Member for probe card or member for printed circuit board inspection jig, and method for manufacturing same

Abstract

Provided is a member for a probe card or a member for a printed circuit board inspection jig, wherein the member comprises a thermoplastic resin composition containing component (A), which is at least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resins (a1) having a melting point of 270°C or higher and amorphous thermoplastic resins (a2) having a glass transition temperature of 200°C or higher, and component (B), which is an inorganic filler that contains zirconium oxide (b1), the component (b1) content being 2-40 parts by mass per 100 parts by mass of the component (A), and the component (B) content being 2-60 parts by mass per 100 parts by mass of the component (A). Also provided is a method for producing the member.

Description

Probe card member or printed circuit board inspection jig member, and manufacturing method thereof

[0001] The present invention relates to a member for a probe card or a member for a printed circuit board inspection jig, and a method for manufacturing the same.

[0002] Engineering plastics are thermoplastic resins with excellent moldability, heat resistance, strength, and other properties, and are used in a wide range of fields, including automotive parts, machine parts, and electrical and electronic components. Thermoplastic resin compositions containing functional fillers in engineering plastics are also known. For example, Patent Document 1 describes a low-contamination injection-molded article formed from a resin composition containing a thermoplastic resin component containing a crystalline thermoplastic resin and an amorphous thermoplastic resin, a carbon precursor, and a conductive filler in predetermined amounts, which can precisely control the surface resistivity to a desired value within the semiconductive range and produce significantly less foreign particulate matter. Patent Document 2 discloses a flame-retardant polyimide molding material containing a semi-aromatic polyimide resin and a predetermined amount of graphite, carbon fiber, etc., which exhibits excellent moldability and high flame retardancy.

[0003] It is known that in devices using contact probe pins, such as wafer inspection probe cards and printed circuit board inspection jigs, a plate-shaped thermoplastic resin molded body, in which multiple precision holes are machined into a super engineering plastic or ceramic molded body, is used as a holding portion or guide portion of the contact probe pin (see, for example, Patent Document 3). When holes are drilled into the thermoplastic resin molded body, there is a problem of burrs forming around the drilled openings. Patent Document 3 discloses that this problem can be solved by drilling holes with a drill bit of a specific diameter in a resin molded body obtained by molding a resin composition containing a thermoplastic resin having predetermined thermal properties.

[0004] JP 2005-290328 A International Publication No. 2021 / 024624 JP 2007-90492 A

[0005] The cutting method for a thermoplastic resin molded body according to the technology disclosed in Patent Document 3 involves drilling holes in the resin molded body with a drill bit. However, when finer holes are required for components for probe cards and printed circuit board inspection jigs, cutting with a drill has limitations in processing accuracy. Laser processing, however, enables finer processing than cutting with a drill. However, the physical properties required for the thermoplastic resin molded body, which is the workpiece, may differ depending on the processing method.

[0006] The object of the present invention is to provide a probe card member or a printed circuit board inspection jig member that has been subjected to high-precision micromachining, with minimal generation of burrs, particularly when fine through-holes are formed by laser processing, and a method for manufacturing the same.

[0007] The present inventors have found that the above-mentioned problems can be solved by using a predetermined thermoplastic resin composition in a probe card member or a printed circuit board inspection jig member and in the manufacture thereof. That is, the present invention relates to the following: [1] A probe card member or a printed circuit board inspection jig member, the member comprising: component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher; and component (B): an inorganic filler containing zirconium oxide (b1), wherein the content of component (b1) is 2 to 40 parts by mass per 100 parts by mass of component (A), and the content of component (B) is 2 to 60 parts by mass per 100 parts by mass of component (A). [2] The member according to [1], wherein the component (a1) comprises a polyimide resin (a1-1) containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) is 20 to 70 mol %. (R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) [3] The member according to [1] or [2], wherein the zirconium oxide (b1) has a volume median particle size (D50) of 1 μm or less. [4] The member according to any one of [1] to [3], wherein the total content of the component (A) and the component (B) in the thermoplastic resin composition is 50 mass% or more. [5] The member according to any one of [1] to [4], wherein the component (B) further contains an inorganic filler (b2) other than the component (b1), and the inorganic filler (b2) contains at least one selected from the group consisting of talc, mica, silica, alumina, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, calcium carbonate, and titanium oxide. [6] The member according to [5], wherein the content of the inorganic filler (b2) per 100 parts by mass of the component (A) in the thermoplastic resin composition is 1 to 40 parts by mass. [7] The member according to any one of [1] to [6], wherein the member has a plate-like portion, and the plate-like portion has a plurality of through-holes, each of which has a substantially circular opening diameter of 400 μm or less, or a substantially square opening with a side length of 400 μm or less. [8] The member according to any one of [1] to [7], wherein the member is a probe holding member or a probe guide member. [9] A method for producing a member for a probe card or a member for a printed circuit board inspection jig according to any one of [1] to [8], which comprises the following steps (I) and (II) in that order:

[10] The method according to [9], wherein the thermoplastic resin composition in step (I) is an injection molding method, an extrusion molding method, or a compression molding method.

[11] The manufacturing method according to [9] or

[10] , wherein the processing method in the step (II) is laser processing.

[0008] According to the present invention, it is possible to provide a probe card member or a printed circuit board inspection jig member that has been subjected to high-precision micro-machining, with little generation of burrs, especially when fine through-holes are formed by laser processing, and a method for manufacturing the same.

[0009] 1 is a schematic plan view of a molded body 200 produced in step (I) of Example 1. FIG. 2 is an observation image of a through hole produced in Example 1, the opening of which is circular. FIG. 3 is an observation image of a through hole produced in Example 1, the opening of which is square. FIG. 4 is an observation image of a through hole produced in Example 2, the opening of which is circular. FIG. 5 is an observation image of a through hole produced in Example 2, the opening of which is square.

[0010] [Definition] As used herein, "high-precision microfabricated (component)" means that a large number of through holes are formed in the component at a narrow pitch, and there is little breakage of the partitions between the openings of the through holes, little occurrence of discoloration, little occurrence of burrs, and little variation in the opening shape. Furthermore, when the opening shape is square, the corners are not rounded, resulting in high shape reproducibility. The through holes referred to here are fine through holes whose opening diameter or the length of one side of the opening is preferably 400 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, even more preferably less than 50 μm, even more preferably 40 μm or less, and even more preferably 30 μm or less. Furthermore, "narrow pitch" as used herein means, for example, a pitch in the range of more than 1 to 5 times the opening diameter or the length of one side of the opening. The microfabrication precision of the component can be specifically evaluated by the method described in the Examples.

[0011] [Probe Card Component or Printed Circuit Board Inspection Jig Component] The probe card component or printed circuit board inspection jig component of the present invention (hereinafter also referred to simply as "the component (of the present invention)") comprises a thermoplastic resin composition containing: component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher; and component (B): an inorganic filler containing zirconium oxide (b1), wherein the content of component (b1) per 100 parts by mass of component (A) is 2 to 40 parts by mass, and the content of component (B) per 100 parts by mass of component (A) is 2 to 60 parts by mass. As described below, the volume median particle size (D50) of zirconium oxide (b1) is preferably 1 μm or less. By virtue of the above-described configuration, the present invention can provide a probe card component or a printed circuit board inspection jig component that has been subjected to high-precision micromachining, with minimal burrs being generated, particularly when fine through-holes are formed by laser processing.

[0012] The reason why the above-mentioned effects are achieved in the present invention is unclear, but is thought to be as follows. The member of the present invention is made of the thermoplastic resin composition, and the composition contains, as the thermoplastic resin (A), at least one selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher. The inclusion of component (A) in the thermoplastic resin composition allows members of any shape to be easily produced by thermoforming. Furthermore, when the member of the present invention is, for example, a probe holding member or guide member, a process is required in which the thermoplastic resin is thermoformed to produce a molded body, and then fine through-holes are formed at a narrow pitch in the molded body by drill cutting, laser processing, or the like. Here, because the thermoplastic resin (A) has a predetermined or higher heat resistance, it can withstand the thermal energy generated during drill cutting and laser processing when forming fine through-holes in a molded body made of the thermoplastic resin composition. Therefore, it is thought that melting and dimensional changes during processing of the molded body are suppressed, allowing for the formation of fine through-holes with high precision. Furthermore, the thermoplastic resin composition contains a predetermined amount of inorganic filler as component (B), and the inorganic filler contains zirconium oxide (b1). By using submicron-level fine zirconium oxide (b1) particles as the inorganic filler, the unevenness caused by the particles in the resulting molded body is suppressed, and when fine through-holes are formed in the molded body, the wall surfaces of the fine through-holes are also kept smooth, which is thought to improve microfabrication accuracy and suppress breakage of the partition walls between the openings of the through-holes and variations in the opening shapes. It is also presumed that by adding a predetermined amount of high-hardness component (b1) to the thermoplastic resin (A), the material becomes moderately embrittled, thereby suppressing the generation of burrs.

