first non-small portions, When the length per unit area is L1 (μm/μm ² ), the length L1 (L1/AW1) with respect to the occupied area AW1 is 7 μm ⁻¹ or more.
A protective casing member for a battery unit for a mobile object, characterized in that:
[2 ]
Furthermore , (d) the protective housing member for a battery unit for a mobile object according to [1] , which contains a phosphate ester compound.
[ 3 ]
Furthermore, it contains (e) phosphinates,
The component (e) is a phosphinate salt represented by the following general formula (1)

[wherein R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; M ¹ is , calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion, and a protonated nitrogen base; a is 1 to 3; m is an integer of 1 to 3; a=m], and a diphosphinate represented by the following formula (2)

[In the formula, R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; R ²³ is , a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. ^M2 is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; b is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2; b・j=2n]
The protective housing member for a mobile battery unit according to [1] or [2] , which contains at least one phosphinate selected from the group consisting of:

According to the present invention, it is possible to cope with the complexity of the shape of the molded object and the reduction of its weight, and it also has flame retardant properties, and can securely hold various devices installed inside or connect with each structure. It is possible to provide a protective casing for a mobile battery unit that can reliably connect and maintain the battery units.

FIG. 1 is a schematic exploded view showing an example of a known protective housing for housing a mobile battery unit. FIG. 2 is a part of an image (field of view size: 5 x 5 μm) obtained by observing the protective casing member of the mobile battery unit of Example 2 using an SEM, showing the formation of a mesh-like phase structure. There is. FIG. 3 is a part of an image (field of view size: 5 x 5 μm) obtained by observing the protective casing member of the mobile battery unit of Example 10 using an SEM, showing the formation of a mesh-like phase structure. There is.

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

[Protective housing member for mobile battery unit]
The protective casing member of the battery unit for a mobile object according to the present embodiment (hereinafter, the "protective casing member of the battery unit for a mobile object" is also simply referred to as the "protective casing member") is made of (a) polyphenylene ether It is obtained by molding a resin composition containing a resin composition, and the critical strain amount in the chemical resistance evaluation of the resin composition is 0.5% or more, and the bending measured according to ISO-178. The elastic modulus is 2500 MPa or more, and the combustion level measured based on the UL94 vertical combustion test is V-0.

Note that the protective casing member of the battery unit for a mobile object is not particularly limited as long as it forms part of the protective casing of the battery unit for a mobile object; (including railway vehicles, motorcycles, electrically assisted bicycles, etc.), and preferably constitutes a part of a protective casing for protecting a battery unit having a plurality of battery cells. It is preferable that the protective case forms part or all of a protective case that covers the entire surface (six sides in three x, y, and z directions) of the battery unit. Protective casings for battery units used in hybrid and electric vehicles are known, for example, in U.S. Patent Publication No. 2010/0021810, U.S. Patent Application Publication No. 2009/0155679, and International Publication No. 2013/023524. etc. are described.
FIG. 1 is a schematic exploded view showing an example of a known protective housing for housing a mobile battery unit. Hereinafter, the configuration of the protective casing of the mobile battery unit will be described using FIG. 1.

In FIG. 1, the protective case that houses the battery unit 1 is composed of a protective case bottom plate 5, a protective case top plate 7, two protective case baffle structures 11, and two protective case side plates 15. There is.
Battery cells 2 constituting the battery unit 1 are connected to each other at their ends by connectors 3 and separated from each other on their sides by separators 4.
The protective case bottom plate 5 and the protective case top plate 7 are arranged parallel to each other with the battery cell 2 sandwiched between them, and restrict movement of the battery cell 2 in a direction perpendicular to the bottom plate 5 and the top plate 7. . The two protective housing baffle structures 11 are arranged on the side surfaces of the battery cell 2 parallel to the side surfaces and cooperate with each other to limit the movement of the battery cell 2 in the direction perpendicular to the baffle structures 11 . The two protective housing side plates 15 are arranged on opposite ends of the battery cell 2 and extend along the width direction of the battery cell 2 to restrict movement of the battery cell 2 in a direction perpendicular to the side plates 15. do.
The bottom plate 5, the top plate 7, and the baffle structure 11, and the bottom plate 5, the top plate 7, and the side plates 15 can be fitted and fixed by seal elements 6, respectively. Thereby, a watertight seal is formed between the top plate 7 and the bottom plate 5.
Since the protective case bottom plate 5, top plate 7, baffle structure 11, and side plate 15 can all be molded with the protective case member of this embodiment, the number of materials required for manufacturing the protective case is reduced. be done.

Each baffle structure 11 includes a baffle plate 12, a baffle reinforcement 13, and a baffle opening 14 at a corner of the baffle structure 11. The baffle opening 14 is configured to receive a drawbar (not shown) that extends between the two baffle structures 11 to secure the battery cells 2 therebetween. The thickness of the entire baffle structure 11, the baffle plate 12, and the baffle reinforcing material 13 can be, for example, 3 to 15 mm, 3 to 5 mm, and 2 to 5 mm, respectively.
An L-shaped structure is provided on the baffle structure 11 with a sealing element 6 arranged to fit onto the top plate 7 and the bottom plate 5 . The top plate 7 and the corresponding L-shaped structure, and the bottom plate 5 and the corresponding L-shaped structure are each provided with an opening in which a pin is accommodated. The pin limits the displacement between the top plate 7 and the baffle structure 11 and the displacement between the bottom plate 5 and the baffle structure 11, and suppresses the movement of the battery cell 2 within the protective case. In addition, via holes (not shown) for mechanical fasteners such as screws are provided in advance at the four corners of the baffle structure 11 for use in fixing the top plate 7 and the bottom plate 5 to the baffle structure 11. Good too.

The top plate 7 and the bottom plate 5 each include a flat plate 8, a reinforcing material 9, and an opening 10. The opening 10 is configured to accommodate a drawbar (not shown), which extends between the top plate 7 and the bottom plate 5. The thickness of the entire top plate 7 and the entire bottom plate 5 can be, for example, 3 to 15 mm. The thicknesses of the flat plate 8 and the reinforcing material 9 can be, for example, 3 to 5 mm and 5 to 10 mm, respectively.
Bolts are embedded in advance on the top plate 7 and the bottom plate 5, and the top plate 7 and the bottom plate 5 can be fixed to the baffle structure 11 and the side plate 15, respectively, using the bolts.
Moreover, if a boss is provided inside the top plate 7, movement of the battery cells 2 in a direction perpendicular to the baffle structure 11 can be restricted.

The side plate 15 has an outer shape that matches the side opening formed when the top plate 7, the bottom plate 5, and the two baffle structures 11 are fixed.

The protective casing member of this embodiment is obtained by molding a resin composition containing (a) PPE-based resin, so the shape of the protective casing of a mobile battery unit obtained from the resin composition is complicated. In addition, the protective casing of the mobile battery unit can be made lightweight.
In addition, the resin composition of the protective casing member of the mobile battery unit has a critical strain of 0.5% or more in chemical resistance evaluation, and a flexural modulus of elasticity measured according to ISO-178. 2500MPa or more, and the combustion level measured based on the UL94 vertical combustion test is V-0, so the safety of the mobile battery unit can be maintained while ensuring the safety of various devices installed inside the protective case. It is possible to securely connect and maintain the connection between the structure and each structure.

In this embodiment, the critical strain amount in chemical resistance evaluation of the protective housing member is 0.5% or more, preferably 0.6% or more, and more preferably 0.7% or more. Further, the bending elastic modulus of the protective housing member measured according to ISO-178 is 2,500 MPa or more, preferably 3,000 MPa or more, and more preferably 3,500 to 20,000 MPa. By setting the critical strain amount to 0.5% or more and the bending elastic modulus to 2500 MPa or more, it is possible to prevent stress in the case of electrolyte leakage or screw holes in the protective case of the mobile battery unit. Even if there is residual cutting oil or electrolyte on the remaining portion and vibration is applied when the automobile is running, damage to the protective housing member can be prevented.

Here, in this embodiment, the critical strain amount in chemical resistance evaluation is measured by the following method.
The pellets of the resin composition for the protective housing member were supplied to a small injection molding machine (product name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) whose cylinder temperature was set to 280°C, and the mold temperature was 70°C and the injection pressure was 75 MPa. A flat plate of 120 mm x 80 mm x 3 mm was formed under the conditions of injection time of 20 seconds and cooling time of 15 seconds.
A strip-shaped test piece (80 mm x 12.5 mm x 3 mm) whose longitudinal direction is perpendicular to the flow direction is cut out from this flat plate. This test piece was placed on the curved surface of a bending bar whose vertical cross section was shaped like a parabola expressed by the equation y ² = 6x (x≧0, y≧0), with the horizontal direction as the x-axis and the vertical direction as the y-axis. , Attach using a jig so that there is no gap between the bar and the test piece. In addition, the position of the bending bar on its vertical cross section where x = 0, y = 0 is the placement position of the measurement starting point side end of the test piece, and the position where x>0 and y>0 is the position where the test piece is measured. It is located at the distal end.
After attaching the test piece to the bending bar as described above, 5-56 (manufactured by Kure Kogyo Co., Ltd.) was applied to the surface of the test piece and left for 48 hours at 23° C. and 50 RH%. If a crack occurs on the surface of the test piece after 48 hours, the critical position where the crack occurs (the position where the value of x is largest in the x-axis direction of the bending bar) is read.
To read the critical position where a crack occurs, transfer the scale of the x-axis coordinate of the bending bar onto the test piece while it is attached to the bending bar, and after removing the test piece from the bending bar, read the scale of the specified size below. Confirm the presence of a crack and read the position of the crack by comparing it with the transcribed scale (the critical position is the position corresponding to the x-axis coordinate of the bending bar, so it is not the periphery length of the test piece) .
Note that in the present disclosure, a crack is a crack of 200 μm or more in the flow direction that is observed when the surface of a test piece is observed using a microscope such as VHX-5000 (manufactured by Keyence Corporation).
Then, the critical strain is calculated using the following formula from the thickness of the test piece and the critical position where cracks occur.
(Critical strain) = d x 3 ^1/2 / {2 x (3 + 2x) ^3/2 } x 100 (%)
d: Thickness of test piece (inch)
x: Position in the x-axis direction (inch)
In addition, although the test piece is produced from the pellet of a resin composition in the above, a test piece can also be produced from a protective housing member (molded article), and a physical property may be measured.

In this embodiment, the bending elastic modulus of the protective housing member measured according to ISO-178 is 2500 MPa or more, preferably 3000 MPa or more, and more preferably 3500 to 20000 MPa. By falling within this range, the rigidity can be applied to the protective case.
In order to have a flexural modulus of 2,500 MPa or more, in the production of the resin composition, the melt-kneading temperature and screw rotation speed must be within a predetermined range, and the extrusion rate must be adjusted to prevent the resin temperature from becoming too high. It can be adjusted as appropriate.
In addition, for the test of the bending elastic modulus, a test piece made from pellets of the resin composition may be used, or a test piece made from a protective housing member (molded product) may be used.

In this embodiment, the combustion level of the resin composition of the protective housing member measured based on the UL94 vertical combustion test is V-0.
Note that the measurement is performed with the resin composition having a thickness of 3.0 mm. Further, the UL94 vertical combustion test can also be performed using a test piece made from a protective housing member (molded product).

