Probe card member or printed board inspection jig member, and method for manufacturing the same

Abstract

A member and a method for manufacturing the same, the member being a member for a probe card or a member for a printed board inspection jig, the member being composed of 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), the content of the component (b1) being 2 to 40 parts by mass per 100 parts by mass of the component (A), and the content of the component (B) being 2 to 60 parts by mass per 100 parts by mass of the component (A).

Description

Technical Field

[0001] This invention relates to components for probe cards or components for printed circuit board inspection fixtures, and methods for manufacturing them. Background Technology

[0002] Engineering plastics are thermoplastic resins with excellent properties such as molding processability, heat resistance, and strength. They are used in a wide range of fields, including automotive parts, mechanical parts, and electrical / electronic parts.

[0003] Thermoplastic resin compositions containing functional fillers in engineering plastics are also known. For example, Patent Document 1 describes a low-pollution injection molded article formed from a resin composition containing a specified amount of a thermoplastic resin component containing crystalline thermoplastic resin and an amorphous thermoplastic resin, a carbon precursor, and a conductive filler, which can strictly control the surface resistivity to a desired value in the semi-conductive field, and the amount of foreign particles generated is significantly reduced.

[0004] Patent document 2 discloses a flame-retardant polyimide molding material containing a semi-aromatic polyimide resin and a specified amount of graphite, carbon fiber, etc., which has excellent molding processability and can exhibit high flame retardancy.

[0005] However, in devices that use contact probes, such as wafer inspection probe cards and printed circuit board inspection fixtures, it is known that the holding part and guiding part of the contact probe use a plate-shaped thermoplastic resin molded body with multiple precision holes machined on a super engineering plastic molded body or a ceramic molded body (see, for example, Patent Document 3).

[0006] Here, if a hole is drilled in a thermoplastic resin molded body, burrs are generated around the opening of the hole. Patent Document 3 discloses that when drilling a hole in a resin molded body formed from a resin composition containing a thermoplastic resin having specified thermal properties, the above-mentioned problem can be solved by drilling with a drill bit of a specific diameter.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2005-290328

[0010] Patent Document 2: International Publication No. 2021 / 024624

[0011] Patent Document 3: Japanese Patent Application Publication No. 2007-90492 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] The cutting method for thermoplastic resin molded articles disclosed in Patent Document 3 utilizes a drill bit to perform hole-making on the resin molded article. However, in components used for probe cards and printed circuit board inspection fixtures, there are limitations in the machining accuracy of cutting with a drill bit when finer hole-making is required.

[0014] Laser processing allows for finer machining compared to cutting with a drill bit. However, the required physical properties of the thermoplastic resin molded body vary depending on the processing method.

[0015] The objective of this invention is to provide a probe card component or a printed circuit board inspection fixture component that achieves high-precision micro-machining, particularly when laser processing is used to form fine through holes, resulting in less burr generation and a high degree of precision. The invention also includes a method for manufacturing the same.

[0016] Solution for solving the problem

[0017] The inventors have discovered that the above-mentioned problems can be solved by using a specified thermoplastic resin composition in the manufacture of components for probe cards or components for printed circuit board inspection fixtures and the same.

[0018] That is, the present invention relates to the following.

[0019] [1] A component, which is a component for a probe card or a component for a printed circuit board inspection fixture.

[0020] The component is composed of a thermoplastic resin composition, the thermoplastic resin composition containing:

[0021] Component (A): At least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resins (a1) with a melting point of 270°C or higher and amorphous thermoplastic resins (a2) with a glass transition temperature of 200°C or higher, and

[0022] Component (B): Inorganic filler material containing zirconium oxide (b1),

[0023] 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).

[0024] [2] According to the component described in [1], wherein the component (a1) comprises a polyimide resin (a1-1), the polyimide resin (a1-1) comprising repeating structural units shown in formula (1) and repeating structural units shown in formula (2), wherein the content of repeating structural units of formula (1) is 20 to 70 mol% relative to the total of repeating structural units of formula (1) and repeating structural units of formula (2).

[0025]

[0026] (R1 is a divalent group with 6 to 22 carbons containing at least one alicyclic hydrocarbon structure, R2 is a divalent chain aliphatic group with 5 to 16 carbons, and X1 and X2 are each independently a tetravalent group with 6 to 22 carbons containing at least one aromatic ring.)

[0027] [3] The component according to [1] or [2], wherein the median volume diameter (D50) of the zirconium oxide (b1) is less than 1 µm.

[0028] [4] The component 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% by mass or more.

[0029] [5] The component according to any one of [1] to [4], wherein the component (B) further comprises an inorganic filler material (b2) other than the component (b1), the inorganic filler material (b2) comprising at least one selected from the group consisting of talc, mica, silicon dioxide, alumina, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, calcium carbonate and titanium oxide.

[0030] [6] According to the component described in [5], the content of the inorganic filler (b2) is 1 to 40 parts by mass relative to 100 parts by mass of component (A) in the thermoplastic resin composition.

[0031] [7] The component according to any one of [1] to [6], wherein the component has a plate-shaped portion and a plurality of through holes in the plate-shaped portion that are approximately circular with an opening diameter of 400µm or less or approximately square with one side of the opening having a length of 400µm or less.

[0032] [8] The component according to any one of [1] to [7], wherein the component is a probe holding component or a probe guiding component.

[0033] [9] A method for manufacturing a probe card component or a printed circuit board inspection fixture component as described in any one of [1] to [8], the method comprising the following steps (I) and (II) in sequence.

[0034] Step (I) is a step in which the following thermoplastic resin composition is molded by thermoforming to obtain a molded body having a plate-like portion.

[0035] The thermoplastic resin composition contains:

[0036] Component (A): At least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resins (a1) with a melting point of 270°C or higher and amorphous thermoplastic resins (a2) with a glass transition temperature of 200°C or higher, and

[0037] Component (B): Inorganic filler material containing zirconium oxide (b1),

[0038] 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).