[0013] In this specification, "probe card member" means a member that constitutes at least a part of a probe card, and "printed circuit board inspection jig member" means a member that constitutes at least a part of a printed circuit board inspection jig. Note that a probe card is a device used in the so-called front-end process of semiconductor manufacturing, and a printed circuit board inspection jig is a jig used to inspect printed circuit boards. Therefore, these members are different from members for inspection IC sockets that are used in the back-end process of semiconductor manufacturing.

[0014] The member of the present invention is not particularly limited as long as it is a member for a probe card or a member for a printed circuit board inspection jig, but from the viewpoint of requiring high-precision microfabrication, it is preferably a probe holding member or a probe guide member in a member for a probe card or a member for a printed circuit board inspection jig.

[0015] The member of the present invention preferably has a plate-like portion and a plurality of through holes penetrating the plate-like portion in the thickness direction. More specifically, the member of the present invention preferably has a plate-like portion and a plurality of through holes in the plate-like portion, each of which has a substantially circular opening diameter of 400 μm or less, or a substantially square opening with a side length of 400 μm or less. The diameter of the opening or the side length of the opening is more preferably 200 μm or less, even more preferably 100 μm or less, even more preferably less than 50 μm, even more preferably 40 μm or less, and even more preferably 30 μm or less. Furthermore, from the viewpoint of use as a probe holding member or a probe guide member, the diameter of the opening or the side length of the opening is preferably 5 μm or more, more preferably 10 μm or more. The plurality of through holes are preferably arranged regularly, and the pitch of the through holes is, for example, in the range of more than 1 to 5 times, more preferably 1.1 to 3 times, the diameter of the opening or the side length of the opening. The diameter of the opening or the length of one side of the opening, and the pitch can be measured, for example, using a high-precision image dimension measuring device according to the method described in Examples. The through holes do not need to be formed over the entire surface of the plate-like portion, but may be formed in at least a part of the plate-like portion.

[0016] <Thermoplastic resin composition> The thermoplastic resin composition constituting the member of the present invention is a thermoplastic resin composition containing: component (A): at least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher; and component (B): an inorganic filler containing zirconium oxide (b1), wherein the content of component (b1) is 2 to 40 parts by mass per 100 parts by mass of component (A), and the content of component (B) is 2 to 60 parts by mass per 100 parts by mass of component (A).

[0017] <Thermoplastic Resin (A)> The thermoplastic resin (A) used in the present invention (hereinafter also referred to simply as "component (A)" or "thermoplastic resin (A)") is at least one selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher. In this specification, a crystalline thermoplastic resin refers to a resin having a melting point and a glass transition temperature, and an amorphous thermoplastic resin refers to a resin having a glass transition temperature but no melting point. Note that resins that are essentially crystalline but have an extremely slow crystallization rate and can only be processed in an amorphous state in various molding methods are classified as amorphous thermoplastic resins.

[0018] (Crystalline Thermoplastic Resin (a1)) The crystalline thermoplastic resin (a1) used as component (A) (hereinafter also referred to simply as "component (a1)") is a crystalline thermoplastic resin having a melting point of 270°C or higher from the viewpoint of producing a highly accurate microfabricated member. From the viewpoint of producing a highly accurate microfabricated member, the melting point of component (a1) is preferably 280°C or higher, more preferably 290°C or higher, and even more preferably 300°C or higher. From the viewpoint of ease of thermoforming, it is preferably 400°C or lower, more preferably 380°C or lower, and even more preferably 350°C or lower. The melting point of component (a1) can be measured using a differential scanning calorimeter, specifically by the method described in the examples.

[0019] The glass transition temperature (Tg) of component (a1) is not particularly limited, but from the viewpoint of producing highly accurate microfabricated parts, it is preferably 130° C. or higher, more preferably 140° C. or higher, and even more preferably 150° C. or higher, and from the viewpoint of ease of thermoforming, it is preferably 250° C. or lower, more preferably 230° C. or lower, and even more preferably 200° C. or lower. The glass transition temperature of component (a1) can be measured using a differential scanning calorimeter, specifically by the method described in the Examples.

[0020] (Amorphous Thermoplastic Resin (a2)) The amorphous thermoplastic resin (a2) used as component (A) (hereinafter also simply referred to as "component (a2)") is an amorphous thermoplastic resin having a glass transition temperature of 200°C or higher from the viewpoint of producing a member that has been subjected to high-precision microfabrication. The glass transition temperature (Tg) of component (a2) is preferably 210°C or higher, more preferably 230°C or higher, and even more preferably 250°C or higher from the viewpoint of producing a member that has been subjected to high-precision microfabrication. Furthermore, from the viewpoint of ease of thermoforming, it is preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower. The glass transition temperature of component (a2) can be measured by the same method as described above.

[0021] Examples of component (A) include thermoplastic resins corresponding to either component (a1) or component (a2) among polyimide resins, polyamide resins, polyetherimide resins, polyetherimide sulfone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyether ketone ketone resins, polycarbonate resins, polyamide imide resins, polysulfone resins, polyether sulfone resins, polyarylate resins, liquid crystal polymers, wholly aromatic polyester resins other than liquid crystal polymers, polyether ketone resins, polyether ether ketone ketone resins, polybenzimidazole resins, and polyphenylene ether resins. Among the above, from the viewpoint of producing a highly accurate microfabricated component, component (A) preferably comprises at least one selected from the group consisting of polyimide resin, polyetherimide resin, polyetherimide sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, polyether ketone ketone resin, liquid crystal polymer, and wholly aromatic polyester resin other than liquid crystal polymer, and more preferably comprises at least one selected from the group consisting of polyimide resin, polyetherimide resin, polyphenylene sulfide resin, and polyether ether ketone resin. Note that, when low dielectric properties are required for the component, component (A) is more preferably a polyimide resin, and among these, a polyimide resin having an aliphatic structure (other than wholly aromatic) or a polyimide resin having a bulky structure such as a halogen atom.

[0022] Component (A) can be component (a1), component (a2), or a mixture of component (a1) and component (a2). Using a thermoplastic resin with a high melting point and / or glass transition temperature as component (A) is preferable because it can suppress dimensional change of the component at high temperatures. In particular, when component (A) contains a crystalline thermoplastic resin (a1), the reinforcing effect of combining component (A) and component (B) is enhanced, further suppressing dimensional change of the resulting component at high temperatures. For example, it is possible to reduce the linear expansion coefficient of the component at temperatures of 25 to 200°C to 100 ppm / K or less. By increasing the amount of crystalline thermoplastic resin (a1) or using an additive that shrinks at high temperatures, it is possible to reduce the linear expansion coefficient of the component at temperatures of tens of ppm / K to several ppm / K at temperatures of 25 to 200°C. In addition, since the crystalline thermoplastic resin (a1) can suppress water absorption, it can also suppress dimensional change of the component due to moisture absorption. For example, it is possible to make the coefficient of moisture expansion of the member 20 ppm / % RH or less.

[0023] From the viewpoint of producing a highly accurate microfabricated member, it is preferable that component (A) contains component (a1), which is a crystalline thermoplastic resin. From the viewpoint of producing a highly accurate microfabricated member, the content of component (a1) in component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, and is 100% by mass or less.

[0024] When component (A) contains component (a1), from the viewpoint of producing highly accurate microfabricated members and from the viewpoint of ease of thermoforming, component (a1) more preferably contains a polyimide resin, and more preferably contains a polyimide resin (a1-1) containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), wherein the content of the repeating structural unit of formula (1) relative to the total of the repeating structural units of formula (1) and the repeating structural units of formula (2) is 20 to 70 mol %. From the viewpoint of producing highly accurate microfabricated members, the content of polyimide resin (a1-1) in component (a1) is preferably 50 mass % or more, more preferably 60 mass % or more, even more preferably 70 mass % or more, still more preferably 80 mass % or more, and still more preferably 90 mass % or more, but not more than 100 mass %. (R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.