In the present embodiment, the bending vibration fatigue properties (number of repetitions until failure) of the resin composition of the protective housing member measured in accordance with ASTM D671 method B are preferably 80,000 times or more, more preferably is 100,000 times or more, more preferably 120,000 times or more.
In addition, the ratio of the number of repetitions mentioned above when chemicals (cutting oil) are attached to the stress-applied area to the number of repetitions mentioned above when no chemicals are attached, that is, the retention rate, must be 70 to 100%. is preferable, more preferably 80 to 100%, still more preferably 90 to 100%. By being within this range, it is possible to reliably hold various devices inside the battery as a protective casing member even in an environment where chemicals may adhere, or to reliably connect and maintain connections between each structure.
In addition, in this embodiment, the bending vibration fatigue characteristics are measured by the following method.
The pellets of the resin composition for the protective housing member were supplied to a small injection molding machine (product name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) whose cylinder temperature was set to 280°C, and the mold temperature was 70°C and the injection pressure was 60 MPa. Under these conditions, a cantilever bending fatigue test piece of "TYPE A" of ASTM D671 B method is obtained. Based on method B of ASTM D671, periodically varying bending stress (repetitive stress: 40 MPa) is applied to the test piece under the following test conditions, and the number of repetitions until each fracture is measured is measured. For each composition, three test pieces were used for measurement without applying cutting oil and when applying cutting oil, and the average of the results was taken as the measurement result. In addition, when applying cutting oil, apply cutting oil to one side of the vibrating part (curved part that is not fixed with a jig) of the cantilever bending fatigue test piece, and keep it under the conditions of 23°C x 50RH% for 3 hours. Do the test after leaving it alone.
Testing machine: Repeated bending vibration fatigue tester B-70 manufactured by Toyo Seiki Seisakusho Co., Ltd.
Repetition frequency: 30Hz (repetition speed 1800 times/min)
Measurement temperature: room temperature (23℃)
Repeated stress: 40MPa
Cutting oil: Honilo988 (manufactured by Castrol)
In addition, although the test piece is produced from the pellet of a resin composition in the above, a test piece can also be produced from a protective housing member (molded article), and a physical property may be measured.

Here, from the viewpoint of having the critical strain amount and bending elastic modulus in the above-mentioned predetermined chemical resistance evaluation, the protective housing member according to the present embodiment contains the component (a) in the morphology image described below. It is preferable that a phase structure having a continuous phase or a sea phase is formed, and specifically, it is preferable that the protective housing member has the morphology shown in the first modification below.
In addition, in this specification, the morphology of the protective housing member includes components (a) to (f) described later, and components (i) that are compatible with components (a) to (f). It refers to the morphology of a part, and parts containing components that are incompatible with components (a) to (f) among component (h) and component (i), which will be described later, are considered to be excluded.

-First modification of this embodiment-
The protective housing member according to the first modification of the present embodiment includes (b) at least one polymer block mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound. A hydrogenated block copolymer in which at least a portion of the block copolymer containing the hydrogenated block copolymer is hydrogenated, and/or a modified product of the hydrogenated block copolymer, and/or (c) an olefin polymer consisting of an olefin. However, it has the following network-like phase structure in the morphology image.
Specifically, the protective housing member of the first modification has a mesh-like phase in a morphology image obtained by dyeing a cross section of the protective housing member with ruthenium tetroxide and observing it using a scanning electron microscope (SEM). Show the structure. In the ruthenium tetroxide staining, a predetermined portion of the polymer chain is generally stained and observed as relatively white in the morphology image. Therefore, as shown in FIG. 2, the protective housing member of the first modification contains component (a) and appears relatively white (gray) in a morphological image observed under predetermined conditions described below. A network-like phase structure having a continuous phase and a linear dispersed phase that contains the (b) component and/or (c) component present in the continuous phase and is observed in a relatively black color. It is formed. The dispersed phase, which corresponds to the network part of the network-like phase structure, has an elongated structure and is formed by bending or branching domains. The connection is repeated. In addition, in the morphological image, the linear dispersed phase does not necessarily have to extend continuously in order to form a network phase structure, and there may be discontinuous portions.

In the protective housing member of the first modification, the morphological image is binarized under predetermined conditions to be described later, so that relatively white (gray) parts in the morphological image are made white, and relatively black parts are made white. In the first processed image (not shown) in which the portion is blackened, the area occupied per unit area (1 μm ² ) of the first white portion that is white after the binarization processing is set as AW1 (μm ² /μm ² ). , the total circumference of the first non-small portions having an area of 15×10 ⁻⁴ μm ² or more among the first black portions that are black after the binarization processing, the sum of the circumferences of the first non-small portions; When the length per unit area (1 μm ² ) is L1 (μm/μm ² ), the length L1 (L1/AW1) with respect to the occupied area AW1 is preferably 7 μm ⁻¹ or more.
In other words, in the protective housing member of the first modification, in the first processed image, the first black portion has a certain size relative to the area occupied by the first white portion per unit area (1 μm ² ). The total length of the circumference (length of the boundary between the white part and the black part) per unit area (1 μm ² ) of the first non-small part (area of 15 × 10 ^-4 μm ² or more) is Because of the length, in morphology, the continuous phase has a boundary of a predetermined length per unit area relative to the dispersed phase having a certain size.

In addition, in this embodiment including the first modification, the area and circumference of the black part after the binarization process are determined by the area and circumference of the black part in the processed image obtained by binarizing the morphological image (digital image) photographed by the method described later. For each pixel, the area and length of each pixel are calculated from the shooting conditions of the morphological image using the software described later, and the number of pixels in the black part after binarization processing and the black color are calculated using the software. It can be determined by calculating the number of pixels around the part, and then multiplying the number of pixels by the area or length per pixel. In addition, for each part of the binarized processed image that is black after the binarization process, the number of pixels located around the black part can be determined by using the software described below. can.
In addition, in the present embodiment including the first modification, the occupied area (μm 2 /μm 2 ) per unit area (1 μm ² ) of a portion that is white after the binarization process, and the occupied area (μm ² /μm ² ) of the portion that is white after the binarization process and the predetermined ^The length (μm/μm ² ) per unit area (1 μm ² ) of the total circumference of the portion having an area (μm 2 ) of , in 5 different image parts with a predetermined area (9 μm ² or 25 μm ² ), sum the area of the white part (μm ² ) and the circumference of the black part with a predetermined area (μm ² ). Then, the area (μm ² ) obtained in the five image parts and the total circumference are added together to obtain an average value, and the average value is calculated as the predetermined average value. shall mean the value obtained by dividing by the area of The predetermined area is set to 9 μm ² or 25 μm ² because, for example, if the dispersed phase is large as a whole, it becomes difficult to calculate the total circumference of the first black portion with an area ^of 9 μm ² . This is because it is appropriate to calculate as follows.

In this embodiment, the morphology image and the first processed image of the protective housing member of the first modification can be obtained by the following method.
First, a measurement cross section is prepared from a fragment of the core portion (center portion in the thickness direction) of the protective housing member using an ultramicrotome. Note that the core portion specifically refers to a central portion that is not easily affected by the injection speed during injection molding and that is 1 μm or more away from the surface layer of the protective housing member in the thickness direction. After staining the measurement section with ruthenium tetroxide, it was photographed using "HITACHI SU-8220" (manufactured by Hitachi High-Tech Fielding Co., Ltd.) at a magnification of 10,000 times, an acceleration voltage of 1.0 kV, a detector: secondary electrons (upper UPPER: Shoot with LA) settings. A digital image (pixel count: 1280×960) of a cross-sectional SEM image is obtained by photographing, and this is used as a morphological image of the protective housing member of this embodiment.
Next, the photographed morphological image is binarized using the image processing software "imageJ" (version 1.50i) in the following manner.
First, a morphological image is opened and a range (the number of pixels corresponding to a 3 μm square or a 5 μm square) to be binarized is selected. The selected image is smoothed using "median filter" of image processing software "imageJ" and binarized using "Threshold" to obtain a first processed image. At this time, the binarization processing algorithm is set to "Default", and the threshold value is set to "Auto".
In the first processed image obtained above, all parts that are black after binarization are extracted using "Analyze Particles" of the image processing software "imageJ", and the number of pixels of that part itself and its By calculating the number of pixels around the portion, the total circumference (μm/μm ² ) of the circumferences of the first non-small portion can be determined. In addition, by extracting all the parts that are white after binarization and calculating the number of pixels, it is possible to calculate the area occupied per unit area of the first white part (μm ² /μm ² ), etc. can.
In this embodiment, five first processed images are created from one protective housing member. For each measurement result, use a numerical value obtained by averaging the respective measurement values obtained from these five images.
Note that defects that occur in the measured cross-section (such as scratches during cross-section preparation with an ultramicrotome or voids inherent in the resin) may be visible in the morphological image, but the image range to be binarized is limited to such defects. The selection shall be made so as not to include any negative parts. In addition, in a binarized image, the part that is black after binarization may be cut off at the edge of the image, and the length of the edge of the image is calculated as a part of the circumference of that part. However, the fact that the length of the end is included can be ignored as an error range.
Furthermore, in the present embodiment, when a morphological image is binarized, pixels 2×2 are cut off because the dispersed phase is too small or there is a possibility of noise.

The functions and effects of the protective housing member of the first modification will be described below.
In the protective housing member of the first modification, the component (b) and/or (c) is contained in the protective housing member, so that a component that contributes to chemical resistance is present in the protective housing member. As a result, chemical resistance is improved compared to the case of using only component (a).
In addition, in ^the first processed image ^, the length L1 (L1/ When AW1) is 7 μm ⁻¹ or more, in the morphology of the protective housing member of the first modification, an effective network can be formed without the dispersed phase being mixed too uniformly in the continuous phase. .
Specifically, the length L1 (L1/AW1) per unit area of the total circumference of the first non-small portion with respect to the occupied area AW1 of the first white portion per unit area is 7 μm ⁻ If it is ¹ or more, the first white portion has a boundary with the first non-small portion having a certain length per unit area. Therefore, the dispersed phase (relatively high in chemical resistance) extends in contact with the continuous phase (relatively low in chemical resistance). Therefore, the dispersed phase exists so as to surround the continuous phase, and can improve chemical resistance, and the dispersed phase can also suppress the extension of cracks caused by chemicals that are temporarily generated in the continuous phase. The reason why the first non-small portion is the first black portion with an area of 15×10 ⁻⁴ μm ² or more is because the dispersed phase, which has a relatively small area, cannot exist so as to wrap around the continuous phase. This is because there is a tendency that the extension of cracks caused by chemicals that occur in the continuous phase cannot be suppressed. Further, the length L1 (L1/AW1) per unit area of the total circumference of the first non-small portion with respect to the occupied area AW1 of the first white portion per unit area is less than 25 μm ⁻¹ . This can occur when the (a) component and (b) component and/or (c) component are melted and kneaded excessively in the process of manufacturing the protective housing member, resulting in dispersion. There is a risk that the phase will be finely dispersed in the continuous phase and the network phase structure will collapse, making it impossible to sufficiently improve chemical resistance.
Therefore, the protective housing member of the first modification has an effective mesh-like phase structure formed by a large number of dispersed phases having a certain size and an elongated and curved shape, so that it has good chemical resistance. This can be effectively improved, and a predetermined critical strain amount in chemical resistance evaluation can be suitably satisfied.

In addition, when the (a) component and the (b) component and/or (c) component are melt-kneaded, if the (b) component and/or (c) component becomes too mixed in the (a) component, the protective casing In the morphology of the body member, the dispersed phase will be finely and finely dispersed. In such a state, the number of first non-small portions decreases and the total circumference thereof becomes short, which tends to reduce chemical resistance.