[0039] Step (II) is a step in which multiple through holes are formed in the plate-shaped portion of the formed body by cutting or laser processing.

[0040]

[10] According to the manufacturing method described in [9], the thermoforming method in the process (I) is injection molding, extrusion molding or compression molding.

[0041]

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

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

[0042] The effects of the invention

[0043] According to the present invention, a probe card component or a printed circuit board inspection fixture component, which has achieved high-precision micro-machining, is provided, particularly when laser processing is used to form fine through holes, resulting in less burr generation and a high degree of precision. A method for manufacturing the same is also provided. Attached Figure Description

[0044] Figure 1 This is a plan view of the molded body 200 produced in process (I) of Example 1.

[0045] Figure 2 This is an observation image of the through hole with a circular opening shape made in Example 1.

[0046] Figure 3 This is an observation image of the through hole with a square opening shape made in Example 1.

[0047] Figure 4 This is an observation image of the through hole with a circular opening shape made in Example 2.

[0048] Figure 5 This is an observation image of the through hole with a square opening shape made in Example 2. Detailed Implementation

[0049] [definition]

[0050] In this specification, "a component that has undergone high-precision micro-machining" refers to a component in which multiple through holes are formed at a narrow spacing. This results in minimal breakage and scorching of the partition walls between the openings of these through holes, minimal burr formation, and minimal deviations in the shape of the openings. Furthermore, when the opening shape is square, the corners do not become rounded, and the shape reproducibility is high. The through holes referred to here are preferably micro-through holes with an opening diameter or the length of one side of the opening of 400µm or less, more preferably 200µm or less, even more preferably 100µm or less, even more preferably less than 50µm, even more preferably 40µm or less, and even more preferably 30µm or less. Additionally, the narrow spacing referred to here is, for example, a range exceeding one and less than five times the opening diameter or the length of one side of the opening.

[0051] Regarding the precision of the micro-machining of the components, specifically, it can be evaluated using the methods described in the examples.

[0052] [Components for probe cards or components for printed circuit board inspection fixtures]

[0053] The probe card component or printed circuit board inspection fixture component of the present invention (hereinafter referred to as "the component of the present invention") is composed of a thermoplastic resin composition.

[0054] The thermoplastic resin composition contains:

[0055] Component (A): At least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resins (a1) with a melting point of 270°C or higher and amorphous thermoplastic resins (a2) with a glass transition temperature of 200°C or higher, and

[0056] Component (B): Inorganic filler material containing zirconium oxide (b1),

[0057] 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). As will be described later, the volume median particle size (D50) of zirconium oxide (b1) is preferably 1 µm or less.

[0058] By having the above-described configuration, the present invention provides a probe card component or a printed circuit board inspection fixture component that achieves high-precision micro-machining, particularly when forming fine through holes using laser processing, with less burr generation and more.

[0059] The reasons for achieving the above-mentioned effects in this invention are not yet clear, but are believed to be as follows.

[0060] The component of the present invention is composed of the aforementioned thermoplastic resin composition, which contains at least one thermoplastic resin (A) selected from the group consisting of a crystalline thermoplastic resin (a1) with a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) with a glass transition temperature of 200°C or higher. By including component (A) in the thermoplastic resin composition, components of arbitrary shapes can be easily manufactured by thermoforming. Furthermore, in the case where the component of the present invention is, for example, a holding member or guiding member for a probe, the following steps are required: thermoforming the thermoplastic resin to form a molded body, and then forming fine through-holes at narrow intervals on the molded body by cutting with a drill bit, laser processing, or the like. Here, by making the thermoplastic resin (A) have a specified or higher heat resistance, it can withstand the heat energy generated during the forming of fine through-holes on the molded body composed of the thermoplastic resin composition, during cutting with a drill bit, and during laser processing. Therefore, it is considered that melting and dimensional changes during the processing of the molded body are suppressed, and the formation of fine through-holes can be achieved with high precision.

[0061] Furthermore, the thermoplastic resin composition contains a specified amount of inorganic filler as component (B), which includes zirconium oxide (b1). It is believed that by using submicron-sized, minute zirconium oxide (b1) particles as the inorganic filler, unevenness caused by the particles in the resulting molded body can be suppressed. When forming fine through-holes on the molded body, the walls of the fine through-holes also remain smooth, thus improving micro-machining precision and suppressing the breakage of the partition walls between the openings of the through-holes, as well as suppressing deviations in the shape of the openings. Moreover, it is presumed that by containing a specified amount of a high-hardness component (b1) relative to the thermoplastic resin (A), the material is moderately embrittled, which can suppress the generation of burrs.

[0062] In this specification, "component for probe card" refers to a component that constitutes at least a part of a probe card, and "component for printed circuit board inspection fixture" refers to a component that constitutes at least a part of a printed circuit board inspection fixture.

[0063] It should be noted that probe cards are devices used in the so-called front-end processes of semiconductor manufacturing, while printed circuit board inspection fixtures are fixtures used for inspecting printed circuit boards. Therefore, these components are different from the components used for inspecting IC sockets in subsequent processes of semiconductor manufacturing.

[0064] There are no particular limitations on the components of the present invention as long as they are components for probe cards or components for printed circuit board inspection fixtures. From the viewpoint of requiring high-precision micro-machining, probe holding components or probe guiding components in probe card components and components for printed circuit board inspection fixtures are preferred.

[0065] The component of the present invention preferably has a plate-like portion and a plurality of through holes extending through the thickness direction of the plate-like portion.

[0066] More specifically, the component of the present invention is preferably a component having a plate-like portion and having a plurality of through holes in the plate-like portion that are approximately circular with an opening diameter of 400µm or less, or approximately square with one side of the opening having a length of 400µm or less. The opening diameter or the length of one side of the opening is more preferably 200µm or less, further preferably 100µm or less, even more preferably less than 50µm, even more preferably 40µm or less, and even more preferably 30µm or less.