[0025] The polyimide resin (a1-1) is a crystalline thermoplastic resin, and is preferably in the form of powder or pellets. This polyimide resin is distinguished from polyimide resins that do not have a glass transition temperature (Tg) or that decompose at a temperature lower than the glass transition temperature, and are formed by molding a polyimide precursor such as polyamic acid and then closing the imide ring.

[0026] When manufacturing the member of the present invention, particularly when the molded body is laser-processed to form fine through-holes, the thermoplastic resin composition and the molded body thereof require laser processing suitability. According to the studies of the present inventors, laser processing suitability is not necessarily the same as cutting processing suitability; for example, it has been found that the higher the melting point or glass transition temperature of the thermoplastic resin (A), the better the laser processing suitability. Although the reason is unclear, when polyimide resin (a1-1) is used as the thermoplastic resin (A), the heat resistance balance against laser is ensured, melting and evaporation of the thermoplastic resin composition in the laser-irradiated area is easily promoted, preventing the generation of burrs and residual evaporated material, and the heat resistance around the laser-irradiated area is sufficiently guaranteed, so it is presumed that melting and dimensional changes due to laser irradiation are suppressed. Therefore, it is presumed that the molded body has excellent processing suitability when laser-processing to form multiple through-holes, and a highly precise finely processed member can be obtained.

[0027] The repeating structural unit of formula (1) is described in detail below. １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. Here, the alicyclic hydrocarbon structure refers to a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and may be monocyclic or polycyclic. Examples of alicyclic hydrocarbon structures include, but are not limited to, cycloalkane rings such as a cyclohexane ring, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane, and bicycloalkene rings such as norbornene. Among these, a cycloalkane ring is preferred, a cycloalkane ring having 4 to 7 carbon atoms is more preferred, and a cyclohexane ring is even more preferred. R １ has 6 to 22 carbon atoms, preferably 8 to 17. １ contains at least one alicyclic hydrocarbon structure, preferably 1 to 3.

[0028] R １ is preferably a divalent group represented by the following formula (R1-1) or (R1-2): (m １１and m １２ are each independently an integer of 0 to 2, preferably 0 or 1. １３ ~m １５ are each independently an integer of 0 to 2, preferably 0 or 1.

[0029] R １ is particularly preferably a divalent group represented by the following formula (R1-3): In the divalent group represented by the above formula (R1-3), the positional relationship of the two methylene groups with respect to the cyclohexane ring may be either cis or trans, and the ratio of cis to trans may be any value.

[0030] X １ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited to these. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. X １ has 6 to 22 carbon atoms, preferably 6 to 18. １ contains at least one aromatic ring, preferably 1 to 3.

[0031] X １ is preferably a tetravalent group represented by any one of the following formulae (X-1) to (X-4). (R １１ ~R １８ are each independently an alkyl group having 1 to 4 carbon atoms. １１ ~p １３ are each independently an integer of 0 to 2, preferably 0. １４ , p １５ , p １６ and p １８ are each independently an integer of 0 to 3, preferably 0. １７ is an integer of 0 to 4, preferably 0. １１ ~L １３ are each independently a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms. １is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, and therefore, R １２ , R １３ , p １２ and p １３ is selected so that the number of carbon atoms in the tetravalent group represented by formula (X-2) is in the range of 10 to 22. Similarly, L in formula (X-3) １１ , R １４ , R １５ , p １４ and p １５ is selected so that the number of carbon atoms of the tetravalent group represented by formula (X-3) is in the range of 12 to 22, and L in formula (X-4) １２ , L １３ , R １６ , R １７ , R １８ , p １６ , p １７ and p １８ is selected so that the number of carbon atoms in the tetravalent group represented by formula (X-4) falls within the range of 18 to 22.

[0032] X １ is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6).

[0033] Next, the repeating structural unit of formula (2) will be described in detail below. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms. Here, the chain aliphatic group means a group derived from a chain aliphatic compound, and the chain aliphatic compound may be saturated or unsaturated, linear or branched, and may contain a heteroatom such as an oxygen atom. ２ is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, even more preferably an alkylene group having 7 to 12 carbon atoms, and among these, an alkylene group having 8 to 10 carbon atoms is preferred. The alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group. ２is preferably at least one selected from the group consisting of an octamethylene group and a decamethylene group, and more preferably an octamethylene group.

[0034] Also, R ２ Another preferred embodiment of the group R2-1 is a divalent chain aliphatic group containing an ether group and having 5 to 16 carbon atoms. The number of carbon atoms is preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10. Among these, a divalent group represented by the following formula (R2-1) or (R2-2) is preferred. (m ２１ and m ２２ are each independently an integer of 1 to 15, preferably 1 to 13, more preferably 1 to 11, and even more preferably 1 to 9. ２３ ~m ２５ are each independently an integer of 1 to 14, preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms), and therefore, m in formula (R2-1) ２１ and m ２２ is selected so that the carbon number of the divalent group represented by formula (R2-1) is in the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms). ２１ +m ２２ is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10). ２３ ~m ２５ is selected so that the carbon number of the divalent group represented by formula (R2-2) is in the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms). ２３ +m ２４ +m ２５ has 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms).

[0035] X ２is X in formula (1). １ The definitions and preferred embodiments are the same as above.

[0036] The content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is 20 to 70 mol%. When the content ratio of the repeating structural unit of formula (1) is within the above range, it is possible to sufficiently crystallize the polyimide resin (a1-1) even in a typical injection molding cycle. If the content ratio is less than 20 mol%, thermoformability decreases, and if it exceeds 70 mol%, crystallinity decreases, resulting in decreased heat resistance. From the viewpoint of achieving high crystallinity, the content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is preferably 65 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 45 mol% or less, and even more preferably 42 mol% or less. In particular, it is preferable that the content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is 20 mol% or more but less than 40 mol%. Within this range, the crystallinity of the polyimide resin (a1-1) is high, and a resin composition having better heat resistance can be obtained. From the viewpoint of producing a highly accurate microfabricated member, the content ratio is preferably 25 mol% or more, more preferably 28 mol% or more, even more preferably 30 mol% or more, and still more preferably 32 mol% or more, and from the viewpoint of exhibiting high crystallinity, it is even more preferably 38 mol% or less, even more preferably 36 mol% or less, and still more preferably 35 mol% or less.

[0037] The combined content of the repeating structural units of formula (1) and formula (2) relative to all repeating structural units constituting the polyimide resin (a1-1) is preferably 50 to 100 mol %, more preferably 75 to 100 mol %, even more preferably 80 to 100 mol %, and still more preferably 85 to 100 mol %.

[0038] The polyimide resin (a1-1) may further contain a repeating structural unit of the following formula (3). In this case, the content ratio of the repeating structural unit of formula (3) relative to the total of the repeating structural units of formula (1) and formula (2) is preferably 25 mol% or less. On the other hand, there is no particular lower limit, as long as it is greater than 0 mol%. From the viewpoint of improving heat resistance, the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, the content ratio is preferably 20 mol% or less, more preferably 15 mol% or less. (R ３ is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. ３ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.

[0039] R ３ is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited to these. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. R ３ has 6 to 22 carbon atoms, preferably 6 to 18. ３ contains at least one aromatic ring, preferably 1 to 3. The aromatic ring may have a monovalent or divalent electron-withdrawing group bonded thereto. Examples of the monovalent electron-withdrawing group include a nitro group, a cyano group, a p-toluenesulfonyl group, halogen, a halogenated alkyl group, a phenyl group, and an acyl group. Examples of the divalent electron-withdrawing group include a fluorinated alkylene group (e.g., -C(CF ３ ) ２ -, - (CF ２ ) ｐ In addition to halogenated alkylene groups such as - (where p is an integer from 1 to 10), -CO-, -SO ２ -, -SO-, -CONH-, -COO- and the like.

[0040] R ３ is preferably a divalent group represented by the following formula (R3-1) or (R3-2). (m ３１ and m ３２ are each independently an integer of 0 to 2, preferably 0 or 1. ３３ and m ３４ are each independently an integer of 0 to 2, preferably 0 or 1. ２１ , R ２２ , and R ２３ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. ２１ , p ２２ and p ２３ is an integer of 0 to 4, preferably 0. ２１ is a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms. ３ is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, and therefore, m ３１ , m ３２ , R ２１ and p ２１ is selected so that the number of carbon atoms of the divalent group represented by formula (R3-1) is in the range of 6 to 22. Similarly, L in formula (R3-2) ２１ , m ３３ , m ３４ , R ２２ , R ２３ , p ２２ and p ２３ is selected so that the number of carbon atoms in the divalent group represented by formula (R3-2) falls within the range of 12 to 22.