Here, in ^the first modification ^, the length L1 (L1/ AW1) is preferably 7 μm ⁻¹ or more, more preferably 7.5 μm ⁻¹ or more, and still more preferably 8 μm ⁻¹ or more. Thereby, the predetermined critical strain amount in chemical resistance evaluation can be more suitably satisfied.
Further, the length L1 (L1/AW1) of the total circumference of the first non-small portion per unit area (1 μm ² ) with respect to the occupied area AW1 per unit area (1 μm ² ) of the first white portion is 40 μm ⁻¹ It is preferable that it is below. When L1/AW1 exceeds 40 μm ⁻¹ , it may occur when the content of component (b) and/or component (c) is relatively large with respect to component (a). There is a possibility that sufficient moldability, dimensional stability, and low specific gravity cannot be obtained.

In the case where the protective housing member of the first modification contains the (a) component and (b) component but does not contain the (c) component, the total of the (a) component and (b) component is 100% by mass, and ( The content of component a) is preferably 60 to 90% by weight, more preferably 63 to 87% by weight, even more preferably 66 to 84% by weight. Further, the content of component (b) is preferably 10 to 40 mass %, more preferably 13 to 37 mass %, and even more preferably is 16 to 34% by mass. By setting the (a) component and (b) component within the above range, the number of first non-small portions in the first processed image can be made to preferably fall within a predetermined range.
In addition, in the case where the protective housing member of the first modification contains the (a) component and the (c) component but does not contain the (b) component, the total of the (a) component and the (c) component is assumed to be 100% by mass. The content of component (a) is preferably 60 to 85% by mass, more preferably 63 to 82% by mass, and still more preferably 66 to 79% by mass. Further, the content of component (c) is preferably 15 to 40 mass%, more preferably 18 to 37 mass%, and even more preferably is 21 to 34% by mass.
In addition, in the case where the protective housing member of the first modification contains the (a) component, the (b) component, and the (c) component, the (a) component, the (b) component, and the (c) component. The content of component (c) is preferably 3 to 30% by mass, more preferably 6 to 27% by mass, and even more preferably 9 to 24% by mass, assuming the total of 100% by mass. Further, the content of component (b) is preferably 3 to 20% by mass, more preferably 6 to 20% by mass, assuming that the total of components (a), (b), and (c) is 100% by mass. It is 17% by weight, more preferably 9 to 14% by weight. Furthermore, in such a case, the ratio of the content of component (c) to the content of component (b) (component (c):component (b)) is preferably 1:2 to 5:1, and more preferably Preferably the ratio is 1:1.5 to 4.5:1.
By setting the component (a), the component (b), and/or the component (c) within the above ranges, the number of first non-small portions can easily be suitably within a predetermined range.

In the protective housing member of the first modification, the resin component in the composition constituting the protective housing member is 100% by mass, and (a) component, (b) component and/or (c) component The total content of is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more. If the composition constituting the protective housing member contains a resin component that is compatible with component (a), the resin component in the composition constituting the protective housing member is taken as 100% by mass. , the total content of component (a), component (b) and/or component (c) is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass. The content is particularly preferably 99% by mass or more.
Furthermore, in the protective housing member of the first modification, the total content of component (a), component (b), and/or component (c) is 100% by mass of the composition constituting the protective housing member. The amount is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more.

--About (a) Ingredients--
The polyphenylene ether resin (a) used in the first modification is not particularly limited, and examples thereof include polyphenylene ether, modified polyphenylene ether, and mixtures thereof. Component (a) may be used alone or in combination of two or more.

The reduced viscosity of component (a) is preferably 0.25 dL/g or more, more preferably 0.28 dL/g or more, from the viewpoint of further improving the flame retardance of the protective housing member. , preferably 0.60 dL/g or less, more preferably 0.57 dL/g or less, particularly preferably 0.55 dL/g or less. Reduced viscosity can be controlled by polymerization time and catalyst amount.
The reduced viscosity can be measured using a chloroform solution with η _sp /c: 0.5 g/dL at a temperature of 30° C. using an Ubbelohde viscosity tube.

［式中、Ｒ^３１、Ｒ^３２、Ｒ^３３、及びＲ^３４は、各々独立して、水素原子、ハロゲン原子、炭素原子数１～７の第１級のアルキル基、炭素原子数１～７の第２級のアルキル基、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、及び少なくとも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より選ばれる一価の基である。］ -Polyphenylene ether-
The polyphenylene ether is not particularly limited, and includes, for example, a homopolymer having a repeating unit structure represented by the following formula (3), and/or a copolymer having a repeating unit structure represented by the following formula (3). Examples include polymers.

[In the formula, R ³¹ , R ³² , R ³³ , and R ³⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, or a primary alkyl group having 1 to 7 carbon atoms. Selected from the group consisting of secondary alkyl groups, phenyl groups, haloalkyl groups, aminoalkyl groups, hydrocarbonoxy groups, and halohydrocarbonoxy groups in which at least two carbon atoms separate the halogen atom and the oxygen atom. It is a monovalent group. ]

Such polyphenylene ether is not particularly limited, and known polyphenylene ethers can be used. Specific examples of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl- Homopolymers such as 6-phenyl-1,4-phenylene ether) and poly(2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol, 2,3,6-trimethylphenol, and - Copolymers such as copolymers with other phenols such as methyl-6-butylphenol; etc., such as poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

The method for producing polyphenylene ether is not particularly limited, and conventionally known methods can be used. A specific example of a method for producing polyphenylene ether is, for example, US Pat. No. 3,306,874, in which polyphenylene ether is produced by oxidative polymerization of 2,6-xylenol using a complex of a cuprous salt and an amine as a catalyst. methods described in books, etc., U.S. Patent No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. Examples include the method described in JP-A-63-152628 and the like.

---Modified polyphenylene ether---
The modified polyphenylene ether is not particularly limited, and examples thereof include those obtained by grafting and/or adding a styrene polymer and/or a derivative thereof to the above polyphenylene ether. The proportion of mass increase due to grafting and/or addition is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less based on 100% by mass of modified polyphenylene ether. The content is preferably 7% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

The method for producing modified polyphenylene ether is not particularly limited, and for example, in the presence or absence of a radical generator, in a molten state, a solution state, or a slurry state, under conditions of 80 to 350 ° C. Examples include a method of reacting polyphenylene ether with a styrene polymer and/or a derivative thereof.

When component (a) is a mixture of polyphenylene ether and modified polyphenylene ether, the mixing ratio of the polyphenylene ether and modified polyphenylene ether is not particularly limited and may be any ratio.

--About (b) component--
Component (b) used in the first modification is a block copolymer containing at least one polymer block mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound. A hydrogenated block copolymer in which at least a portion of the hydrogenated block copolymer is hydrogenated and/or a modified product of the hydrogenated block copolymer. In other words, the component (b) used in the first modification is not particularly limited, and includes, for example, a hydrogenated block copolymer (unmodified hydrogenated block copolymer), a modified hydrogenated block copolymer, (modified hydrogenated block copolymer), and mixtures of both. Component (b) may be used alone or in combination of two or more.
Hereinafter, a polymer block mainly composed of a vinyl aromatic compound is also referred to as a polymer block A, and a polymer block mainly composed of a conjugated diene compound is also referred to as a polymer block B.

--- Polymer block A ---
Examples of the polymer block A mainly composed of a vinyl aromatic compound include a homopolymer block of a vinyl aromatic compound, a copolymer block of a vinyl aromatic compound and a conjugated diene compound, and the like. Among these, homopolymer blocks of vinyl aromatic compounds, copolymer blocks of vinyl aromatic compounds and conjugated diene compounds containing more than 50% by mass (preferably 70% by mass or more) of vinyl aromatic compound units, etc. are preferred. .
Here, in the polymer block A, "consisting mainly of vinyl aromatic compounds" means that the polymer block A before hydrogenation contains more than 50% by mass of vinyl aromatic compound units; The content of the compound unit is preferably 70% by mass or more, and more preferably 80% by mass or more. Further, the vinyl aromatic compound unit may be 100% by mass or less in the polymer block A before hydrogenation.

The vinyl aromatic compound is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Among them, styrene is preferred.
Examples of the conjugated diene compound include the conjugated diene compounds described below, with butadiene, isoprene, and combinations thereof being preferred.
These may be used alone or in combination of two or more.

In polymer block A, the distribution of vinyl aromatic compounds, conjugated diene compounds, etc. in the molecular chain of the polymer block can be random, tapered (monomer components increase or decrease along the molecular chain), or partially block-like. Alternatively, it may be composed of any combination thereof.

When there are two or more polymer blocks A in component (b), each polymer block A may have the same structure or different structures. Moreover, when two or more types of (b) components are combined, the polymer blocks A in each (b) component may be the same or different.

The number average molecular weight (Mn) of the polymer block A is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, from the viewpoint of obtaining even better chemical resistance. . Moreover, from the same viewpoint, it is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less.

--- Polymer block B ---
Examples of the polymer block B mainly composed of a conjugated diene compound include a homopolymer block of a conjugated diene compound, a random copolymer block of a conjugated diene compound and a vinyl aromatic compound, and the like. Among these, a homopolymer block of a conjugated diene compound, a copolymer block of a conjugated diene compound and a vinyl aromatic compound containing more than 50% by mass (preferably 70% by mass or more) of conjugated diene compound units, and the like are preferred.
Here, in the polymer block B, "containing mainly a conjugated diene compound" means that the polymer block B contains more than 50% by mass of conjugated diene compound units, from the viewpoint of improving the fluidity of the resin composition. Therefore, the content of conjugated diene compound units is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

The conjugated diene compound is not particularly limited, but examples include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene, isoprene and combinations thereof are preferred.
Examples of the vinyl aromatic compound include the vinyl aromatic compounds described above, with styrene being preferred.
These may be used alone or in combination of two or more.

In polymer block B, the distribution of conjugated diene compounds, vinyl aromatic compounds, etc. in the molecular chain of the polymer block can be random, tapered (monomer components increase or decrease along the molecular chain), or partially block-like. Alternatively, it may be composed of any combination thereof.

When there are two or more polymer blocks B in component (b), each polymer block B may have the same structure or may have a different structure. In addition, when two or more types of (b) components are combined, the polymer block B in each component (b) and the polymer block B in the component (b-2) are the same. It may be different or it may be different.

The hydrogenation rate for the ethylenic double bonds in the conjugated diene compound units in the polymer block B is preferably 20% or more from the viewpoint of obtaining chemical resistance. Note that the hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).

The total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to the ethylenic double bonds in the conjugated diene compound unit in the polymer block B is determined from the viewpoint of obtaining even better chemical resistance. It is preferably 25 to 90%, more preferably 30 to 80%.
In this specification, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (total vinyl bond amount) refers to the conjugated diene compound units in the conjugated diene compound-containing polymer block before hydrogenation. The sum of the 1,2-vinyl bond amount, the 3,4-vinyl bond amount, and the 1,4-conjugated bond amount of the total of the 1,2-vinyl bond amount and 3,4-vinyl bond amount in Refers to the percentage of The total vinyl bond amount was measured using an infrared spectrophotometer, and was measured using an infrared spectrophotometer, as described in Analytical Chemistry, Volume 21, No. 8, August 1949.

The number average molecular weight (Mn) of the polymer block B is preferably 20,000 or more, more preferably 30,000 or more, still more preferably 40,000 or more, from the viewpoint of obtaining even better chemical resistance. 000 or more. Further, the number average molecular weight (Mn) is preferably 100,000 or less, more preferably 80,000.