[0067] Furthermore, from the viewpoint of serving as a holding member or a guiding member for a probe, the diameter of the opening or the length of one side of the opening is preferably 5µm or more, and more preferably 10µm or more.

[0068] Preferably, the plurality of through holes are arranged regularly, and the spacing between the through holes is, for example, more than 1 and less than 5 times the diameter of the opening or the length of one side of the opening, more preferably in the range of 1.1 to 3 times.

[0069] The diameter of the opening or the length of one side of the opening and the spacing can be measured, for example, using a high-precision image size measuring instrument and the method described in the embodiments.

[0070] The through hole does not need to be formed on the entire surface of the plate-shaped portion; it only needs to be formed on at least a portion of the plate-shaped portion.

[0071] <Thermoplastic Resin Composition>

[0072] The thermoplastic resin composition constituting the component of the present invention comprises: component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) with a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) with a glass transition temperature of 200°C or higher; and component (B): an inorganic filler material 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).

[0073] <Thermoplastic Resin (A)>

[0074] The thermoplastic resin (A) used in this invention (hereinafter also referred to as "component (A)" or "thermoplastic resin (A)") is selected from at least one of the group consisting of crystalline thermoplastic resin (a1) with a melting point of 270°C or higher and amorphous thermoplastic resin (a2) with a glass transition temperature of 200°C or higher.

[0075] In this specification, crystalline thermoplastic resin refers to resin with a melting point and a glass transition temperature, while amorphous thermoplastic resin refers to resin with a glass transition temperature but no melting point. It should be noted 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.

[0076] (Crystall thermoplastic resin (a1))

[0077] From the perspective of manufacturing components that have undergone high-precision micro-processing, the crystalline thermoplastic resin (a1) used as component (A) (hereinafter also referred to as "component (a1)") is a crystalline thermoplastic resin with a melting point of 270°C or higher.

[0078] From the viewpoint of manufacturing components that have undergone high-precision micro-machining, 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. Furthermore, 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.

[0079] The melting point of component (a1) can be determined using a differential scanning calorimeter, specifically by the method described in the examples.

[0080] The glass transition temperature (Tg) of component (a1) is not particularly limited. From the viewpoint of manufacturing components with high-precision micro-machining, it is preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher. 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.

[0081] The glass transition temperature of component (a1) can be determined using a differential scanning calorimeter, specifically by the method described in the examples.

[0082] (Amorphous thermoplastic resin (a2))

[0083] From the perspective of manufacturing components that have undergone high-precision micro-processing, the amorphous thermoplastic resin (a2) used as component (A) (hereinafter also referred to as "component (a2)") is an amorphous thermoplastic resin with a glass transition temperature of 200°C or higher.

[0084] From the viewpoint of manufacturing components with high-precision micro-machining, 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. 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.

[0085] The glass transition temperature of component (a2) can be determined by the same method described above.

[0086] As component (A), examples include, for example, thermoplastic resins equivalent to any of component (a1) or component (a2) from polyimide resin, polyamide resin, polyetherimide resin, polyetherimide sulfone resin, polyphenylene sulfide resin, polyetheretherketone resin, polyetherketone ketone resin, polycarbonate resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, liquid crystal polymer, fully aromatic polyester resin other than liquid crystal polymer, polyetherketone resin, polyetheretherketone ketone resin, polybenzimidazole resin and polyphenylene ether resin.

[0087] From the viewpoint of manufacturing components that have undergone high-precision micro-processing, component (A) preferably comprises at least one selected from the group consisting of polyimide resin, polyetherimide resin, polyetherimide sulfone resin, polyphenylene sulfide resin, polyetheretherketone resin, polyetherketoneketone resin, liquid crystal polymer, and all-aromatic polyester resin other than liquid crystal polymer. More preferably, it comprises at least one selected from the group consisting of polyimide resin, polyetherimide resin, polyphenylene sulfide resin, and polyetheretherketone resin. It should be noted that when low dielectric properties are required for the component, component (A) is more preferably a polyimide resin, especially a polyimide resin with an aliphatic structure (other than all-aromatic) or a polyimide resin with a halogen or other bulky structure.

[0088] As component (A), component (a1), component (a2), or a mixture of component (a1) and component (a2) may be used.

[0089] When using a thermoplastic resin with a high melting point and / or glass transition temperature as component (A), dimensional changes in the high-temperature region of the component can be suppressed, which is therefore preferable. Particularly when component (A) includes a crystalline thermoplastic resin (a1), the reinforcing effect of compounding component (A) with component (B) is strongly exerted, further suppressing dimensional changes in the high-temperature region of the resulting component. For example, the coefficient of linear expansion of the component at temperatures of 25–200°C can be made to be 100 ppm / K or less. This can be achieved by increasing the amount of crystalline thermoplastic resin (a1) in the formulation, or by using it in conjunction with additives that shrink at high temperatures, resulting in a coefficient of linear expansion of the component at temperatures of 25–200°C of tens to several ppm / K. Furthermore, the crystalline thermoplastic resin (a1) can suppress water absorption, thus also suppressing dimensional changes in the component relative to moisture absorption. For example, the coefficient of hygroscopic expansion of the component can be set to 20 ppm / %RH or less.

[0090] From the viewpoint of manufacturing components that have undergone high-precision micro-processing, component (A) preferably includes component (a1) as a crystalline thermoplastic resin.

[0091] From the viewpoint of manufacturing components that have undergone high-precision micro-machining, 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, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and is 100% by mass or less.

[0092] When component (A) includes component (a1), from the viewpoint of manufacturing components with high precision micro-machining and ease of thermoforming, component (a1) more preferably includes polyimide resin, and more preferably includes polyimide resin (a1-1) which includes repeating structural units shown in formula (1) and repeating structural units shown in formula (2). The content ratio of repeating structural units in formula (1) is 20 to 70 mol relative to the total of repeating structural units in formula (1) and repeating structural units in formula (2).