[0041] X ３ is X in formula (1). １ The definitions and preferred embodiments are the same as above.

[0042] The polyimide resin (a1-1) may further contain a repeating structural unit represented by the following formula (4): (R ４ Ha-SO ２ - or -Si(R ｘ ) (R ｙ ) is a divalent group containing O—, and R ｘ and R ｙeach independently represents a chain aliphatic group having 1 to 3 carbon atoms or a phenyl group. ４ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. ４ is X in formula (1). １ The definitions and preferred embodiments are the same as above.

[0043] The terminal structure of the polyimide resin (a1-1) is not particularly limited, but it is preferable that the polyimide resin (a1-1) has a chain aliphatic group having 5 to 14 carbon atoms at the terminal. The chain aliphatic group may be saturated or unsaturated, and may be linear or branched. When the polyimide resin (a1-1) has the above-mentioned specific group at the terminal, a resin composition having excellent heat aging resistance can be obtained. Examples of saturated chain aliphatic groups having 5 to 14 carbon atoms include an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, a lauryl group, an n-tridecyl group, an n-tetradecyl group, an isopentyl group, a neopentyl group, a 2-methylpentyl group, a 2-methylhexyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, an isooctyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, an isononyl group, a 2-ethyloctyl group, an isodecyl group, an isododecyl group, an isotridecyl group, and an isotetradecyl group. Examples of unsaturated chain aliphatic groups having 5 to 14 carbon atoms include 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, and tetradecenyl groups. Among these, the chain aliphatic groups are preferably saturated chain aliphatic groups, and more preferably saturated linear chain aliphatic groups. Furthermore, from the viewpoint of obtaining heat aging resistance, the chain aliphatic groups preferably have 6 or more carbon atoms, more preferably 7 or more carbon atoms, and even more preferably 8 or more carbon atoms, and preferably have 12 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably have 9 or less carbon atoms. The chain aliphatic groups may be of one type, or two or more types. The chain aliphatic group is particularly preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group, further preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, and an isononyl group, and most preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, and a 2-ethylhexyl group.From the viewpoint of heat aging resistance, the polyimide resin (a1-1) preferably has, at its terminal, in addition to a terminal amino group and a terminal carboxy group, only a chain aliphatic group having 5 to 14 carbon atoms. When a group other than the above is present at its terminal, the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, relative to the chain aliphatic group having 5 to 14 carbon atoms.

[0044] From the viewpoint of exhibiting excellent heat aging resistance, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (a1-1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more, based on 100 mol% of the total of all repeating structural units constituting the polyimide resin (a1-1). Furthermore, in order to ensure a sufficient molecular weight and obtain good mechanical properties, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (a1-1) is preferably 10 mol% or less, more preferably 6 mol% or less, and even more preferably 3.5 mol% or less, based on 100 mol% of the total of all repeating structural units constituting the polyimide resin (a1-1). Here, "the total of all repeating structural units constituting the polyimide resin (a1-1)" refers to the sum of the repeating structural units represented by the formulas (1), (2), (3), and (4). The content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (a1-1) can be determined by depolymerizing the polyimide resin (a1-1).

[0045] The polyimide resin (a1-1) preferably has a melting point of 360 ° C. or less and a glass transition temperature of 150 ° C. or more. From the viewpoint of producing a member that has been subjected to high-precision microfabrication, the melting point of the polyimide resin (a1-1) is more preferably 280 ° C. or more, even more preferably 290 ° C. or more, and from the viewpoint of ease of thermoforming, it is preferably 345 ° C. or less, more preferably 340 ° C. or less, even more preferably 335 ° C. or less. Furthermore, from the viewpoint of producing a member that has been subjected to high-precision microfabrication, the glass transition temperature of the polyimide resin (a1-1) is more preferably 160 ° C. or more, more preferably 170 ° C. or more, and from the viewpoint of ease of thermoforming, it is preferably 250 ° C. or less, more preferably 230 ° C. or less, even more preferably 200 ° C. or less.

[0046] The crystallization temperature Tc of the polyimide resin (a1-1) is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 250°C or higher from the viewpoint of heat resistance, and is preferably 350°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower from the viewpoint of moldability.

[0047] From the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the polyimide resin (a1-1) preferably has a heat of fusion Hm of 5.0 mJ / mg or more, more preferably 10 mJ / mg or more, and even more preferably 17 mJ / mg or more. The upper limit of the heat of fusion Hm is not particularly limited, but is usually 45 mJ / mg or less. The heat of fusion Hm of the polyimide resin (a1-1) is calculated from the area of ​​the heat of fusion peak (endothermic peak) near the melting point observed when the polyimide resin (a1-1) is heated at a heating rate of 10°C / min to melt at a temperature above the melting point, then cooled at a heating rate of 20°C / min, and then heated again at a heating rate of 10°C / min to melt.

[0048] Furthermore, from the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the polyimide resin (a1-1) preferably has a heat of crystallization Hc of 5.0 mJ / mg or more, more preferably 10 mJ / mg or more, and even more preferably 17 mJ / mg or more. The upper limit of the heat of crystallization Hc is not particularly limited, but is usually 45 mJ / mg or less. The heat of crystallization Hc of the polyimide resin (a1-1) means the heat of the exothermic crystallization peak observed when the polyimide resin (a1-1) is melted and then cooled at a temperature decrease rate of 20°C / min by differential scanning calorimetry. The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, heat of fusion Hm, and heat of crystallization Hc of the polyimide resin (a1-1) can be specifically measured by the methods described in the Examples.

[0049] The logarithmic viscosity of a 0.5 mass % solution of polyimide resin (a1-1) in concentrated sulfuric acid at 30°C is preferably in the range of 0.2 to 2.0 dL / g, more preferably 0.3 to 1.8 dL / g. If the logarithmic viscosity is 0.2 dL / g or higher, the resulting molded article and part will have sufficient mechanical strength, and if it is 2.0 dL / g or lower, the thermoformability and handleability will be good. The logarithmic viscosity μ is determined by measuring the flow times of concentrated sulfuric acid and the polyimide resin solution at 30°C using a Cannon-Fenske viscometer, and then using the following formula: μ = ln(ts / t ０ ) / C t ０ : Time during which concentrated sulfuric acid flows ts: Time during which polyimide resin solution flows C: 0.5 (g / dL)

[0050] The weight average molecular weight Mw of the polyimide resin (a1-1) is preferably in the range of 10,000 to 150,000, more preferably 15,000 to 100,000, even more preferably 20,000 to 80,000, even more preferably 30,000 to 70,000, and even more preferably 35,000 to 65,000. If the weight average molecular weight Mw of the polyimide resin (a1-1) is 10,000 or more, the mechanical strength of the resulting molded article and part will be good, if it is 40,000 or more, the stability of the mechanical strength will be good, and if it is 150,000 or less, the thermoformability will be good. The weight average molecular weight Mw of the polyimide resin (a1-1) can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.

[0051] (Method for Producing Polyimide Resin (a1-1)) The polyimide resin (a1-1) can be produced by reacting a tetracarboxylic acid component with a diamine component. The tetracarboxylic acid component contains a tetracarboxylic acid and / or a derivative thereof containing at least one aromatic ring, and the diamine component contains a diamine containing at least one alicyclic hydrocarbon structure and a chain aliphatic diamine.

[0052] The tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxy groups are directly bonded to the aromatic ring, and may contain an alkyl group within the structure. The tetracarboxylic acid preferably has 6 to 26 carbon atoms. The tetracarboxylic acid preferably contains at least one selected from the group consisting of pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. Among these, pyromellitic acid is more preferred.

[0053] Examples of the derivative of a tetracarboxylic acid containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring. The tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms. Examples of the anhydrides of tetracarboxylic acids include pyromellitic acid monoanhydride, pyromellitic acid dianhydride, 2,3,5,6-toluenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 1,4,5,8-naphthalenetetracarboxylic acid dianhydride. Examples of alkyl esters of tetracarboxylic acids include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, dimethyl 3,3',4,4'-diphenylsulfonetetracarboxylate, dimethyl 3,3',4,4'-benzophenonetetracarboxylate, dimethyl 3,3',4,4'-biphenyltetracarboxylate, dimethyl 1,4,5,8-naphthalenetetracarboxylate, etc. In the alkyl esters of tetracarboxylic acids, the alkyl group preferably has 1 to 3 carbon atoms.