The glass transition temperature of polymer block B after hydrogenation is preferably 0°C or lower, more preferably -10°C or lower, from the viewpoint of obtaining even better chemical resistance.
In addition, in this specification, the glass transition temperature of a block copolymer and the glass transition temperature of a polymer block in a block copolymer are measured by measuring a sample formed into a film using a dynamic viscoelasticity measurement device, for example. It can be measured using a tensile mode, a temperature scan rate of 3° C./min, a frequency of 1 Hz, and a nitrogen atmosphere.

---Structure of hydrogenated block copolymer---
The structure of the hydrogenated block copolymer in component (b) is, for example, AB type, ABA type, if the polymer block A is “A” and the polymer block B is “B”. type, B-A-B-A type, (A-B-)n-X type (where n is an integer of 1 or more, and X is the reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride). group or a residue of an initiator such as a polyfunctional organolithium compound), and structures such as ABAB-A type.
In component (b), it is preferable that the structure of the hydrogenated block copolymer contains a hydrogenated block copolymer having two polymer blocks A, more preferably two polymer blocks A. and contains a hydrogenated block copolymer having one polymer block B.
Regarding the block structure, the polymer block B is a homopolymer block of a conjugated diene compound, or a conjugated diene compound containing more than 50 mass% (preferably 70 mass% or more) of conjugated diene compound units and a vinyl aromatic compound. A copolymer block with a compound, in which the polymer block A is a homopolymer block of a vinyl aromatic compound, or a vinyl aromatic compound containing more than 50% by mass (preferably 70% by mass or more) of a vinyl aromatic compound. A copolymer block of a conjugated diene compound and a conjugated diene compound is preferable.
Note that the component (b) may contain blocks other than the polymer block A and the polymer block B.

The molecular structure of the hydrogenated block copolymer in component (b) is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof.

--- Content of vinyl aromatic compound units ---
The content of vinyl aromatic compound units (hydrogenated block copolymer constitutional units derived from vinyl aromatic compounds) in component (b) before hydrogenation is not particularly limited, but is determined by the heat resistance and mechanical properties of the protective housing member. From the viewpoint of physical strength, the content is preferably 10 to 70% by weight, more preferably 20 to 70% by weight, more preferably 20 to 60% by weight, and still more preferably 30 to 50% by weight. In addition, not only one type of (b) component having a vinyl aromatic compound unit content within these ranges, but also two or more types of (b) components having different vinyl aromatic compound unit contents can be used in combination. .

---Total vinyl bond amount---
(b) The total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to ethylenic double bonds in the conjugated diene compound unit contained in component is preferably 25% or more and 90% or less. .
The method for controlling the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds within the above range is not particularly limited, but for example, in the production of component (b), the amount of 1,2-vinyl bonds Examples include a method of adding a regulator and a method of adjusting the polymerization temperature.
"The total of 1,2-vinyl bonds and 3,4-vinyl bonds with respect to the double bonds in the conjugated diene compound unit" refers to the conjugated diene compound in the block copolymer before hydrogenation of the hydrogenated block copolymer. Refers to the total of 1,2-vinyl bonds and 3,4-vinyl bonds relative to the double bonds (ethylenic double bonds) in the unit. For example, the block copolymer before hydrogenation can be measured using an infrared spectrophotometer and calculated using the Hampton method. Moreover, it can also be calculated using NMR from the block copolymer after hydrogenation.

--- Hydrogenation rate ---
In component (b), the hydrogenation rate for ethylenic double bonds (double bonds in conjugated diene compound units) in the block copolymer is preferably more than 0% from the viewpoint of chemical resistance, It is more preferably 10% or more, still more preferably 20% or more, particularly preferably 20% or more. Further, the hydrogenation rate is preferably 100% or less.
Component (b) having such a hydrogenation rate is used, for example, to reduce the amount of hydrogen consumed to a desired hydrogenation rate (for example, 10% or more and less than 80%) in the hydrogenation reaction of ethylenic double bonds in a block copolymer. ) can be easily obtained by controlling the range.
The hydrogenation rate can be determined by, for example, quantifying the amount of double bonds remaining in the polymer block B by NMR measurement.

--- Number average molecular weight (Mn) of block copolymer before hydrogenation ---
The number average molecular weight (Mn) of the block copolymer before hydrogenation is preferably 5,000 or more, more preferably 10,000 or more, particularly preferably 30,000 or more, and , is preferably 1,000,000 or less, more preferably 800,000 or less, and particularly preferably 500,000 or less.

--- (b) When containing a specific component as component ---
From the viewpoint of chemical resistance, the component (b) preferably contains a component (b') having a molecular weight peak of 10,000 to 200,000 after hydrogenation in terms of standard polystyrene measured by GPC. More preferably, the molecular weight peak of component (b') is 30,000 to 200,000. Furthermore, component (b) preferably contains the following components (b-1) or (b-2), each having a different molecular weight peak, and more preferably component (b-1) and (b-2). Contains ingredients. The molecular weight peak of the component (b-1) measured by GPC after hydrogenation in terms of standard polystyrene is 80,000 to 200,000, preferably 100,000 to 200,000, from the viewpoint of chemical resistance. In addition, from the viewpoint of chemical resistance, the molecular weight peak of component (b-2) after hydrogenation measured by GPC in terms of standard polystyrene is 10,000 or more and less than 80,000, and 30,000 or more and less than 80,000. preferable.
The method for controlling the molecular weight peak of the component (b) within the above range is not particularly limited, but includes, for example, a method of adjusting the amount of catalyst in the polymerization step.
In this specification, the molecular weight peak can be measured using gel permeation chromatography System 21 manufactured by Showa Denko KK under the following conditions. In this measurement, a column consisting of one K-G manufactured by Showa Denko K.K., one K-800RL, and one K-800R connected in series was used, and the column temperature was 40°C. The solvent is chloroform, the solvent flow rate is 10 mL/min, and the sample concentration is 1 g of hydrogenated block copolymer/1 liter of chloroform solution. In addition, a calibration curve is created using standard polystyrene (the molecular weights of standard polystyrene are 3650000, 2170000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, and 550). Furthermore, the wavelength of UV (ultraviolet light) of the detection part is set to 254 nm for both standard polystyrene and hydrogenated block copolymer.
In addition, the number average molecular weight (MnbA) of the polymer block A forming the component (b) is, for example, when the component (b) has an ABA type structure, the number average molecular weight (Mnb) of the component (b) Based on this, assuming that component (b) has one molecular weight distribution and two polymer blocks A mainly composed of vinyl aromatic compounds exist with the same molecular weight, (MnbA) = (Mnb) x bond. It can be calculated using the formula: ratio of vinyl aromatic compound amount divided by 2. In addition, if the sequence of block structure A and block structure B is clear at the stage of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, the measurement was performed without depending on the above calculation formula ( b) It may be calculated from the proportion of block structure A based on the number average molecular weight (Mnb) of component.

In addition, the components (b'), (b-1), and (b-2) preferably have the following physical properties from the viewpoint of obtaining even better chemical resistance.
That is, component (b'), component (b-1), and component (b-2) preferably have a number average molecular weight (Mn) of polymer block A of 5,000 to 25,000, more preferably is 10,000 to 25,000.
Further, the hydrogenation rate with respect to the ethylenic double bonds in the conjugated diene compound units in the polymer block B is preferably 20% or more and less than 80%, more preferably 20% or more and less than 70%.
The number average molecular weight (Mn) of the polymer block B is preferably 20,000 to 100,000, more preferably 20,000 to 90,000, even more preferably 20,000 to 80,000.
The glass transition temperature of polymer block B after hydrogenation is preferably -50°C or lower, more preferably -60°C or lower, and even more preferably -70°C or lower.
The total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to ethylenic double bonds in the conjugated diene compound unit is preferably 25% or more and less than 60%, and 25% or more and 55% or less. It is more preferable that the amount is 25% or more and 50% or less. In addition, it is preferable that the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds is 25% or more from the viewpoint of improving compatibility with component (b-3) described below, which can be optionally included. .
The hydrogenation rate for ethylenic double bonds (double bonds in conjugated diene compound units) in the block copolymer is preferably more than 0% and less than 80%, more preferably 10% or more and less than 80%, More preferably 20% or more and less than 80%, still more preferably 20 to 70%, particularly preferably 20% or more and less than 70%.
The content of vinyl aromatic compound units (hydrogenated block copolymer constitutional units derived from vinyl aromatic compounds) before hydrogenation is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, More preferably 20 to 60% by weight, still more preferably 30 to 50% by weight, particularly preferably 30 to 40% by weight.
The molecular weight distribution (Mw/Mn) before hydrogenation is preferably 1.01 to 1.50, more preferably 1.03 to 1.40. The molecular weight distribution (Mw/Mn) can be determined by dividing the weight average molecular weight (Mw) determined using GPC (moving phase: chloroform, standard material: polystyrene) by the number average molecular weight (Mn) described above. It can be calculated.
In component (b'), component (b-1), and component (b-2), the structure of the hydrogenated block copolymer contains a hydrogenated block copolymer having two polymer blocks A. is preferable, and more preferably contains a hydrogenated block copolymer having two polymer blocks A and one polymer block B.

For polymer block B, the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to ethylenic double bonds in the conjugated diene compound units contained in polymer block B is 25% or more and 60%. A polymer block mainly composed of a conjugated diene compound in which the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 25 to 45%. Mainly composed of a conjugated diene compound having both B1 and a polymer block B2 mainly composed of a conjugated diene compound in which the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds is 45% or more and less than 70%. It may also be a polymer block.
The structure of the block copolymer having polymer block B1 and polymer block B2 is such that the polymer block A is "A", the polymer block B1 is "B1", and the polymer block B2 is "B2". For example, it can be obtained by a known polymerization method in which the amount of vinyl bonds is controlled based on the feed sequence of each monomer unit, which is indicated by A-B2-B1-A, A-B2-B1, etc. can.

When component (b) contains the above-mentioned components (b-1) and (b-2), the molecular weight peak calculated by GPC measurement in terms of standard polystyrene is 80,000 to 200,000 as component (b-1). The ratio (b-1):(b-2) of the component (b-2) with a molecular weight peak of 10,000 or more and less than 80,000 in terms of standard polystyrene by GPC measurement is determined from the viewpoint of obtaining even better chemical resistance. , 10:90 to 50:50, more preferably 20:80 to 40:60.
Note that the ratio of the component (b-1) and the component (b-2) can be determined by calculating the area ratio of each peak during GPC measurement similar to the measurement of the molecular weight peak described above.
The method of controlling the ratio of component (b-1) and component (b-2) within the above range is not particularly limited, but for example, a method of adjusting the amount of coupling agent during the coupling treatment after polymerization. etc.