[0093] From the viewpoint of manufacturing components that have undergone high-precision micro-processing, the content of polyimide resin (a1-1) in component (a1) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and is 100% by mass or less.

[0094]

[0095] (R1 is a divalent group with 6 to 22 carbons containing at least one alicyclic hydrocarbon structure, R2 is a divalent chain aliphatic group with 5 to 16 carbons, and X1 and X2 are each independently a tetravalent group with 6 to 22 carbons containing at least one aromatic ring).

[0096] Polyimide resin (a1-1) is a crystalline thermoplastic resin, preferably in powder or granule form. This polyimide resin differs from polyimide resins that do not have a glass transition temperature (Tg) due to ring closure of the imide ring after molding in the form of a polyimide precursor such as polyamic acid, or polyimide resins that decompose at temperatures below the glass transition temperature.

[0097] When manufacturing the components of the present invention, especially when laser processing is performed on the molded body to form fine through holes, the thermoplastic resin composition and the molded body require laser processing adaptability. According to the research of the inventors, laser processing adaptability is not necessarily the same as machining adaptability; for example, a higher melting point or glass transition temperature of the thermoplastic resin (A) does not necessarily mean better laser processing adaptability. The reason is not yet certain, but it is speculated that if polyimide resin (a1-1) is used as the thermoplastic resin (A), a heat resistance balance to laser can be ensured, melting / evaporation of the thermoplastic resin composition in the laser-irradiated area can be easily performed, burr generation and evaporation residue can be prevented, and the heat resistance around the laser-irradiated area can be sufficiently ensured, thus suppressing melting and dimensional changes caused by laser irradiation. Therefore, it is speculated that the processing adaptability is excellent when laser processing is performed on the molded body to form multiple through holes, and components with high-precision micro-machining can be obtained.

[0098] The repeating structural unit of equation (1) will be described in detail below.

[0099] R1 is a divalent group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure. Here, an alicyclic hydrocarbon structure refers to a ring derived from an alicyclic hydrocarbon compound, which can be saturated or unsaturated, and can be monocyclic or polycyclic.

[0100] Examples of alicyclic hydrocarbon structures include cycloalkane rings such as cyclohexane rings, cycloolefin rings such as cyclohexene rings, bicyclic alkane rings such as norbornane rings, and bicyclic olefin rings such as norbornene rings, but these are not limited to these. Among them, cycloalkane rings are preferred, more preferably cycloalkane rings with 4 to 7 carbon atoms, and even more preferably cyclohexane rings.

[0101] The number of carbon atoms in R1 is 6 to 22, preferably 8 to 17.

[0102] R1 contains at least one alicyclic hydrocarbon structure, preferably one to three.

[0103] R1 is preferably a divalent group as shown in formula (R1-1) or (R1-2).

[0104]

[0105] (m 11 and m 12 Each is an independent integer from 0 to 2, preferably 0 or 1. 13 ~m 15 Each is an independent integer from 0 to 2, preferably 0 or 1.

[0106] R1 is particularly preferred to be a divalent group as shown in the following formula (R1-3).

[0107]

[0108] It should be noted that in the divalent groups shown in the above formula (R1-3), the positional relationship of the two methylene groups relative to the cyclohexane ring can be either cis or trans. In addition, the ratio of cis to trans can be any value.

[0109] X1 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring. The aromatic ring can be a monocyclic or fused ring, and examples include benzene rings, naphthalene rings, anthracene rings, and tetraphenyl benzo[a]benzene rings, but are not limited to these. Among them, benzene rings and naphthalene rings are preferred, and benzene rings are more preferred.

[0110] X1 has 6 to 22 carbon atoms, preferably 6 to 18.

[0111] X1 contains at least one aromatic ring, preferably one to three.

[0112] X1 is preferably a tetravalent group represented by any of the following formulas (X-1) to (X-4).

[0113]

[0114] (R 11 ~R 18 Each is an alkyl group having 1 to 4 carbon atoms. 11 ~p 13 Each is an independent integer from 0 to 2, preferably 0. 14 p 15 p 16 and p 18 Each is an independent integer from 0 to 3, preferably 0. 17 It is an integer from 0 to 4, preferably 0. L 11 ~L 13 Each group can be independently a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.

[0115] It should be noted that X1 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring, therefore R in formula (X-2) 12 R 13 p 12 and p 13 The method is chosen such that the number of carbon atoms in the tetravalent group shown in formula (X-2) falls within the range of 10 to 22.

[0116] Similarly, L in equation (X-3) 11 R 14 R 15 p 14 and p 15 The choice of L in formula (X-4) is made in such a way that the number of carbon atoms in the tetravalent group shown in formula (X-3) falls within the range of 12 to 22. 12 L 13 R 16 R 17 R 18 p 16 p 17 and p 18 The method is chosen such that the number of carbon atoms in the tetravalent group shown in formula (X-4) falls within the range of 18 to 22.

[0117] X1 is particularly preferred to be a tetravalent group as shown in formula (X-5) or (X-6).

[0118]

[0119] Next, the repeating structural unit of equation (2) will be described in detail below.

[0120] R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, preferably with 6 to 14 carbon atoms, more preferably with 7 to 12 carbon atoms, and even more preferably with 8 to 10 carbon atoms. Here, the chain aliphatic group refers to a group derived from a chain aliphatic compound, which can be saturated or unsaturated, straight-chain or branched, and can contain heteroatoms such as oxygen atoms.

[0121] R2 is preferably an alkylene group having 5 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 7 to 12 carbon atoms, with 8 to 10 carbon atoms being the most common. The alkylene group can be a straight-chain alkylene group or a branched alkylene group, with a preference for a straight-chain alkylene group.

[0122] R2 is preferably selected from at least one of the groups consisting of octamethylene and decamethylene, more preferably octamethylene.

[0123] Another preferred form of R2 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. Preferably, it is a divalent group represented by the formula (R2-1) or (R2-2) below.