[0054] The tetracarboxylic acid and / or derivative thereof containing at least one aromatic ring may be at least one compound selected from the above, which may be used alone, or two or more compounds may be used in combination.

[0055] The diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, and examples thereof include 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), carvonediamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.0] ... ２，６ It is preferable that the diamine contains at least one compound selected from the group consisting of decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodicyclohexylpropane. These compounds may be used alone, or two or more compounds selected from these may be used in combination. Of these, 1,3-bis(aminomethyl)cyclohexane is preferably used. Note that diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis / trans isomers is not limited.

[0056] The chain aliphatic diamine may be linear or branched, and preferably has 5 to 16 carbon atoms, more preferably 6 to 14, and even more preferably 7 to 12. In addition, when the number of carbon atoms in the chain portion is 5 to 16, an ether bond may be contained therein. The chain aliphatic diamine preferably includes at least one selected from the group consisting of 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 2,2'-(ethylenedioxy)bis(ethyleneamine). The chain aliphatic diamine may be used alone or in combination. Among these, chain aliphatic diamines having 8 to 10 carbon atoms can be preferably used, and in particular, at least one selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine can be preferably used.

[0057] When producing polyimide resin (a1-1), the molar ratio of the amount of diamine containing at least one alicyclic hydrocarbon structure charged to the total amount of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine is preferably 20 to 70 mol%. This molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 32 mol% or more. From the viewpoint of exhibiting high crystallinity, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 45 mol% or less, still more preferably 42 mol% or less, still more preferably less than 40 mol%, still more preferably 38 mol% or less, still more preferably 36 mol% or less, and still more preferably 35 mol% or less.

[0058] The diamine component may also contain a diamine containing at least one aromatic ring. The diamine containing at least one aromatic ring preferably has 6 to 22 carbon atoms, and examples thereof include ortho-xylylenediamine, meta-xylylenediamine, para-xylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynylbenzenediamine, 1,4-diethynylbenzenediamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, α,α'-bis(4-aminophenyl)1,4-diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,4-diisopropylbenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,6-diaminonaphthalene, and 1,5-diaminonaphthalene.

[0059] In the above, the molar ratio of the amount of diamine containing at least one aromatic ring charged to the total amount of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine is preferably 25 mol% or less. On the other hand, the lower limit is not particularly limited, as long as it is greater than 0 mol%. From the viewpoint of improving heat resistance, the molar ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less. Furthermore, from the viewpoint of reducing coloration of polyimide resin (a1-1), the molar ratio is preferably 12 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, and even more preferably 0 mol%.

[0060] When producing the polyimide resin (a1-1), the ratio of the amount of the tetracarboxylic acid component to the amount of the diamine component charged is preferably 0.9 to 1.1 moles of the diamine component per mole of the tetracarboxylic acid component.

[0061] Furthermore, when producing the polyimide resin (a1-1), a terminal-capping agent may be mixed in addition to the tetracarboxylic acid component and the diamine component. The terminal-capping agent is preferably at least one selected from the group consisting of monoamines and dicarboxylic acids. The amount of terminal-capping agent used may be any amount sufficient to introduce the desired amount of terminal groups into the polyimide resin (a1-1), and is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, and even more preferably 0.002 to 0.035 mol per mol of the tetracarboxylic acid and / or its derivative. Among these, monoamine terminal-capping agents are preferred. From the viewpoint of introducing the aforementioned linear aliphatic group having 5 to 14 carbon atoms to the terminal of the polyimide resin (a1-1) to improve heat aging resistance, monoamines having a linear aliphatic group having 5 to 14 carbon atoms are more preferred, and monoamines having a saturated linear aliphatic group having 5 to 14 carbon atoms are even more preferred. The end-capping agent is particularly preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, more preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and even more preferably at least one selected from the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

[0062] As a polymerization method for producing the polyimide resin (a1-1), a known polymerization method can be applied, and the method described in WO 2016 / 147996 can be used.

[0063] From the viewpoint of producing a highly accurate microfabricated member and from the viewpoint of ease of thermoforming, the content of polyimide resin (a1-1) in component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, but 100% by mass or less.

[0064] The content of component (A) in the thermoplastic resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, still more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, from the viewpoint of producing a highly accurate microfabricated member and from the viewpoint of ease of thermoforming. Also, from the viewpoint of producing a highly accurate microfabricated member, it is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0065] <Component (B): Inorganic Filler Containing Zirconium Oxide (b1)> The thermoplastic resin composition used in the present invention contains an inorganic filler containing zirconium oxide (b1) as component (B). By using the thermoplastic resin (A) and the inorganic filler (B) containing a predetermined amount of zirconium oxide (b1), it is possible to produce a highly accurate microfabricated member.

[0066] (Component (b1): Zirconium oxide) The shape of the zirconium oxide (b1) used in the present invention is not particularly limited, and examples thereof include spherical, plate-like, scaly, columnar, and fibrous shapes. Among these, from the viewpoint of producing highly accurate microfabricated members, spherical or plate-like particles are preferred, and spherical particles are more preferred. From the viewpoint of producing highly accurate microfabricated members and from the viewpoint of availability, it is preferable that the zirconium oxide (b1) has a small particle size. For example, from the viewpoint of producing highly accurate microfabricated members, the volume median particle size (D50) of component (b1) is preferably 1 μm or less, more preferably 0.80 μm or less, even more preferably 0.60 μm or less, still more preferably 0.50 μm or less, and still more preferably 0.40 μm or less. Furthermore, from the viewpoints of producing highly accurate microfabricated components, availability, and ease of handling, the particle size is usually 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.05 μm or more. The D50 of component (b1) can be measured using a laser diffraction light scattering particle size distribution analyzer.

[0067] Examples of commercially available zirconium oxide particles that can be used as component (b1) include the KZ series manufactured by Kyoritsu Material Co., Ltd., the TZ series manufactured by Tosoh Corporation, and the UEP series manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. Among these, the KZ series high-purity zirconia "KZ-0Y-LSF" manufactured by Kyoritsu Material Co., Ltd. can be suitably selected.

[0068] From the viewpoint of producing a highly accurate microfabricated member, the content of component (b1) in component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and is 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

[0069] The content of component (b1) in the thermoplastic resin composition relative to 100 parts by mass of component (A) is 2 to 40 parts by mass, preferably 5 to 35 parts by mass, more preferably 5 to 30 parts by mass, even more preferably 10 to 30 parts by mass, and still more preferably 20 to 30 parts by mass, from the viewpoint of ease of thermoforming and the viewpoint of producing a highly accurate microfabricated part.

[0070] (Component (b2): Inorganic Filler Other Than Component (b1)) Component (B) may be an inorganic filler consisting solely of component (b1), or may further contain an inorganic filler (b2) other than component (b1). Examples of component (b2) include talc, mica, silica, alumina, wollastonite, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, calcium carbonate, titanium oxide, zinc oxide, calcium oxide, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, antimony trisulfide, tin sulfide, copper sulfide, iron sulfide, bismuth sulfide, and zinc sulfide, and one or more of these may be used. Among the above, from the viewpoint of producing a highly accurate microfabricated member, component (b2) preferably contains at least one selected from the group consisting of talc, mica, silica, alumina, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, calcium carbonate, and titanium oxide, more preferably contains at least one selected from the group consisting of talc, mica, silica, and titanium oxide, even more preferably contains at least one selected from the group consisting of talc and silica, and still more preferably is talc.

[0071] The shape of component (b2) is not particularly limited, and examples thereof include spherical, plate-like, scale-like, columnar, and fibrous shapes. Among these, spherical or plate-like particles are preferred from the viewpoint of producing highly accurate microfabricated components and from the viewpoint of availability.

[0072] The volume median particle size (D50) of component (b2) is preferably 3 μm or less, more preferably 2 μm or less, even more preferably 1.5 μm or less, even more preferably 1.2 μm or less, and even more preferably 1 μm or less, from the viewpoints of producing highly accurate microfabricated components and availability. Furthermore, from the viewpoints of producing highly accurate microfabricated components, availability, and improved handling, it is usually 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. The D50 of component (b2) can be measured in the same manner as for component (b1).

[0073] When component (b2) is used, the content of component (b2) in component (B) is, from the viewpoint of ease of thermoforming and the viewpoint of producing a highly accurate microfabricated part, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less, and is also preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, and still more preferably 30% by mass or more.