Furthermore, component (b) may be used in addition to component (b'), component (b-1), and component (b-2), or component (b'), component (b-1), and component (b-2). It is preferable to include component (b-3) in place of component -2) (component (b-3) is included in component (b'), component (b-1), and component (b-2). (Ingredients that are not included) More preferably, component (b) contains the above-mentioned component (b') and component (b-3), and even more preferably, component (b-1), component (b-2), and component (b-3). Contains ingredients. Component (b-3) preferably has the following physical properties from the viewpoint of obtaining even better chemical resistance.
That is, in component (b-3), the number average molecular weight (Mn) of polymer block A is preferably 15,000 or more, more preferably 20,000 or more, and 25,000 or more. is more preferably 26,000 or more, particularly preferably 26,000 or more, preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less.
The hydrogenation rate to the ethylenic double bonds in the conjugated diene compound units contained in the polymer block B is preferably 80% or more, more preferably 90% or more.
The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (total vinyl bond amount) with respect to the ethylenic double bonds in the conjugated diene compound units contained in polymer block B is 50% or more. It is preferably 55% or more, still more preferably 65% or more, and preferably 90% or less.
The number average molecular weight (Mn) of polymer block B is preferably 30,000 to 100,000, more preferably 40,000 to 100,000. The glass transition temperature of polymer block B after hydrogenation is preferably higher than -50°C, more preferably higher than -50°C and lower than 0°C, even more preferably between -40 and -10°C.
The ratio of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the ethylenic double bonds in the conjugated diene compound unit is preferably more than 50% and 90% or less, more preferably 60 to 90%. It is 90%.
The hydrogenation rate with respect to ethylenic double bonds (double bonds in conjugated diene compound units) in the block copolymer is preferably 80 to 100%, more preferably 90 to 100%.
(b-3) From the viewpoint of improving the fluidity and appearance of the component and reducing the occurrence of welds, the content of vinyl aromatic compound units in the block copolymer before hydrogenation is 30% by mass or more. The content is preferably 32% by mass or more, more preferably more than 40% by mass, further preferably 50% by mass or less, and even more preferably 48% by mass or less. Note that the content of the vinyl aromatic compound can be measured using an ultraviolet spectrophotometer.
The molecular weight distribution (Mw/Mn) before hydrogenation is preferably 10 or less, more preferably 8 or less, and particularly preferably 5 or less.

---Production method---
The method for producing the hydrogenated block copolymer in component (b) is not particularly limited, and any known production method may be used, including known methods such as anionic polymerization without particular limitation. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, and JP-A-56-10542. JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent No. 1130770, US Pat. No. 3,281,383, US Pat. No. 3,639,517, UK Examples include methods described in Japanese Patent No. 1020720, US Pat. No. 3,333,024, and US Pat. No. 4,501,857.

---Modified hydrogenated block copolymer---
As the modified hydrogenated block copolymer in component (b), for example, the above hydrogenated block copolymer (especially unmodified hydrogenated block copolymer) and α,β-unsaturated carboxylic acid or its A modified hydrogenated block obtained by reacting a derivative (ester compound or acid anhydride compound) at 80 to 350°C in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state. Examples include polymers. In this case, the α,β-unsaturated carboxylic acid or its derivative is preferably grafted or added to the unmodified hydrogenated block copolymer in a proportion of 0.01 to 10% by mass; The proportion is more preferably 7% by mass or less, particularly preferably 5% by mass or less.
When using both an unmodified hydrogenated block copolymer and a modified hydrogenated block copolymer as component (b), the mixing ratio of the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer is You can decide without any particular restrictions.

--(c) Olefin polymer --
The component (c) used in the first modification is not particularly limited, and examples thereof include homopolymers of olefin monomers, copolymers of two or more types of monomers including olefin monomers, etc. . Among these, from the viewpoint of low-temperature impact resistance, copolymers of ethylene and α-olefins other than ethylene are preferred. Here, from the viewpoint of chemical resistance and impact resistance of the resulting resin composition, it is preferable that the monomer units constituting component (c) do not contain propylene units.
In addition, in the case of "olefin polymer consisting of olefin", "does not contain propylene units" includes cases where propylene is contained as a constitutional unit to an extent that does not impede the effects of the invention. For example, in component (c), It means that the content of propylene units in all the structural units constituting component (c) is less than 0.1% by mass.

Component (c) includes, for example, a copolymer of ethylene and one or more C3 to C20 α-olefins. Among these, copolymers of ethylene and one or more C3 to C8 α-olefins are more preferable, and copolymers of ethylene and 1-propylene, 1-butene, 1-hexene, 4-methyl- It is more preferably a copolymer with one or more comonomers selected from the group consisting of 1-pentene and 1-octene, and particularly preferably a copolymer of ethylene and 1-butene. . By using such a copolymer as component (c), a resin composition having higher impact resistance and higher chemical resistance tends to be obtained.
Component (c) may be used alone or in combination of two or more. Furthermore, two or more types of ethylene-α-olefin copolymers may be used as component (c).

From the viewpoint of flexibility of the resin composition, the content of ethylene in component (c) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, based on the total amount of the olefin polymer.
The content of α-olefin other than ethylene in component (c) is not particularly limited, and from the viewpoint of flexibility of the resin composition, it is preferably 5% by mass or more based on the total amount of the olefin polymer. , more preferably 20% by mass or more, and from the viewpoint of rigidity of the resin composition, preferably 50% by mass or less, and more preferably 48% by mass or less.

The embrittlement temperature of component (c) is -50°C or lower, preferably -60°C or lower, and preferably -70°C or lower from the viewpoint of obtaining even better impact resistance and chemical resistance. is more preferable.
In addition, the said embrittlement temperature can be measured according to ASTM D746.

The density (density at the raw material stage before kneading) of component (c) measured in accordance with JIS K7112 is preferably 0.87 g/cm 3 or more, and 0.87 g/cm ³ or more from the viewpoint of chemical resistance of the resin composition. More preferably, it is .90 g/cm ³ or more.
The method for controlling the density of component (c) within the above range is not particularly limited, but includes, for example, a method of adjusting by controlling the content ratio of ethylene units.

The melt flow rate (MFR, density at the raw material stage before kneading, measured at 190°C and a load of 2.16 kgf according to ASTM D-1238) of the resin composition of the (c) component is From the viewpoint of stabilizing the morphology by dispersing into the resin composition and impact resistance of the resin composition, the amount is preferably 0.1 to 5.0 g/10 minutes, more preferably 0.3 to 4.0 g/10 minutes.
The method of controlling the melt flow rate of component (c) within the above range is not particularly limited, but includes, for example, a method of adjusting the polymerization temperature and polymerization pressure when producing component (c), a method of controlling the melt flow rate of component (c), , a method of adjusting the molar ratio between the concentration of monomers such as α-olefin and the concentration of hydrogen, and the like.

Component (c) may be, for example, an olefin polymer rubber made of olefin.
The torsional rigidity of component (c) is preferably 1 to 30 MPa, more preferably 1 to 25 MPa, from the viewpoint of imparting sufficient impact resistance to the composition. Note that the torsional rigidity of component (c) can be measured in accordance with ASTM D 1043.
The Shore A of component (c) is preferably from 40 to 110, more preferably from 50 to 100, from the viewpoint of imparting sufficient impact resistance to the composition. Note that the Shore A of component (c) can be measured in accordance with JIS K 6253.

The method for preparing component (c) is not particularly limited, and catalysts (e.g., titanium, metallocene, or vanadium-based Examples include methods using catalysts such as Among these, methods using metallocene catalysts and titanium chloride catalysts are preferred from the viewpoint of stability in structural control. As a method for producing the ethylene-α-olefin copolymer, known methods described in JP-A No. 6-306121, Japanese Patent Application Publication No. 7-500622, etc. can be used.

--Method for manufacturing protective casing member according to first modification --
--- Method for producing resin composition for protective housing member ---
The resin composition of the protective housing member according to the first modification is prepared by melt-kneading the above-mentioned (a) component, (b) component and/or (c) component, and, if necessary, each component described below. It can be manufactured by

As a method for producing the resin composition of the first modification, when the component (b) is not included but the component (a) and the component (c) are included, the following steps (1-1) and (1-2) are carried out. Preferably, the manufacturing method includes.
(1-1): A step of melting and kneading the component (a) to obtain a kneaded product.
(1-2): A step of adding the component (c) to the kneaded material obtained in the step (1-1) and melting and kneading it.
In the step (1-1), the component (a) may be added in its entirety or in part.
In the above step (1-2), component (c) may be added in its entirety or in part. When a portion of component (c) is added in step (1-2), the entire amount of component (c) may be added in step (1-1) and step (1-2). The step (1-2) is preferably a step in which the entire amount of the component (c) is added to the kneaded material obtained in the step (1-1), and the mixture is melt-kneaded.
As in this production method, by adding component (c) in step (1-2) during melt-kneading (particularly by adding the entire amount of component (c) in step (1-2)), Component (c) is appropriately dispersed in component (a), resulting in a resin composition with even better chemical resistance.

Further, in the method for producing the resin composition of the first modification, when the component (b) is contained in addition to or in place of the component (c), the above step (1-1) and In (1-2), the entire amount of component (b) is added to step (1-1) or step (1-2), or a part of component (b) is added to step (1-1) or step (1-2). -2) is preferably added. Components (b) and (c) are appropriately dispersed in component (a), resulting in a resin composition with even better chemical resistance.

In addition, as the method for producing the resin composition of the first modification, when the component (c) and the component (b) are contained, and the component (b) contains the component (b-3), the above step (1-1) and (1-2) are preferably carried out as the following steps.
(1-1): A step of melting and kneading the component (a) and the component (b-3) to obtain a kneaded product.
(1-2): A step of adding the component (c) to the kneaded material obtained in the step (1-1) and melting and kneading it.
In the step (1-1), the component (a) may be added in its entirety or in part. Further, the above component (b-3) may be added in its entirety or in part. Among these, the step (1-1) is preferably a step of melt-kneading the entire amount of the component (a) and, if necessary, the entire amount or part of the component (b-3) to obtain a kneaded product. .
In the step (1-2), the component (c) may be added in its entirety or in part. When a portion of component (c) is added in step (1-2), the entire amount of component (c) may be added in step (1-1) and step (1-2). The step (1-2) is preferably a step in which the entire amount of the component (c) is added to the kneaded material obtained in the step (1-1), and the mixture is melt-kneaded.
As in this production method, by adding component (c) in step (1-2) during melt-kneading (particularly by adding the entire amount of component (c) in step (1-2)), Component (c) is appropriately dispersed in component (a), resulting in a resin composition with even better chemical resistance.

In addition, as a method for manufacturing the resin composition of the first modification, when the component (c) and the component (b) are contained, and the component (b) contains the component (b'), the following steps are performed. It is preferable that That is, in such a case, it is preferable to add the component (b') together with the component (c) in step (1-2). In the step (1-2), the component (b') may be added in its entirety or in part. When a portion of component (b') is added in step (1-2), the entire amount of component (b') may be added in step (1-1) and step (1-2). It is more preferable that the step (1-2) is a step in which the entire amount of the component (b') is added to the kneaded material obtained in the step (1-1), and the mixture is melt-kneaded. As in this production method, during melt-kneading, the component (b') is added in step (1-2) (particularly, the entire amount of component (b') is added in step (2-2)). ) and (b') are appropriately dispersed in component (a), resulting in a resin composition with even better chemical resistance and impact resistance. Component (b') can also be used as component (b-1) and component (b-2).

The melt kneader suitably used to melt and knead each component in the method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a single screw extruder, a twin screw extruder, etc. Examples include extruders such as a multi-screw extruder, heated melt kneaders such as rolls, kneaders, Brabender Plastographs, Banbury mixers, etc., but twin-screw extruders are particularly preferred from the viewpoint of kneading properties. Specific examples of the twin-screw extruder include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Japan Steel Works, Ltd.
The type and specifications of the extruder are not particularly limited, and may be any known extruder.

Hereinafter, preferred embodiments will be described in which an extruder such as a multi-screw extruder such as a single-screw extruder or a twin-screw extruder is used.
The L/D (barrel effective length/barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, and preferably 75 or less, and more preferably 60 or less. preferable.