[0124]

[0125] (m 21 and m 22 Each is an integer from 1 to 15, preferably from 1 to 13, more preferably from 1 to 11, and even more preferably from 1 to 9. 23 ~m 25 Each of the integers is independently an integer from 1 to 14, preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.

[0126] It should be noted that R2 is a divalent chain aliphatic group with 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), therefore m in formula (R2-1) 21 and m 22 The method of selection is such that the number of carbons in the divalent group shown in formula (R2-1) falls within the range of 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10). That is, m 21 +m 22 The value is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10).

[0127] Similarly, m in equation (R2-2) 23 ~m 25 The method of selection is such that the number of carbons in the divalent group shown in formula (R2-2) falls within the range of 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10). That is, m 23 +m 24 +m 25 The carbon number is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10).

[0128] X2 is defined in the same way as X1 in equation (1), and the preferred method is also the same.

[0129] The content ratio of the repeating structural units in formula (1) is 20-70 mol%, relative to the sum of the repeating structural units in formula (1) and formula (2). When the content ratio of the repeating structural units in formula (1) is within the above range, the polyimide resin (a1-1) can be sufficiently crystallized even in a normal injection molding cycle. If the content ratio is less than 20 mol%, the thermoformability decreases; if it exceeds 70 mol%, the crystallinity decreases, and therefore the heat resistance decreases.

[0130] From the viewpoint of exhibiting high crystallinity, the content of the repeating structural unit in formula (1) 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, relative to the total of the repeating structural units in formula (1) and formula (2).

[0131] Of which, relative to the total of the repeating structural units of formula (1) and formula (2), the content of the repeating structural units of formula (1) is preferably 20 mol% or more and less than 40 mol%. When it is in this range, the crystallinity of the polyimide resin (a1-1) becomes higher, and a resin composition with better heat resistance can be obtained.

[0132] From the viewpoint of manufacturing components that have undergone high-precision micro-machining, the above-mentioned content ratio is preferably 25 mol% or more, more preferably 28 mol% or more, even more preferably 30 mol% or more, and even more preferably 32 mol% or more. From the viewpoint of exhibiting high crystallinity, it is even more preferably 38 mol% or less, even more preferably 36 mol% or less, and even more preferably 35 mol% or less.

[0133] The total content of the repeating structural units of formula (1) and formula (2) relative to all repeating structural units constituting polyimide resin (a1-1) is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, even more preferably 80 to 100 mol%, and even more preferably 85 to 100 mol%.

[0134] The polyimide resin (a1-1) may further contain repeating structural units of formula (3) below. In this case, the content ratio of repeating structural units of formula (3) is preferably 25 mol% or less, relative to the total of repeating structural units of formula (1) and repeating structural units of formula (2). On the other hand, there is no particular limitation on the lower limit, and it is acceptable to exceed 0 mol%.

[0135] From the viewpoint of improving heat resistance, the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less.

[0136]

[0137] (R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring. X3 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring.)

[0138] R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring. The aromatic ring can be a monocyclic or fused ring, and examples include benzene rings, naphthalene rings, anthracene rings, and tetraphenylbenzene rings, but are not limited to these. Among them, benzene rings and naphthalene rings are preferred, and benzene rings are more preferred.

[0139] The number of carbon atoms in R3 is 6 to 22, preferably 6 to 18.

[0140] R3 contains at least one aromatic ring, preferably one to three.

[0141] Furthermore, monovalent or divalent electron-withdrawing groups can be bonded to the aromatic ring. Examples of monovalent electron-withdrawing groups include nitro, cyano, p-toluenesulfonyl, halogen, haloalkyl, phenyl, and acyl groups. Examples of divalent electron-withdrawing groups include fluoroalkylene groups (e.g., -C(CF3)2-, -(CF2)). p Besides alkyl halides such as -(where p is an integer from 1 to 10), other examples include -CO-, -SO2-, -SO-, -CONH-, -COO-, etc.

[0142] R3 is preferably a divalent group as shown in formula (R3-1) or (R3-2).

[0143]

[0144] (m 31 and m 32 Each is an independent integer from 0 to 2, preferably 0 or 1. 33 and m 34 Each is an independent integer from 0 to 2, preferably 0 or 1. R 21 R 22 and R 23 Each can be 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 It is an integer from 0 to 4, preferably 0. L 21 It can be a single bond, ether group, carbonyl group, or an alkylene group having 1 to 4 carbon atoms.

[0145] It should be noted that R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring, therefore m in formula (R3-1) 31m 32 R 21 and p 21 The method is chosen such that the number of carbons in the divalent group shown in formula (R3-1) falls within the range of 6 to 22.

[0146] Similarly, L in equation (R3-2) 21 m 33 m 34 R 22 R 23 p 22 and p 23 The method is chosen such that the number of carbon atoms in the divalent group shown in formula (R3-2) falls within the range of 12 to 22.

[0147] X3 is defined in the same way as X1 in equation (1), and the preferred method is also the same.

[0148] The polyimide resin (a1-1) may further contain repeating structural units as shown in formula (4).

[0149]

[0150] (R4 represents -SO2- or -Si(R) x (R) y The divalent group of O-, R x and R y Each of the following groups independently represents a chain-like aliphatic group or a phenyl group having 1 to 3 carbon atoms. X4 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.

[0151] X4 is defined in the same way as X1 in equation (1), and the preferred method is also the same.

[0152] The end structure of the polyimide resin (a1-1) is not particularly limited, but it is preferred to have a chain aliphatic group with 5 to 14 carbon atoms at the end.

[0153] The chain-like aliphatic group can be saturated or unsaturated, and can be linear or branched. When the polyimide resin (a1-1) has the above-mentioned specific groups at the ends, a resin composition with excellent heat aging resistance can be obtained.

[0154] Examples of saturated chain aliphatic groups with 5 to 14 carbon atoms include n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, lauryl, n-tetrazyl, n-tetradecyl, isopentyl, neopentyl, 2-methylpentyl, 2-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, isooctyl, 2-ethylhexyl, 3-ethylhexyl, isononyl, 2-ethyloctyl, isodecyl, isododecyl, isotridecyl, isotetradecyl, etc.