[0074] When component (b2) is used, the content of component (b2) relative to 100 parts by mass of component (A) in the thermoplastic resin composition is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, even more preferably 5 to 30 parts by mass, and still more preferably 10 to 20 parts by mass, from the viewpoint of producing a highly accurate microfabricated member.

[0075] The content of component (B) per 100 parts by mass of component (A) in the thermoplastic resin composition is 2 to 60 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, even more preferably 15 to 45 parts by mass, still more preferably 20 to 45 parts by mass, still more preferably 25 to 45 parts by mass, and still more preferably 30 to 45 parts by mass, from the viewpoint of ease of thermoforming and the viewpoint of producing a member that has been subjected to high-precision microfabrication.

[0076] <Additives> The thermoplastic resin composition may contain additives other than component (B), such as reinforcing fibers, delustering agents, plasticizers, antistatic agents, coloring inhibitors, antigelling agents, colorants, sliding properties improvers, antioxidants, conductive agents, organic heat-resistant materials (thermosetting resin powders), and resin modifiers, as needed. In particular, graphite, carbon black, graphite, ketjen black, or carbon nanotubes can be used as antistatic agents, because sufficient antistatic effects can be achieved even with small amounts that do not impair the properties of the thermoplastic resin composition. Carbon nanotubes are particularly preferred because they achieve sufficient antistatic effects even with small amounts and can suppress deterioration of micromachining and thermoforming properties. Commercially available carbon nanotubes include the NTF series manufactured by Koatsu Gas Kogyo Co., Ltd., the K-nanos series manufactured by Kumho Petrochemical, and the NC series manufactured by Nanocyl. When the above-mentioned additives are used, there are no particular restrictions on the amount of the additives used. However, from the viewpoint of exerting the effects of the additives, the amount of the additives used in the thermoplastic resin composition is usually 50% by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.001 to 15% by mass, and even more preferably 0.01 to 10% by mass.

[0077] Furthermore, the thermoplastic resin composition can contain other resins than the thermoplastic resin (A) as long as the properties of the thermoplastic resin composition are not impaired. When the thermoplastic resin (A) and other resins are used in combination, there are no particular limitations on the blending ratio as long as the properties of the thermoplastic resin composition are not impaired.

[0078] However, from the viewpoint of ease of thermoforming and the viewpoint of producing highly accurate microfabricated parts, the total content of component (A) and component (B) in the thermoplastic resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, but is 100% by mass or less.

[0079] The thermoplastic resin composition can take any form, but is preferably in the form of pellets. The thermoplastic resin composition used in the present invention can be prepared, for example, by dry-blending the thermoplastic resin (A), the inorganic filler (B), and, if necessary, various optional components, or by separately feeding the inorganic filler (B) and optional components from a location separate from the feed of the thermoplastic resin (A) into the extruder, melt-kneading the mixture in the extruder to extrude strands, and then cutting the strands to form pellets. Furthermore, the pellets can be introduced into various molding machines and thermoformed using the method described below to easily produce the molded articles described below. Alternatively, the molded articles can be obtained without going through the pelletized form. For example, the thermoplastic resin (A), the inorganic filler (B), and, if necessary, various optional components can be dry-blended, and then the blended material can be placed in a mold and subjected to heat pressing to perform compression molding, thereby directly obtaining molded articles. From the perspective of forming pellets and performing compression molding, the thermoplastic resin composition used in the present invention preferably does not contain a solvent. Specifically, the solvent content in the thermoplastic resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.

[0080] The thermoplastic resin composition used in the present invention can also be used for applications other than the components of the present invention, such as gears, bearings, wristwatch housings, semiconductor manufacturing machine jigs, transport components, optical connectors, 3D printer components, and aerospace components.

[0081] [Method for manufacturing a member] The present invention further provides a method for manufacturing the probe card member or the printed circuit board inspection jig member of the present invention, which comprises the following steps (I) and (II) in this order: Step (I): A step of molding the following thermoplastic resin composition by a thermoforming method to obtain a molded article having a plate-like portion: Component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher; and Component (B): an inorganic filler containing zirconium oxide (b1), wherein the content of Component (b1) is 2 to 40 parts by mass per 100 parts by mass of Component (A), and the content of Component (B) is 2 to 60 parts by mass per 100 parts by mass of Component (A). Step (II): A step of forming a plurality of through holes in the plate-like portion of the molded article by cutting or laser processing.

[0082] <Step (I)> In step (I), the thermoplastic resin composition is molded by a thermoforming method to obtain a molded article having a plate-like portion. The thermoplastic resin composition and its preferred embodiments are the same as those described above. The molded article obtained in step (I) has a plate-like portion. This is because through holes that penetrate the plate-like portion of the molded article in the thickness direction are formed in step (II), which will be described later. The molded article having a plate-like portion may be a molded article in which at least a portion is plate-like, or may be a flat molded article in which the entire body is plate-like. The thickness of the plate-like portion varies depending on the type of member to be manufactured, but is preferably in the range of 0.1 to 20 mm, more preferably 0.5 to 10 mm, and even more preferably 0.5 to 5 mm.

[0083] A molded article having a plate-like portion can be produced by thermoforming the thermoplastic resin composition. Thermoforming methods include injection molding, extrusion molding, compression molding, inflation molding, blow molding, vacuum molding, pressure molding, laser molding, welding, and welding. Any molding method that involves a thermal melting step can be used. From the viewpoint of thermoforming using pellets of the thermoplastic resin composition and cutting or laser processing the resulting molded article in step (II) to form through-holes, the thermoforming method is preferably injection molding, extrusion molding, or compression molding. In particular, injection molding is preferred from the viewpoint of improving production efficiency, and extrusion molding is preferred from the viewpoint of obtaining higher dimensional stability.

[0084] The thermoforming conditions for step (I) vary depending on the melting point or glass transition temperature of the thermoplastic resin (A) used. When the thermoplastic resin (A) contains the polyimide resin (a1-1), step (I) preferably comprises thermoforming the thermoplastic resin composition at 290 to 380°C. Thermoforming at temperatures above 380°C to 400°C is also possible, but from the viewpoint of suppressing deterioration of the thermoplastic resin (A) and other components, thermoforming at a temperature of 380°C or less is preferred. Specific procedures include, for example, the following method. First, the inorganic filler (B) and various optional components, if necessary, are added to the thermoplastic resin (A) and dry-blended, and the mixture is then introduced into an extruder, melted preferably at 290 to 380°C, and melt-kneaded and extruded in the extruder to produce pellets. Alternatively, the thermoplastic resin (A) may be introduced into an extruder, melted preferably at 290 to 380°C, and then the inorganic filler (B) and various optional components, if necessary, are introduced thereto, melt-kneaded with the thermoplastic resin (A) in the extruder, and extruded to produce the pellets. After drying the pellets, they can be introduced into various molding machines and thermoformed preferably at 290 to 380°C to produce a molded article having a plate-like portion.

[0085] The molded article obtained by the thermoforming may be further subjected to cutting or the like to form a desired shape. For example, an injection-molded article may be produced using the thermoplastic resin composition, and then the molded article may be subjected to cutting to obtain a molded article having a desired shape.

[0086] The molded article obtained by the thermoforming is preferably further annealed from the viewpoint of further improving the cutting processability of the molded article and the micromachining processability in step (II). The molded article obtained by thermoforming the thermoplastic resin composition and then annealing it has a low surface roughness on the cut surface when cut, and in the case of a flat molded article, a flat plate with little warping can be obtained. Furthermore, using the flat plate, multiple through holes can be formed with higher precision. The annealing process of the molded article is preferably performed after the thermoforming in step (I) and before the cutting process. Alternatively, the annealing process may be performed after the thermoforming in step (I) and before the cutting process, and then again after the cutting process. The annealing temperature can be set according to the type of thermoplastic resin (A) used. When the thermoplastic resin (A) is a crystalline thermoplastic resin (a1), the annealing temperature is a temperature below the melting point of the crystalline thermoplastic resin (a1) from the viewpoint of avoiding deformation of the molded body, and from the viewpoint of further improving the machinability and micromachinability of the molded body, and from the viewpoint of avoiding deformation of the molded body, when the melting point of the crystalline thermoplastic resin (a1) is Tm (°C), it is preferably in the range of Tm-100 ° C to Tm-20 ° C. When the thermoplastic resin (A) is an amorphous thermoplastic resin (a2), the annealing temperature is a temperature below the glass transition temperature of the amorphous thermoplastic resin (a2) from the viewpoint of avoiding deformation of the molded body, and from the viewpoint of further improving the machinability and micromachinability of the molded body, and from the viewpoint of avoiding deformation of the molded body, when the glass transition temperature of the amorphous thermoplastic resin (a2) is Tg (°C), it is preferably in the range of Tg-100 ° C to Tg-20 ° C. When the thermoplastic resin (A) contains the polyimide resin (a1-1), specific examples of the annealing temperature are, from the viewpoint of further improving the machinability and micromachinability of the molded article and from the viewpoint of avoiding deformation of the molded article, preferably in the range of 200 to 360 ° C., more preferably 220 to 340 ° C., even more preferably 240 to 330 ° C., and still more preferably 250 to 320 ° C. The annealing time is not particularly limited, but from the viewpoint of further improving the machinability and micromachinability of the molded article and from the viewpoint of improving production efficiency, it is preferably in the range of 1 to 180 minutes, more preferably 5 to 150 minutes.The annealing treatment of the molded body can be carried out using a known heating device. After the annealing treatment, the molded body is slowly cooled to a temperature of preferably 100° C. or less in order to prevent the molded body from warping due to residual stress.