The configuration of the extruder is not particularly limited, and may include, for example, a first raw material supply port upstream in the direction in which the raw materials flow, a first vacuum vent downstream of the first raw material supply port, and a first vacuum vent located downstream from the first vacuum vent. A second raw material supply port is downstream of the second raw material supply port, a first liquid addition pump is downstream of the second raw material supply port, a third raw material supply port is downstream of the first liquid addition pump, and downstream of the third raw material supply port. A second vacuum vent may be provided, and a second liquid addition pump may be provided downstream of the second vacuum vent.

In addition, the method of feeding raw materials at the second and third raw material supply ports is not particularly limited, and may be simply added from the upper open port of the raw material supply port, or may be simply added from the side open port using a forced side feeder. It is also possible to add it, and from the viewpoint of stable supply, it is particularly preferable to add it from the side opening using a forced side feeder.

When melt-kneading each component, the melt-kneading temperature (barrel setting temperature) may be 200 to 370° C. without particular limitation, and the screw rotation speed may be 300 to 800 rpm without particular limitation.

When adding a liquid raw material, it can be added by directly feeding the liquid raw material into the cylinder system using a liquid addition pump or the like in the extruder cylinder section. The liquid addition pump is not particularly limited, and examples thereof include gear pumps and flange type pumps, and gear pumps are preferred. At this time, from the viewpoint of reducing the load on the liquid addition pump and improving the operability of the raw material, it is necessary to install a tank for storing the liquid raw material, piping between the tank and the liquid addition pump, and a connection between the pump and the extruder cylinder. It is preferable that the viscosity of the liquid raw material be reduced by heating the portion that serves as a flow path for the liquid raw material, such as the piping between the two, using a heater or the like.

In the method for manufacturing the resin composition of the protective housing member according to the first modification, the control method for forming the network phase structure of the protective housing member as described above is, for example, based on the content of the component (a). , (b) component and/or (c) component, and by adjusting the structure and molecular weight of each block portion of (b) component. For example, component (b) may contain component (b'), or components (b-1) and (b-2), and the structure and molecular weight of each of these block parts may be adjusted; It can be controlled by including component (b-3) and appropriately selecting the structure and molecular weight of each block portion of component (b-3). Further, in the production of the resin composition, the melt-kneading temperature and screw rotation speed can be controlled within the above ranges, or by adjusting the extrusion rate to prevent the resin temperature from becoming too high. Furthermore, in the production of the resin composition, it can be controlled by performing steps (1-1) and (1-2) of the above production method.

--- Manufacturing method of protective housing member ---
The protective housing member (molded body) according to the first modification can be manufactured by molding the resin composition described above. The method for producing the molded product is not particularly limited, and examples thereof include injection molding, extrusion molding, extrusion profile molding, blow molding, compression molding, etc. From the viewpoint of obtaining the effects of the present invention more effectively, Injection molding is preferred.

Here, in the resin composition of the protective casing member of the mobile battery unit according to the present embodiment (including the above-mentioned first modification), the following components can be optionally included or not included. You can do it like this.

-(d) Phosphoric ester compound-
In the resin composition of the protective housing member according to this embodiment, (d) a phosphoric acid ester compound can be optionally used. (d) The phosphoric ester compound is not particularly limited, and may be any phosphoric ester compound in general (phosphoric ester compounds, condensed phosphoric ester compounds, etc.) that has the effect of improving the flame retardance of the resin composition. , for example triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bis neopentyl phosphate, phenyl-bis(3,5,5'-trimethyl-hexyl phosphate), ethyl diphenyl phosphate, 2-ethyl-hexyl di(p-tolyl) Phosphate, bis-(2-ethylhexyl)-p-tolyl phosphate, tritolyl phosphate, bis-(2-ethylhexyl) phenyl phosphate, tri-(nonylphenyl) phosphate, di(dodecyl)-p-tolyl phosphate, tricresyl Phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolylbis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, bisphenol A bis(diphenyl phosphate), diphenyl-(3-hydroxy) phenyl) phosphate, bisphenol A bis(dicresyl phosphate), resorcin bis(diphenyl phosphate), resorcin bis(dixylenyl phosphate), 2-naphthyl diphenyl phosphate, 1-naphthyldiphenyl phosphate, di(2-naphthyl) Examples include phenyl phosphate.

［式（４）中、Ｑ^４１、Ｑ^４２、Ｑ^４３、Ｑ^４４は、各々独立して、炭素原子数１～６のアルキル基であり；Ｒ^４１、Ｒ^４２は、各々独立して、メチル基であり；Ｒ^４３、Ｒ^４４は、各々独立して、水素原子又はメチル基であり；ｘは０以上の整数であり；ｐ_１、ｐ_２、ｐ_３、ｐ_４は、それぞれ、０～３の整数であり；ｑ_１、ｑ_２は、それぞれ、０～２の整数である］、及び
下記式（５）

［式（５）中、Ｑ^５１、Ｑ^５２、Ｑ^５３、Ｑ^５４は、各々独立して、炭素原子数１～６のアルキル基であり；Ｒ^５１は、メチル基であり；ｙは０以上の整数であり；ｒ_１、ｒ_２、ｒ_３、ｒ_４は、それぞれ、０～３の整数であり；ｓ_１は、それぞれ、０～２の整数である］
で表される芳香族縮合リン酸エステル化合物よりなる群から選ばれる少なくとも１種を主成分とするもの好ましい。
なお、上記式（４）及び上記式（５）で表される縮合リン酸エステル化合物は、それぞれ複数種の分子を含んでよく、各分子について、ｎは、１～３の整数であることが好ましい。 In particular, as the (d) phosphoric acid ester compound, the following formula (4) is used.

[In formula (4), Q ⁴¹ , Q ⁴² , Q ⁴³ , and Q ⁴⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ⁴¹ and R ⁴² are each independently methyl R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or a methyl group; x is an integer of 0 or more; p ₁ , p ₂ , p ₃ , and p ₄ are each 0 to is an integer of 3; q ₁ and q ₂ are each an integer of 0 to 2], and the following formula (5)

[In formula (5), Q ⁵¹ , Q ⁵² , Q ⁵³ , and Q ⁵⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ⁵¹ is a methyl group; y is 0 or more r ₁ , r ₂ , r ₃ , r ₄ are each an integer of 0 to 3; s ₁ is an integer of 0 to 2, respectively]
Preferably, the main component is at least one selected from the group consisting of aromatic condensed phosphoric acid ester compounds represented by the following.
The condensed phosphate ester compounds represented by the above formulas (4) and (5) may each contain multiple types of molecules, and for each molecule, n is an integer from 1 to 3. preferable.

In the preferred (d) phosphate ester compound containing at least one type selected from the group consisting of condensed phosphate ester compounds represented by the above formula (4) and the above formula (5) as a main component, x , y preferably has an average value of 1 or more. The above-mentioned preferred (d) phosphate ester compound can generally be obtained as a mixture containing 90% or more of compounds in which x and y are 1 to 3, and other than compounds in which x and y are 1 to 3. This includes multimers and other by-products in which x and y are 4 or more.

(d) The content of the phosphate ester compound is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on 100% by mass of the composition constituting the protective housing member.

［式（１）中、Ｒ^１１及びＲ^１２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｍ^１は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａは、１～３の整数であり；ｍは、１～３の整数であり；ａ＝ｍである］、及び
下記式（２）で表されるジホスフィン酸塩

［式（２）中、Ｒ^２１及びＲ^２２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｒ^２３は、直鎖状若しくは分岐状の炭素原子数１～１０のアルキレン基、炭素原子数６～１０のアリーレン基、炭素原子数６～１０のアルキルアリーレン基、又は炭素原子数６～１０のアリールアルキレン基であり；Ｍ^２は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン、及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂは、１～３の整数であり；ｎは、１～３の整数であり；ｊは、１又は２の整数であり；ｂ・ｊ＝２ｎである］
からなる群より選ばれる少なくとも１種が挙げられる。
また、（ｅ）ホスフィン酸塩類は、上記式（１）で表されるホスフィン酸塩と上記式（２）で表されるジホスフィン酸塩との混合物としてもよい。 -(e) Phosphinates-
In the resin composition of the protective housing member according to this embodiment, (e) phosphinates can be optionally used. (e) As phosphinates, phosphinates represented by the following formula (1)

[In formula (1), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; M ¹ is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; a is is an integer of 1 to 3; m is an integer of 1 to 3; a=m], and a diphosphinate represented by the following formula (2)

[In formula (2), R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; R ²³ is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or a linear or branched alkylene group having 6 to 10 carbon atoms; is an arylalkylene group; ^M2 is at least one member selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; b is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2; b・j=2n]
At least one selected from the group consisting of:
Moreover, (e) phosphinates may be a mixture of a phosphinate represented by the above formula (1) and a diphosphinate represented by the above formula (2).

Such (e) phosphinates are not particularly limited, and include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, and ethylmethylphosphine. Magnesium acid, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, methyl-n-propylphosphine Magnesium acid, Aluminum methyl-n-propylphosphinate, Zinc methyl-n-propylphosphinate, Calcium methane di(methylphosphinate), Magnesium methane di(methylphosphinate), Aluminum methane di(methylphosphinate), Methane di(methylphosphinic acid) ) zinc, benzene-1,4-(dimethylphosphinic acid) calcium, benzene-1,4-(dimethylphosphinic acid) magnesium, benzene-1,4-(dimethylphosphinic acid) aluminum, benzene-1,4-(dimethyl Zinc phosphinate), calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate. Calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate. Aluminum diethylphosphinate is more preferable.
(e) Commercially available phosphinate salts include, without particular limitation, Exolit (registered trademark) OP1230, OP1240, OP1311, OP1312, OP930, OP935, etc. manufactured by Clariant Japan.

(e) The content of phosphinates is preferably 2 to 20% by mass, more preferably 3 to 10% by mass, based on 100% by mass of the composition constituting the protective housing member.
In the resin composition of the protective housing member according to the present embodiment, (d) a phosphoric acid ester compound and (e) a phosphinate salt can optionally be used in combination. In such a case, the ratio of the content of component (e) to the content of component (d) (component (d):component (e)) is preferably 1:1.5 to 5:1, and more preferably Preferably the ratio is 1:1 to 4:1.

-(f) Polypropylene resin-
In the resin composition of the protective housing member according to the present embodiment, from the viewpoint of low-temperature impact resistance, it is preferable that the resin composition does not substantially contain (f) polypropylene resin. Here, "substantially free" means that the content of (f) polypropylene resin in the resin composition is less than 0.1%.
(f) The polypropylene resin is not particularly limited, and examples thereof include polymers containing propylene units such as homopolypropylene, copolymers containing polypropylene blocks, modified polypropylene, and mixtures thereof.
The content of the polypropylene resin in the resin composition can be determined by, for example, freezing and crushing the resin composition into a powder, dissolving the powder in chloroform at 23°C, and dissolving the insoluble content at 150°C. It can be determined by further collecting a fraction that dissolves in o-dichlorobenzene and measuring the fraction by NMR.

-(g) Thermoplastic resin-
The thermoplastic resin (g) other than the components (a) to (c) and (f) optionally used in this embodiment is not particularly limited, and includes, for example, polystyrene, syndiotactic polystyrene, Examples include high impact polystyrene.

- (h) Inorganic or organic fillers and reinforcements -
In the resin composition of the protective housing member according to the present embodiment, from the viewpoint of increasing rigidity, it is preferable to substantially contain the following (h) inorganic or organic filler and reinforcing material.
(h) The content of the inorganic or organic filler and reinforcing material is preferably 5 to 30% by mass, more preferably 7 to 20% by mass, based on 100% by mass of the composition constituting the protective housing member. %.