[0155] Examples of unsaturated chain aliphatic groups with 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.

[0156] The aforementioned chain-like aliphatic group is preferably a saturated chain-like aliphatic group, more preferably a saturated linear aliphatic group. Furthermore, from the viewpoint of obtaining heat aging resistance, the aforementioned chain-like aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, preferably 12 or fewer carbon atoms, more preferably 10 or fewer carbon atoms, and even more preferably 9 or fewer carbon atoms. The aforementioned chain-like aliphatic group may be of only one type or two or more types.

[0157] The aforementioned chain-like aliphatic group is particularly preferably selected from at least one of the group consisting of n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isonyl, n-decyl, and isodexyl; more preferably selected from at least one of the group consisting of n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, and isonyl; and most preferably selected from at least one of the group consisting of n-octyl, isooctyl, and 2-ethylhexyl.

[0158] Furthermore, from the viewpoint of heat aging resistance, the polyimide resin (a1-1) preferably has only chain aliphatic groups with 5 to 14 carbon atoms at its ends, in addition to terminal amino and terminal carboxyl groups. When the ends have groups other than those mentioned above, their content is preferably 10 mol% or less, more preferably 5 mol% or less, relative to the chain aliphatic groups with 5 to 14 carbon atoms.

[0159] From the viewpoint of exhibiting excellent heat aging resistance, the content of the aforementioned chain aliphatic groups with 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, relative to 100 mol% of all repeating structural units constituting the polyimide resin (a1-1). Furthermore, to ensure sufficient molecular weight and obtain good mechanical properties, the content of the aforementioned chain aliphatic groups with 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, relative to 100 mol% of all repeating structural units constituting the polyimide resin (a1-1).

[0160] The “total of all repeating structural units constituting polyimide resin (a1-1)” mentioned here refers to the total of repeating structural units shown in equations (1), (2), (3), and (4).

[0161] The content of the chain aliphatic groups with carbon numbers of 5 to 14 in the polyimide resin (a1-1) can be determined by depolymerizing the polyimide resin (a1-1).

[0162] The polyimide resin (a1-1) preferably has a melting point of 360°C or lower and a glass transition temperature of 150°C or higher. From the viewpoint of manufacturing components with high-precision micro-machining, the melting point of the polyimide resin (a1-1) is more preferably 280°C or higher, and even more preferably 290°C or higher. From the viewpoint of ease of thermoforming, it is preferably 345°C or lower, more preferably 340°C or lower, and even more preferably 335°C or lower. Furthermore, from the viewpoint of manufacturing components with high-precision micro-machining, the glass transition temperature of the polyimide resin (a1-1) is more preferably 160°C or higher, more preferably 170°C or higher. 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.

[0163] From the viewpoint of heat resistance, 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 molding processability, it is preferably 350°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower.

[0164] From the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the heat of fusion Hm of polyimide resin (a1-1) is preferably 5.0 mJ / mg or more, more preferably 10 mJ / mg or more, and even more preferably 17 mJ / mg or more. There is no particular upper limit to the heat of fusion Hm, which is typically 45 mJ / mg or less.

[0165] The heat of fusion Hm of polyimide resin (a1-1) was determined by differential scanning calorimetry and calculated from the area of ​​the heat of fusion peak (endothermic peak) near the melting point observed when 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 cooling rate of 20°C / min and then heated again at a heating rate of 10°C / min to melt.

[0166] Furthermore, from the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the heat of crystallization Hc of the polyimide resin (a1-1) is preferably 5.0 mJ / mg or higher, more preferably 10 mJ / mg or higher, and even more preferably 17 mJ / mg or higher. There is no particular upper limit to the heat of crystallization Hc, which is typically 45 mJ / mg or lower.

[0167] The heat of crystallization Hc of polyimide resin (a1-1) refers to the heat of the crystallization heat peak observed when polyimide resin (a1-1) is melted and cooled at a cooling rate of 20°C / min, as measured by a differential scanning calorimeter.

[0168] 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 determined using the methods described in the examples.

[0169] The logarithmic viscosity of a 0.5% by mass concentrated sulfuric acid solution of polyimide resin (a1-1) at 30°C is preferably 0.2 to 2.0 dL / g, more preferably in the range of 0.3 to 1.8 dL / g. When the logarithmic viscosity is 0.2 dL / g or higher, the resulting molded articles and components can obtain sufficient mechanical strength, and when it is 2.0 dL / g or lower, thermoforming and handling become good. The logarithmic viscosity µ is determined by measuring the flow time of concentrated sulfuric acid and the above-mentioned polyimide resin solution at 30°C using a Cannon-Fensk viscometer, and is calculated by the following formula.

[0170] µ=ln(ts / t0) / C

[0171] t0: Flow time of concentrated sulfuric acid

[0172] ts: Flow time of the polyimide resin solution

[0173] C: 0.5 (g / dL)

[0174] The weight-average molecular weight (Mw) of the polyimide resin (a1-1) is preferably 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 in the range of 35,000 to 65,000. When the weight-average molecular weight (Mw) of the polyimide resin (a1-1) is 10,000 or more, the resulting molded articles and components exhibit good mechanical strength; when it is 40,000 or more, the stability of mechanical strength is good; and when it is 150,000 or less, the thermoformability is good.

[0175] The weight-average molecular weight (Mw) of polyimide resin (a1-1) can be determined by gel filtration chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.

[0176] (Manufacturing method of polyimide resin (a1-1))

[0177] Polyimide resin (a1-1) can be manufactured by reacting a tetracarboxylic acid component with a diamine component. The tetracarboxylic acid component contains a tetracarboxylic acid comprising at least one aromatic ring and / or its derivatives, and the diamine component contains a diamine comprising at least one alicyclic hydrocarbon structure and a chain-like aliphatic diamine.