[0087] The surface of the plate-shaped portion of the molded article preferably has a low surface roughness from the viewpoint of improving the micromachining ability in step (II). For example, the arithmetic mean roughness (Ra) of the surface of the plate-shaped portion of the molded article is preferably 1 μm or less, more preferably 0.8 μm or less, even more preferably 0.6 μm or less, and even more preferably 0.3 μm or less. The arithmetic mean roughness (Ra) of the surface of the plate-shaped portion can be determined, for example, by measuring the arithmetic mean roughness of a continuous region having a length of 20 mm using a 3D shape measuring device (Keyence Corporation "VR-6000").

[0088] <Step (II)> In step (II), a plurality of through holes are formed by cutting or laser processing in the plate-like portion of the molded article obtained in step (I). According to the method for producing a member of the present invention, high-precision microfabrication can be performed even when a large number of through holes are formed at narrow pitches in step (II).

[0089] In step (II), a power drill or the like can be used to form the through-holes by cutting. Furthermore, a laser processing machine or the like can be used to form the through-holes by laser processing. From the viewpoint of performing micromachining with higher precision, the processing method in step (II) is preferably laser processing. The laser processing conditions are not particularly limited, but for example, micromachining can be performed using a laser beam with a wavelength of 266 to 1066 nm. UV lasers around 355 nm and deep ultraviolet lasers around 266 nm are particularly suitable because they have high absorption rates in polyimide-based materials.

[0090] The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, various measurements and evaluations in each production example and example were carried out as follows.

[0091] <Infrared Spectroscopic Analysis (IR Measurement)> IR measurement of the polyimide resin was carried out using a JEOL Ltd. "JIR-WINSPEC50".

[0092] <Logarithmic Viscosity μ> After drying a polyimide resin at 190 to 200°C for 2 hours, 0.100 g of the polyimide resin was dissolved in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Inc.) to prepare a polyimide resin solution as a measurement sample, and measurement was carried out at 30°C using a Cannon-Fenske viscometer. Logarithmic viscosity μ was calculated using the following formula: μ = ln(ts / t ０ ) / C t ０ : Time during which concentrated sulfuric acid flows ts: Time during which polyimide resin solution flows C: 0.5 g / dL

[0093] <Melting Point, Glass Transition Temperature, Crystallization Temperature, Heat of Fusion, Heat of Crystallization> The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, heat of fusion Hm, and heat of crystallization Hc of the polyimide resin were measured using a differential scanning calorimeter (TA Instruments "DSC-25"). Under a nitrogen atmosphere (nitrogen gas flow rate 50 mL / min), the measurement sample was subjected to the following thermal history conditions. The thermal history conditions were a first heating (heating rate 10°C / min), followed by cooling (heating rate 20°C / min), followed by a second heating (heating rate 10°C / min). The melting point Tm was determined by reading the peak top value of the endothermic peak observed during the second heating. The glass transition temperature Tg was determined by reading the value observed during the second heating. The crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. For Tm, Tg, and Tc, when multiple peaks were observed, the peak top value of each peak was read. The heat of fusion Hm (mJ / mg) was calculated from the area of ​​the heat of fusion peak (endothermic peak) observed near the melting point when the measurement sample was heated to a temperature above the melting point at a heating rate of 10 ° C. / min, melted, cooled at a heating rate of 20 ° C. / min, and then melted again at a heating rate of 10 ° C. / min. The heat of crystallization Hc (mJ / mg) was calculated from the area of ​​the crystallization exothermic peak observed when the measurement sample was heated to a temperature above the melting point at a heating rate of 10 ° C. / min, melted, and then cooled at a heating rate of 20 ° C. / min.

[0094] <Crystallization Half Time> The crystallization half time of the polyimide resin was measured using a differential scanning calorimeter (DSC-6220 manufactured by SII Nanotechnology, Inc.). The polyimide resin was held at 420°C for 10 minutes in a nitrogen atmosphere to completely melt it, and then rapidly cooled at a cooling rate of 70°C / min. The time required from the appearance of the observed crystallization peak to the peak top was calculated. In Table 1, crystallization half times of 20 seconds or less are indicated as "<20".

[0095] <Weight-average molecular weight> The weight-average molecular weight (Mw) of the polyimide resin was measured using a gel permeation chromatography (GPC) measuring device "Shodex GPC-101" manufactured by Showa Denko K.K. under the following conditions: Column: Shodex HFIP-806M Mobile phase solvent: HFIP containing 2 mM sodium trifluoroacetate Column temperature: 40°C Mobile phase flow rate: 1.0 mL / min Sample concentration: approximately 0.1% by mass Detector: IR detector Injection volume: 100 μm Calibration curve: standard PMMA

[0096] Production Example 1 (Production of Crystalline Thermoplastic Polyimide Resin 1) 500 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four paddle blades. After nitrogen flow, the mixture was stirred at 150 rpm to obtain a uniform suspension. Meanwhile, using a 500 mL beaker, 49.79 g (0.35 mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio = 7 / 3) and 93.77 g (0.65 mol) of 1,8-octamethylenediamine (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 250 g of 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. This mixed diamine solution was gradually added using a plunger pump. Although heat was generated during the dropwise addition, the internal temperature was adjusted to remain within the range of 40 to 80°C. During the dropwise addition of the mixed diamine solution, nitrogen flow was maintained throughout, and the stirring impeller rotation speed was set to 250 rpm. After the dropwise addition was completed, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.01 mol) of n-octylamine (Kanto Chemical Co., Inc.), an end-capping agent, were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, the stirring speed was increased to 200 rpm, and the polyamic acid solution in the 2-L separable flask was heated to 190°C. During the temperature increase, precipitation of polyimide resin powder and dehydration associated with imidization were observed between 120 and 140°C. After holding at 190°C for 30 minutes, the solution was allowed to cool to room temperature and then filtered. The obtained polyimide resin powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and then dried in a dryer at 180°C for 10 hours to obtain 317 g of powder of crystalline thermoplastic polyimide resin 1 (hereinafter also simply referred to as "polyimide resin 1"). The IR spectrum of polyimide resin 1 was measured, revealing a ν(C=O) 1768, 1697 (cm －１The inherent viscosity was 1.30 dL / g, Tm was 323°C, Tg was 184°C, Tc was 266°C, the heat of fusion was 21.0 mJ / mg, the heat of crystallization was 20.3 mJ / mg, the crystallization half time was 20 seconds or less, and the Mw was 55,000.

[0097] The composition and properties of polyimide resin 1 obtained in Production Example 1 are shown in Table 1. The mole percentages of the tetracarboxylic acid component and diamine component in Table 1 are values ​​calculated from the amounts of each component charged during the production of the polyimide resin.

[0098]

[0099] The abbreviations in Table 1 are as follows: PMDA: pyromellitic dianhydride 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane OMDA: 1,8-octamethylenediamine n-OcA: n-octylamine

[0100] Example 1 [Production of Thermoplastic Resin Composition] Component (A) and component (B) shown in Table 2 were thoroughly mixed by dry blending. The resulting mixed powder was extruded into strands with a diameter of 2 to 3 mm using a co-rotating twin-screw kneading extruder ("HK-25D-41D" manufactured by Parker Corporation, screw diameter: 25 mm) at a barrel temperature of 360°C and a screw rotation speed of 120 rpm. The strands extruded from the extruder were air-cooled and then pelletized using a pelletizer ("Fan Cutter FC-Mini-4 / N" manufactured by Hoshi Plastics Co., Ltd.).