-(h-i)Glass fiber-
In the resin composition of the protective housing member according to the present embodiment, it is particularly preferable that (hi) glass fiber is included. (hi) Glass fiber is blended in the resin composition for the purpose of improving mechanical strength.
(h-i) As the type of glass fiber, known types can be used, and examples thereof include E glass, C glass, S glass, A glass, and the like. (hi) Glass fiber refers to glass in the form of fibers, and is distinguished from lump-like glass flakes and glass powder.
(h-i) The average fiber diameter of the glass fibers should be 5 to 15 μm from the viewpoint of reducing the rigidity, heat resistance, impact resistance, durability, etc. of the molded product due to fiber breakage during extrusion and molding, and from the viewpoint of production stability. Preferably, it is more preferably 7 to 13 μm.
Further, the average fiber length of the glass fiber (hi) is preferably 0.5 to 10 mm, more preferably 1 to 6 mm, from the viewpoint of handleability.
(hi) The glass fiber may be surface-treated with a surface treatment agent, such as a silane compound, from the viewpoint of improving affinity with the resin. The silane compound used as a surface treatment agent is usually used for surface treatment of glass fillers, mineral fillers, and the like. Specific examples include vinylsilane compounds such as vinyltrichlorosilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; and bis-(3-triethoxysilane). Examples include sulfur-based silane compounds such as silylpropyl) tetrasulfide, mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane, and aminosilane compounds such as γ-aminopropyltriethoxysilane and γ-ureidopropyltriethoxysilane. Particularly preferred silane compounds for the purposes of the present invention are aminosilane compounds. These silane compounds may be used alone or in combination of two or more. Further, the surface may be treated with a mixture of these silane compounds and an epoxy-based or urethane-based binding agent.

-(h-ii) Talc-
The resin composition of the protective housing member according to the present embodiment may contain (h-ii) talc as an inorganic reinforcing material, and (h-ii) talc is a substance whose chemical name is hydrated magnesium silicate. It is preferable that the main components are about 60% SiO2, about 30% MgO, and about 4.8% water of crystallization.
(h-ii) The whiteness of talc measured according to JIS K-8123 is preferably 93% or more.
(h-ii) The average particle diameter (D50) of talc measured by a laser diffraction method is preferably more than 1 μm, and preferably less than 20 μm, from the viewpoint of improving the mechanical properties of the resin composition. More preferably, it is 15 μm or less.
(h-ii) Talc may be treated with a known surface treatment agent in order to improve its affinity with the resin. Such surface treatment agents are not particularly limited, and include, for example, silane coupling agents such as aminosilane and epoxysilane; titanate coupling agents; fatty acids (saturated fatty acids, unsaturated fatty acids); alicyclic carboxylic acids. and resin acids; metal soaps and the like. The amount of the surface treatment agent added is not particularly limited, but is preferably 3% by mass or less, more preferably 2% by mass or less, based on (h-ii) 100% by mass of talc, and is substantially Most preferably, it is not added.
(h-ii) Commercial products of talc include, without particular limitation, Talc MS and MS-KY manufactured by Nippon Talc Co., Ltd., Hytron A manufactured by Takehara Chemical Industry Co., Ltd., and the like.

((i) Other additives)
Other additives (i) other than components (a) to (h) that are optionally used in the present embodiment are not particularly limited, and include, for example, vinyl aromatic compounds other than component (b). -Block copolymers of conjugated diene compounds, olefin elastomers other than components (c) and (f), antioxidants, metal deactivators, heat stabilizers, flame retardants other than components (d) and (e) (ammonium polyphosphate compounds, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, zinc borate, etc.), inorganic or organic fillers and reinforcement other than (h-i) and (h-ii) materials (carbon fiber, polyacrylonitrile fiber, aramid fiber, etc.), fluorine-based polymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather resistance (photo) property improvers, nucleating agents for polyolefins, slip agents, various colorants, mold release agents, admixtures (e.g. segment chains with high compatibility with component (a), component (b) and/or (c) copolymers other than those mentioned above, which have segment chains with high compatibility with the components, etc.).

Hereinafter, embodiments of the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

The raw materials used for the resin compositions and molded bodies of Examples and Comparative Examples are shown below.
-(a) Polyphenylene ether resin-
(ai): Polyphenylene ether with a reduced viscosity (η _sp /c: 0.5 g/dL chloroform solution) of 0.51 dL/g obtained by oxidative polymerization of 2,6-xylenol (a-ii): Polyphenylene ether with reduced viscosity (η _sp /c: 0.5 g/dL chloroform solution) of 0.42 dL/g obtained by oxidative polymerization of 2,6-xylenol. Note that the reduced viscosity is η _sp /c: 0 Measurement was performed using a chloroform solution of .5 g/dL at a temperature of 30° C. using an Ubbelohde viscosity tube.

-(b) Hydrogenated block copolymer-
An unmodified block copolymer was synthesized with polymer block A made of polystyrene and polymer block B made of polybutadiene. The physical properties of the obtained block copolymer are shown below.
(bi-i): Mixture of (bi-1) and (bi-2) shown below (bi-2): Content of polystyrene in block copolymer before hydrogenation: 30 mass %, Molecular weight peak of block copolymer after hydrogenation: 65,000, Number average molecular weight (Mn) of polystyrene block: 19,500, Number average molecular weight (Mn) of polybutadiene block: 45,500, Before hydrogenation Molecular weight distribution (Mw/Mn) of block copolymer: 1.10, total of 1,2-vinyl bonds and 3,4-vinyl bonds with respect to double bonds in polybutadiene units: 40%, polybutadiene constituting the polybutadiene block Hydrogenation rate for part: 35%, glass transition temperature of polybutadiene block after hydrogenation: -80°C.
(b-i-1): Content of polystyrene in block copolymer before hydrogenation: 30% by mass, molecular weight peak of block copolymer after hydrogenation: 125,000, number average molecular weight of polystyrene block (Mn ): 18,750, Number average molecular weight (Mn) of polybutadiene block: 87,500, Molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.10, 1 for the double bond in the polybutadiene unit , 2-vinyl bond and 3,4-vinyl bond: 40%, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 35%, glass transition temperature of the polybutadiene block after hydrogenation: -80°C.
Mixing ratio (b-i-1): (b-i-2) = 30:70
Note that the content of the vinyl aromatic compound was measured using an ultraviolet spectrophotometer. The number average molecular weight (Mn) and the molecular weight peak were determined using GPC (moving phase: chloroform, standard substance: polystyrene). Molecular weight distribution (Mw/Mn) is calculated by dividing the weight average molecular weight (Mw) determined by a conventionally known method using GPC (mobile phase: chloroform, standard material: polystyrene) by the number average molecular weight (Mn) described above. It was calculated by The total vinyl bond amount was measured using an infrared spectrophotometer, and was measured using an infrared spectrophotometer, as described in Analytical Chemistry, Volume 21, No. 8, August 1949. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (NMR). The mixing ratio was determined by the peak area ratio during GPC measurement.

(b-ii)
A mixture containing the same components as (bi-1) and (bi-2) described in (bi) above in a ratio of (bi-1):(bi-2) = 5:95 .

(b-iii)
A mixture containing the same components as (bi-1) and (bi-2) described in (bi) above in a ratio of (bi-1):(bi-2) = 55:45 .

(b-iv)
A block copolymer having a BABA block structure was synthesized by a known method, with polymer block A made of polystyrene and polymer block B made of polybutadiene. The synthesized block copolymer was hydrogenated by a known method. No modification of the polymer was performed. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below.
Polystyrene content in block copolymer before hydrogenation: 44% by mass, number average molecular weight (Mn) of block copolymer after hydrogenation: 95,000, number average molecular weight (Mn) of polystyrene block: 41, 800, number average molecular weight (Mn) of polybutadiene block: 53,200, molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.06, 1,2-vinyl to double bond in polybutadiene unit Total of bonds and 3,4-vinyl bonds: 75%, hydrogenation rate with respect to the polybutadiene moiety constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: -15°C.

(b-v)
A block copolymer having an AB block structure was obtained in the same manner as in (b-iv) above. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below.
Polystyrene content in block copolymer before hydrogenation: 50%, number average molecular weight (Mn) of block copolymer before hydrogenation: 60,000, number average molecular weight (Mn) of polystyrene block: 30,000 , Number average molecular weight (Mn) of polybutadiene block: 30,000, Molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.08, 1,2-vinyl bond to double bond in polybutadiene unit and total of 3,4-vinyl bonds: 75%, hydrogenation rate to the polybutadiene part constituting the polybutadiene block: 99.9%

(b-vi)
A polymer was obtained in the same manner as in (b-iv) above. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below.
Polystyrene content in block copolymer before hydrogenation: 44%, number average molecular weight (Mn) of lock copolymer before hydrogenation: 95,000, number average molecular weight (Mn) of polystyrene block: 41,800 , Number average molecular weight (Mn) of polybutadiene block: 53,200, Molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.06, 1,2-vinyl bond to double bond in polybutadiene unit and total of 3,4-vinyl bonds: 75%, hydrogenation rate to the polybutadiene part constituting the polybutadiene block: 99.9%

-(c) Olefin polymer-
(ci): Ethylene-butene copolymer, trade name "Tafmer DF610", manufactured by Mitsui Chemicals, MFR: 1.2 g/10 minutes (190°C, 2.16 kgf conditions), embrittlement temperature: < -70℃, density: 0.862g/ ^cm3

(c-ii): Ethylene-butene copolymer, trade name "Tafmer DF810", manufactured by Mitsui Chemicals, MFR: 1.2 g/10 minutes (190°C, 2.16 kgf conditions), embrittlement temperature: < -70℃, density: 0.885g/ ^cm3

(c-iii)
Ethylene-butene copolymer, trade name "Tafmer DF7350", manufactured by Mitsui Chemicals, MFR: 36 g/10 minutes (190°C, 2.16 kgf conditions), embrittlement temperature: <-70°C, density: 0. 870g/ ^cm3

-(d) Phosphoric ester compound-
(d): “E890” manufactured by Daihachi Chemical Co., Ltd. (condensed phosphate ester compound)

-(e) Phosphinates-
(e): "Exolit OP1230" manufactured by Clariant Japan (corresponds to formula (1))

-(h) Inorganic or organic fillers and reinforcements-
--(hi)Glass fiber--
(h-i-i): Glass fiber with an average fiber diameter of 10 μm and a fiber cut length of 3 mm, surface-treated with an aminosilane compound, product name "EC10 3MM 910 (registered trademark)", manufactured by NSG Vetrotex Co., Ltd.

(h-i-ii): Glass fiber with an average fiber diameter of 13 μm and a fiber cut length of 3 mm, surface-treated with an aminosilane compound, product name "ECS03T-249 (registered trademark)", manufactured by Nippon Electric Glass Co., Ltd.