[0178] The tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxyl groups are directly bonded to the aromatic ring, and the structure may include alkyl groups. Furthermore, the tetracarboxylic acid preferably has 6 to 26 carbon atoms. Preferably, the tetracarboxylic acid comprises 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. More preferably, it comprises pyromellitic acid.

[0179] Examples of tetracarboxylic acid derivatives 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 anhydrides of tetracarboxylic acids include pyromellitic tetracarboxylic anhydride, pyromellitic tetracarboxylic anhydride, 2,3,5,6-toluenetetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, and 1,4,5,8-naphthalenetetracarboxylic anhydride. 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, and dimethyl 1,4,5,8-naphthalenetetracarboxylate. In the above-mentioned alkyl esters of tetracarboxylic acids, the alkyl group preferably has 1 to 3 carbon atoms.

[0180] Tetracarboxylic acids containing at least one aromatic ring and / or their derivatives may be used alone or in combination with at least one of the compounds selected above.

[0181] The diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, and for example, preferably contains 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), carvone diamine, limonene diamine, isophorone diamine, norbornene diamine, bis(aminomethyl)tricyclo[5.2.1.0] 2 ,6At least one compound selected from the group consisting of decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodicyclohexylpropane. These compounds can be used alone or in combination of two or more compounds selected from them. 1,3-bis(aminomethyl)cyclohexane is preferred. It should be noted that diamines containing alicyclic hydrocarbon structures generally have structural isomers, but the cis / trans ratio is not limited.

[0182] The chain-like aliphatic diamine can be linear or branched, and preferably has 5 to 16 carbon atoms, more preferably 6 to 14, and even more preferably 7 to 12. Furthermore, if the chain portion has 5 to 16 carbon atoms, it may contain ether bonds. Preferably, the chain-like aliphatic diamine comprises at least one selected from, for example, 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-tetrazomethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 2,2'-(ethylenedioxy)bis(ethylamine).

[0183] One or a mixture of multiple chain-like aliphatic diamines may be used. Among them, chain-like aliphatic diamines with 8 to 10 carbon atoms are preferred, and at least one selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine is particularly preferred.

[0184] When manufacturing polyimide resin (a1-1), the molar ratio of the amount of diamine containing at least one alicyclic hydrocarbon structure to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is preferably 20 to 70 mol%. This molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, 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, even more preferably 42 mol% or less, even more preferably less than 40 mol%, even more preferably 38 mol% or less, even more preferably 36 mol% or less, and even more preferably 35 mol% or less.

[0185] Furthermore, the aforementioned diamine component may contain a diamine comprising at least one aromatic ring. The diamine comprising at least one aromatic ring preferably has 6 to 22 carbon atoms, and examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,2-diethynylphenylenediamine, 1,3-diethynylphenylenediamine, 1,4-diethynylphenylenediamine, 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.

[0186] In the above, the molar ratio of the amount of diamine containing at least one aromatic ring 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, there is no particular limitation on the lower limit, and it is acceptable to exceed 0 mol%.

[0187] From the viewpoint of improving heat resistance, the molar ratio is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less.

[0188] Furthermore, from the viewpoint of reducing the 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%.

[0189] When manufacturing polyimide resin (a1-1), the ratio of the tetracarboxylic acid component to the diamine component is preferably 0.9 to 1.1 moles of diamine component for every 1 mole of tetracarboxylic acid component.

[0190] In addition, when manufacturing the polyimide resin (a1-1), a capping agent may be mixed in addition to the tetracarboxylic acid component and the diamine component. As the capping agent, at least one type selected from the group consisting of monoamines and dicarboxylic acids is preferred. The amount of capping agent used is sufficient to introduce the desired amount of terminal groups into the polyimide resin (a1-1), preferably 0.0001 to 0.1 mol relative to 1 mol of the tetracarboxylic acid and / or its derivatives, more preferably 0.001 to 0.06 mol, and even more preferably 0.002 to 0.035 mol.

[0191] Among them, monoamine end-capping agents are preferred. From the viewpoint that the heat aging resistance is improved by introducing the aforementioned chain aliphatic groups with 5 to 14 carbons into the end of the polyimide resin (a1-1), monoamines having chain aliphatic groups with 5 to 14 carbons are more preferred, and monoamines having saturated straight-chain aliphatic groups with 5 to 14 carbons are even more preferred.

[0192] The capping agent is particularly preferably selected from at least one of the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isonylamine, n-decylamine, and isodecanamine; more preferably selected from at least one of the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isonylamine; and even more preferably selected from at least one of the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

[0193] As a polymerization method for manufacturing polyimide resin (a1-1), a known polymerization method can be applied, such as the method described in International Publication No. 2016 / 147996.

[0194] From the viewpoint of manufacturing components with high-precision micro-machining and 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, further preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and is 100% by mass or less.

[0195] From the viewpoint of manufacturing components with high-precision micro-machining and ease of thermoforming, the content of component (A) in the thermoplastic resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, even more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more. Furthermore, from the viewpoint of manufacturing components with high-precision micro-machining, it is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0196] <Component (B): Inorganic filler material containing zirconium oxide (b1)>

[0197] The thermoplastic resin composition used in this invention contains an inorganic filler material comprising zirconium oxide (b1) as component (B).

[0198] By using the thermoplastic resin (A) and an inorganic filler material (B) containing a specified amount of zirconium oxide (b1), it is possible to manufacture components that have undergone high-precision micro-machining.

[0199] (Composition (b1): Zirconia)

[0200] The shape of the zirconium oxide (b1) used in this invention is not particularly limited, and examples include spherical, plate-like, flake-like, columnar, and fibrous shapes. From the viewpoint of manufacturing components that have undergone high-precision micro-machining, spherical or plate-like particles are preferred, and spherical particles are more preferred.