[0101] [Step (I): Preparation of a flat plate-shaped molded body] The pellets (thermoplastic resin composition) obtained by the above method were dried at 150 ° C for 10 hours, and then injection molded by the following method to prepare a flat plate-shaped molded body. Using an injection molding machine (FANUC Corporation "ROBOSHOT α-S30iA"), the thermoplastic resin composition was injection molded at a barrel temperature of 375 ° C, a mold temperature of 200 ° C, and a molding cycle of 60 seconds to produce a flat injection molded body 100 having a diameter of 40 mm Φ and a thickness of 4 mm. This was heated at 300 ° C for 60 minutes in a hot air dryer and subjected to an annealing treatment. Next, on one side of the obtained injection molded body 100, a 5 mm × 5 mm × 3 mm deep pocket was engraved by drilling at the position shown in FIG. 1 to prepare a molded body 200. Here, FIG. 1 is a plan view schematic diagram of the molded body 200 prepared in the above step (I) of Example 1, where 201 and 202 are the pockets.

[0102] [Step (II): Formation and Evaluation of Through Holes] Next, a plurality of through holes were formed by laser processing in a portion (center) of the bottom surface of the pockets 201 and 202 of the molded body 200 produced in step (I). Specifically, 1,000 through holes with a circular opening diameter of 25 μmΦ and a pitch of 32 μm and a partition wall of 7 μm were formed in the center of the bottom surface of the pocket 201. Furthermore, 1,000 through holes with a square opening shape and a side length of 30 μm were formed in the center of the bottom surface of the pocket 202 with a partition wall of 7 μm. The laser processing was performed using a laser processing machine manufactured by Kataoka Corporation. The shapes of the formed through holes were evaluated as follows. The evaluation results are shown in Table 2.

[0103] (Microfabrication evaluation-1) The through holes formed by the above method were observed with a digital microscope (Keyence Corporation's "VHX-7000", magnification: 150x), and the microfabrication state was evaluated based on the following items and criteria. <Appearance (presence or absence of partition wall breakage and discoloration)> A: Neither partition wall breakage nor discoloration is observed. C: Partition wall breakage or discoloration is observed. <Burri state> A: No burrs are observed. B: Burrs are present, but can be removed by air blowing treatment. C: Many burrs are present, and removal by air blowing treatment is difficult.

[0104] (Microfabrication Evaluation-2) The opening shapes of the through holes formed by the above method were observed and measured using a high-precision image dimension measuring instrument (LM Series manufactured by Keyence Corporation), and evaluated based on the following items and criteria. <Circularity> A: For all through holes with a circular opening shape, the opening diameter was within the range of 25.0±0.5 μm. C: For all through holes with a circular opening shape, there were through holes with an opening diameter exceeding the range of 25.0±0.5 μm. <Squareness> For all through holes with a square opening shape, the curvature of the right-angled portion of the opening was measured, and the average value of this curvature was shown in Table 2 as the radius R (μm). A smaller R value indicates a closer to a right angle, and higher precision processing was performed.

[0105] Example 2 The same procedures as in Example 1 were used to prepare molded bodies, perform step (II), and perform various evaluations, except that in step (I) of Example 1, the molding method for the plate-shaped molded body was changed to extrusion molding, and the annealing temperature was changed to the temperature shown in the table. The evaluation results are shown in Table 2. Specifically, step (I) was performed as follows. [Step (I)] Pellets (thermoplastic resin composition) obtained by the same method as in Example 1 were dried at 150°C for 10 hours and then extrusion-molded by the following method to prepare a plate-shaped molded body. The thermoplastic resin composition was extruded at an extrusion temperature of 360°C using an extrusion molding machine ("FS30" manufactured by Ikegai Corporation). Subsequently, cutting was performed to prepare a plate-shaped extruded molded body 110 with a diameter of 40 mm and a thickness of 4 mm. This was heated in a hot air dryer at 260°C for 120 minutes and annealed. Two pockets measuring 5 mm x 5 mm x 3 mm deep were carved into one surface of the obtained extrusion-molded product 110 in the same manner as in Example 1, to produce molded product 210. Note that injection-molded product 100 and extrusion-molded product 110, and molded products 200 and 210, have the same shape.

[0106]

[0107] The details of each component shown in Table 2 are as follows: <Thermoplastic resin (A)> (a1-1) Polyimide resin 1 obtained in Production Example 1 <Inorganic filler (B)> (b1) Zirconium oxide, high-purity zirconia "KZ-0Y-LSF" manufactured by Kyoritsu Material Co., Ltd., spherical particles, D50: 0.2 μm (b2) Talc, "Nano Ace D-800" manufactured by Nippon Talc Co., Ltd., plate-like particles, D50: 0.8 μm

[0108] As shown in Table 2, the components of this example exhibited minimal burrs, partition wall breakage, discoloration, and variation in the through-hole opening shape, even when multiple fine through-holes were formed at a narrow pitch. Furthermore, even when the opening shape was square, the reproducibility of the shape was high, demonstrating high-precision microfabrication. Figures 2 to 5 show images of the through-holes formed in step (II) of Examples 1 and 2, observed from above with the digital microscope (magnification: 150x). Figure 2 shows an image of a through-hole with a circular opening made in Example 1, Figure 3 shows an image of a through-hole with a square opening made in Example 1, Figure 4 shows an image of a through-hole with a circular opening made in Example 2, and Figure 5 shows an image of a through-hole with a square opening made in Example 2.

[0109] According to the present invention, it is possible to provide a probe card component or a printed circuit board inspection jig component that has been subjected to high-precision micromachining, with little burrs being generated, especially when fine through-holes are formed by laser processing, and a method for manufacturing the same.

[0110] 200 Molded body produced in step (I) of Example 1 201, 202 Pocket

Claims

1. A member for a probe card or a member for a printed circuit board inspection jig, comprising: component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher; and component (B): an inorganic filler containing zirconium oxide (b1), wherein the content of component (b1) per 100 parts by mass of component (A) is 2 to 40 parts by mass, and the content of component (B) per 100 parts by mass of component (A) is 2 to 60 parts by mass.

2. The member according to claim 1, wherein the component (a1) comprises a polyimide resin (a1-1) containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content of the repeating structural unit of the formula (1) relative to the total of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) is 20 to 70 mol %: (R １ R is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.

3. The member according to claim 1 or 2, wherein the zirconium oxide (b1) has a volume median particle size (D50) of 1 μm or less.

4. The member according to any one of claims 1 to 3, wherein the total content of the component (A) and the component (B) in the thermoplastic resin composition is 50 mass% or more.

5. The member according to any one of claims 1 to 4, wherein the component (B) further contains an inorganic filler (b2) other than the component (b1), and the inorganic filler (b2) contains at least one selected from the group consisting of talc, mica, silica, alumina, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, calcium carbonate, and titanium oxide.

6. The member according to claim 5, wherein the content of the inorganic filler (b2) per 100 parts by mass of the component (A) in the thermoplastic resin composition is 1 to 40 parts by mass.

7. The member according to any one of claims 1 to 6, which has a plate-like portion and has a plurality of through holes in the plate-like portion, the through holes being approximately circular with an opening diameter of 400 μm or less, or approximately square with one side length of 400 μm or less.

8. A member according to any one of claims 1 to 7, wherein the member is a probe holding member or a probe guide member.

9. A method for producing a probe card member or a printed circuit board inspection jig member according to any one of claims 1 to 8, comprising the following steps (I) and (II) in this order: Step (I) A step of forming a thermoplastic resin composition described below by a thermoforming method to obtain a molded body having a plate-like portion: A thermoplastic resin composition containing: component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) having a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) having a glass transition temperature of 200°C or higher; and component (B): an inorganic filler containing zirconium oxide (b1), wherein the content of component (b1) is 2 to 40 parts by mass relative to 100 parts by mass of component (A), and the content of component (B) is 2 to 60 parts by mass relative to 100 parts by mass of component (A). Step (II) A step of forming a plurality of through holes in the plate-like portion of the molded body by cutting or laser processing.

10. The method according to claim 9, wherein the thermoforming method in step (I) is an injection molding method, an extrusion molding method, or a compression molding method.

11. The method according to claim 9 or 10, wherein the processing method in step (II) is laser processing.