--(h-ii) Talc--
(h-ii-i): Manufactured by Nippon Talc Co., Ltd., trade name "Talc MS" (average particle diameter (D50) measured by laser diffraction method = 14 μm)

(h-ii-ii): Manufactured by Takehara Chemical Industry Co., Ltd., trade name "Hytron A" (average particle diameter (D50) measured by laser diffraction method = 3 μm)

-others-
High impact polystyrene (HIPS): Manufactured by PS Japan Co., Ltd., product name "PSJ-Polystyrene H9302"

Methods (1) to (5) for measuring physical properties and morphology in Examples and Comparative Examples are shown below.
(1) Chemical resistance The pellets of the obtained resin composition were supplied to a small injection molding machine (product name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) whose cylinder temperature was set at 280°C, and the mold temperature was set at 70°C. It was molded into a flat plate of 120 mm x 80 mm x 3 mm under the conditions of an injection pressure of 75 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds.
A rectangular test piece (80 mm x 12.5 mm x 3 mm) whose longitudinal direction was perpendicular to the flow direction was cut out from this flat plate. This test piece was placed on the curved surface of a bending bar whose vertical cross section was shaped like a parabola expressed by the equation y ² = 6x (x≧0, y≧0), with the horizontal direction as the x-axis and the vertical direction as the y-axis. The bar and the test piece were attached using a jig so that there was no gap between them. In addition, the position of the bending bar on its vertical cross section where x = 0, y = 0 is the placement position of the measurement starting point side end of the test piece, and the position where x>0 and y>0 is the position where the test piece is measured. It is located at the distal end.
After attaching the test piece to the bending bar as described above, 5-56 (manufactured by Kure Kogyo Co., Ltd.) was applied to the surface of the test piece and left for 48 hours at 23° C. and 50 RH%. If a crack occurred on the surface of the test piece after 48 hours, the critical position where the crack occurred (the position where the value of x was largest in the x-axis direction of the bending bar) was read.
To read the critical position where a crack occurs, transfer the scale of the x-axis coordinate of the bending bar onto the test piece while it is attached to the bending bar, and after removing the test piece from the bending bar, read the scale of the specified size below. The presence of a crack was confirmed, and the position of the crack was read against the scale that was transcribed (the critical position is the position corresponding to the x-axis coordinate of the bending bar, so it is not the periphery length of the test piece. ).
Note that a crack is a crack of 200 μm or more in the flow direction that is observed when the surface of a test piece is observed using a microscope such as VHX-5000 (manufactured by Keyence Corporation).
Then, the critical strain was calculated using the following formula from the thickness of the test piece and the critical position where cracks occur.
(Critical strain) = d x 3 ^1/2 / {2 x (3 + 2x) ^3/2 } x 100 (%)
d: Thickness of test piece (inch)
x: Position in the x-axis direction (inch)

(2) Flexural Modulus The obtained resin composition pellets were dried at 100° C. for 2 hours. JIS K7139 type A test pieces were prepared from the dried resin composition pellets using a Toshiba Machine Co., Ltd. IS-100GN injection molding machine (cylinder temperature set at 280°C and mold temperature set at 80°C). did. Next, using the test piece, the flexural modulus (MPa) at 23° C. was measured in accordance with ISO-178.

(3) Flame retardancy The obtained resin composition pellets were supplied to a small injection molding machine (product name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 280°C, and the mold temperature was set at 70°C. Five specimens (3.0 mm thick) for UL94 vertical combustion test measurement were produced by molding under a pressure of 60 MPa. The flame retardance of these five specimens was evaluated based on the UL94 vertical combustion test method. After 10 seconds of flame contact, the combustion time from when the flame is removed until the flame goes out is t1 (seconds), and after 10 seconds of flame contact again, the combustion time from when the flame is released until the flame goes out is t2 (seconds). ), and the average of t1 and t2 was determined as the average combustion time for each of the five bottles. On the other hand, the maximum combustion time among the ten combustion times including t1 and t2 was determined as the maximum combustion time. Then, V-0, V-1, V-2, and HB were determined based on the UL94 standard.
In particular, when the flame retardancy level was V-1 or higher, it was determined that the flame retardancy was excellent.

(4) Morphology A measurement cross section was prepared using an ultramicrotome from a fragment of the core portion (center portion in the thickness direction) of a test piece prepared in the same manner as in (1) Chemical resistance above. After staining the measurement cross section with ruthenium tetroxide, it was photographed using "HITACHI SU-8220" (manufactured by Hitachi High-Tech Fielding Co., Ltd.) at a magnification of 10,000 times, an acceleration voltage of 1.0 kV, a detector: secondary electrons (upper ): LA). By photographing, a digital image (pixel count: 1280×960) of a cross-sectional SEM image was obtained as a morphology image.
Next, the photographed morphological images were binarized using image processing software "imageJ" (version 1.50i) in the following manner.
First, a morphological image was opened, and a range (the number of pixels corresponding to a 3 μm square or a 5 μm square) to be binarized was selected. The selected image was smoothed using "median filter" of image processing software "imageJ" and binarized using "Threshold" to obtain a first processed image. The algorithm for the binarization process at that time was set to "Default", and the threshold value was set to "Auto".
In the first processed image obtained above, all the parts that are black after binarization are extracted using "Analyze Particles" of the image processing software "imageJ", and the number of pixels of the part itself and the part are calculated. By calculating the number of surrounding pixels, the total circumference (μm/μm ² ) (L1), which is the sum of the circumferences of the first non-small portion, was determined. In addition, by extracting all the parts that are white after binarization and calculating the number of pixels, the area occupied per unit area of the first white part (μm ² /μm ² ) (AW1) is calculated. Ta.
Note that five first processed images subjected to the binarization process were created from one protective housing member. For each measurement result, a numerical value obtained by averaging the respective measurement values obtained from these five images was used. Furthermore, when the morphological image was binarized, 2×2 pixels were cut off.

(5) Bending vibration fatigue properties The obtained resin composition pellets were supplied to a small injection molding machine (product name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) whose cylinder temperature was set at 280°C, and the mold temperature was set at 70°C. A cantilever bending fatigue test piece of "TYPE A" according to method B of ASTM D671 was obtained under conditions of an injection pressure of 60 MPa. Based on method B of ASTM D671, periodically varying bending stress (repetitive stress: 40 MPa) was applied to the test piece under the following test conditions, and the number of repetitions until each fracture was measured. For each composition, three test pieces were used for measurement without applying cutting oil and when applying cutting oil, and the average of the results was taken as the measurement result. In addition, when applying cutting oil, apply cutting oil to one side of the vibrating part (curved part that is not fixed with a jig) of the cantilever bending fatigue test piece, and keep it under the conditions of 23°C x 50RH% for 3 hours. The test was conducted after being left alone.
Resin composition: Resin composition of Example 10 and resin composition of Comparative Example 1 Testing machine: Repeated bending vibration fatigue tester B-70 manufactured by Toyo Seiki Seisakusho Co., Ltd.
Repetition frequency: 30Hz (repetition speed 1800 times/min)
Measurement temperature: room temperature (23℃)
Repeated stress: 40MPa
Cutting oil: Honilo988 (manufactured by Castrol)

(Examples 1 to 24, Comparative Examples 1 to 8)
Each Example and each Comparative Example will be described in detail below.
A twin-screw extruder (manufactured by Coperion, ZSK-25) was used as a melt-kneader for producing the resin compositions of each Example and each Comparative Example. The L/D of the extruder was set to 35.
The configuration of the twin-screw extruder includes a first raw material supply port on the upstream side in the direction in which raw materials flow, a first vacuum vent downstream of the first raw material supply port, and a second raw material supply downstream of the first vacuum vent. A liquid addition pump is provided downstream of the second raw material supply port, a third raw material supply port is downstream of the liquid addition pump, and a second vacuum vent is provided downstream of the third raw material supply port. Moreover, as a method of supplying the raw materials at the second and third raw material supply ports, a method was adopted in which the raw materials were added from the side open ports using a forced side feeder.
The barrel temperature of the twin-screw extruder is 320°C from the first raw material supply port to the first vacuum vent, and 270°C downstream from the second raw material supply port, screw rotation speed is 450 rpm, and extrusion rate is 15 kg/h. Pellets of the resin composition were produced under the following conditions. Table 1 shows the configuration of the twin screw extruder.

Components (a) to (e) and (h) were fed to the twin-screw extruder set as above as shown in Tables 2 and 3 to obtain pellets of the resin composition. In Example 24, the extrusion conditions of Example 1 were set at a screw rotation speed of 300 rpm, and in Comparative Example 8, the extrusion conditions of Example 1 were set at a screw rotation speed of 900 rpm.
Physical property tests were conducted for each Example and each Comparative Example using the measurement methods (1) to (5) described above. The results are shown in Tables 2 to 4.

As shown in Tables 2 and 3, the protective casing member of the example has a predetermined morphology and flame retardancy compared to the protective casing member of the comparative example, and the amount of critical strain in the chemical resistance evaluation. It was found that the bending elastic modulus was within the specified range.

As shown in Table 4, compared to the protective housing member of Comparative Example 1, the protective housing member of Example 10 did not deteriorate in vibration fatigue characteristics even when chemicals (cutting oil) were attached, and It was found that the structure has excellent retention properties and connection maintenance properties of the structure.

According to the present invention, it is possible to cope with the complexity of the shape of the molded object and the reduction of its weight, and it also has flame retardant properties, and can securely hold various devices installed inside or connect with each structure. It is possible to obtain a protective housing member for a battery unit for a mobile object that can reliably connect and maintain the battery units. The protective housing member constitutes a battery cell or a battery unit in a battery unit for a mobile object having multiple battery cells such as a hybrid electric vehicle or an electric vehicle (including railway vehicles, motorcycles, electrically assisted bicycles, etc.). It can be suitably used as a protective case for protecting other equipment.

1 Battery unit 2 Battery cell 3 Connector 4 Separator 5 Protective housing bottom plate 6 Sealing element 7 Protective housing top plate 8 Flat plate 9 Reinforcing material 10 Opening 11 Protective housing baffle structure 12 Baffle plate 13 Baffle reinforcing material 14 Baffle opening 15 Protective housing side plate

Claims (3)

(a) a polyphenylene ether resin; and (b) a block copolymer comprising at least one polymer block mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound. Molding a resin composition containing at least a partially hydrogenated hydrogenated block copolymer and/or a modified product of the hydrogenated block copolymer, and/or (c) an olefinic polymer consisting of an olefin. A protective casing member for a battery unit for a mobile object obtained by
The resin composition has a critical strain of 0.5% or more in chemical resistance evaluation, a flexural modulus of 2500 MPa or more measured according to ISO-178, and a combustion resistance measured based on the UL94 vertical combustion test. The level is V-0,
In the morphological image of the protective casing member of the mobile battery unit, the continuous phase contains the component (a) and the component (b) and/or the component (c) present in the continuous phase. A network phase structure having a linear dispersed phase is formed,
In the first processed image obtained by binarizing the morphological image, the area occupied per unit area of the first white portion that is white after the binarizing process is AW1 (μm 2 /μm 2 ⁾ , ^and the For the first non-small portions that are black after the binarization process and have an area of 15×10 ⁻⁴ μm ² or more, the total circumference of the total circumference of the first non-small portions, When the length per unit area is L1 (μm/μm ² ), the length L1 (L1/AW1) with respect to the occupied area AW1 is 7 μm ⁻¹ or more.
A protective housing member for a battery unit for a mobile object, characterized in that: The protective housing member for a mobile battery unit according to claim 1 , further comprising (d) a phosphate ester compound. Furthermore, it contains (e) phosphinates,
The component (e) is a phosphinate salt represented by the following general formula (1)

[wherein R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; M ¹ is , calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion, and a protonated nitrogen base; a is 1 to 3; m is an integer of 1 to 3; a=m], and a diphosphinate represented by the following formula (2)

[In the formula, R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; R ²³ is , a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. ^M2 is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; b is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2; b・j=2n]
The protective housing member for a mobile battery unit according to claim 1 or 2 , comprising at least one phosphinate selected from the group consisting of:

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