[0201] From the viewpoint of manufacturing components with high-precision micro-machining and from the viewpoint of availability, zirconia (b1) preferably has a small particle size. From the viewpoint of manufacturing components with high-precision micro-machining, for example, the volume median particle size (D50) of component (b1) is preferably 1 µm or less, more preferably 0.80 µm or less, further preferably 0.60 µm or less, even more preferably 0.50 µm or less, and even more preferably 0.40 µm or less. In addition, from the viewpoint of manufacturing components with high-precision micro-machining, and from the viewpoint of improved availability and operability, it is generally 0.01 µm or more, more preferably 0.02 µm or more, and even more preferably 0.05 µm or more.

[0202] The D50 of component (b1) can be determined using a laser diffraction light scattering particle size analyzer.

[0203] Commercially available zirconia particles used as component (b1) include, for example, the KZ series manufactured by Kyoritsu Materials Co., Ltd., the TZ series manufactured by Tosoh Co., Ltd., and the UEP series manufactured by Daiichi Rare Element Chemical Industry Co., Ltd. Among these, the high-purity zirconia "KZ-0Y-LSF" from the KZ series manufactured by Kyoritsu Materials Co., Ltd. is preferred.

[0204] From the viewpoint of manufacturing components that have undergone high-precision micro-machining, the content of component (b1) in component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0205] From the viewpoint of ease of thermoforming and the viewpoint of manufacturing components with high-precision micro-machining, the content of component (b1) is 2 to 40 parts by mass relative to 100 parts by mass of component (A) in the thermoplastic resin composition, preferably 5 to 35 parts by mass, more preferably 5 to 30 parts by mass, further preferably 10 to 30 parts by mass, and even more preferably 20 to 30 parts by mass.

[0206] (Component (b2): Inorganic filler material other than component (b1))

[0207] Component (B) may be an inorganic filler material consisting only of component (b1), or it may further contain inorganic filler material (b2) other than component (b1).

[0208] As a component (b2), examples include talc, mica, silicon dioxide, aluminum oxide, 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, zinc sulfide, etc., and one or more of them may be used.

[0209] From the viewpoint of manufacturing components with high-precision micro-machining, component (b2) preferably includes 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, it includes at least one selected from the group consisting of talc, mica, silica, and titanium oxide. Even more preferably, it includes at least one selected from the group consisting of talc and silica. And even more preferably, it includes talc.

[0210] The shape of component (b2) is not particularly limited, and examples include spherical, plate-like, scaly, columnar, and fibrous shapes. Among these, from the viewpoint of manufacturing components with high-precision micro-processing and from the viewpoint of availability, spherical or plate-like particles are preferred.

[0211] From the viewpoint of manufacturing components with high-precision micro-machining and from the viewpoint of availability, the volume median particle size (D50) of component (b2) is preferably 3µm or less, more preferably 2µm or less, further preferably 1.5µm or less, even more preferably 1.2µm or less, and even more preferably 1µm or less. Furthermore, from the viewpoint of manufacturing components with high-precision micro-machining, and from the viewpoint of improved availability and operability, it is generally 0.01µm or more, more preferably 0.05µm or more, and even more preferably 0.1µm or more.

[0212] The D50 of component (b2) can be determined using the same method as that of component (b1).

[0213] When using component (b2), from the viewpoint of ease of thermoforming and the viewpoint of manufacturing components with high-precision micro-machining, the content of component (b2) in component (B) is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 65% ​​by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more.

[0214] When using component (b2), from the viewpoint of manufacturing components that have undergone high-precision micro-processing, the content of component (b2) is preferably 1 to 40 parts by mass relative to 100 parts by mass of component (A) in the thermoplastic resin composition, more preferably 2 to 30 parts by mass, further preferably 5 to 30 parts by mass, and even more preferably 10 to 20 parts by mass.

[0215] From the viewpoint of ease of thermoforming and the viewpoint of manufacturing components with high-precision micro-machining, the content of component (B) is 2 to 60 parts by mass relative to 100 parts by mass of component (A) in the thermoplastic resin composition, preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, further preferably 15 to 45 parts by mass, even more preferably 20 to 45 parts by mass, even more preferably 25 to 45 parts by mass, and even more preferably 30 to 45 parts by mass.

[0216] <Additives>

[0217] The thermoplastic resin composition can be formulated with additives other than component (B), such as reinforcing fibers, matting agents, plasticizers, antistatic agents, anti-coloring agents, anti-gelling agents, colorants, slip modifiers, antioxidants, conductive agents, organic heat-resistant materials (thermosetting resin powder), and resin modifiers. In particular, the use of graphite, carbon black, graphite, Ketjen black, or carbon nanotubes as antistatic agents provides sufficient antistatic effects even in small amounts without hindering the properties of the thermoplastic resin composition, and is therefore preferred. Carbon nanotubes, in particular, exhibit sufficient antistatic effects even in small amounts and can suppress deterioration of microprocessability and thermoformability, making them even more preferable. It should be noted that commercially available carbon nanotubes include the NTF series manufactured by High Pressure Gas Industry Co., Ltd., the K-nanos series manufactured by Kumho Petrochemical, and the NC series manufactured by Nanocyl.

[0218] When using the above-mentioned additives, there is no particular limitation on their mixing amount. From the viewpoint of demonstrating the effect of the additives, in the thermoplastic resin composition, it is generally 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.

[0219] Furthermore, other resins besides thermoplastic resin (A) may be blended into the thermoplastic resin composition, provided that their properties are not impaired. When thermoplastic resin (A) and other resins besides thermoplastic resin (A) are used together, there are no particular restrictions on their blending ratio, as long as it does not impair the properties of the thermoplastic resin composition.

[0220] From the viewpoint of ease of thermoforming and the viewpoint of manufacturing components with high precision micro-machining, 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, further preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and is 100% by mass or less.

[0221] The thermoplastic resin composition can take any form, preferably granules.

[0222] The thermoplastic resin composition used in this invention can be granulated by, for example, by adding thermoplastic resin (A), inorganic filler (B), and various other optional components as needed, and then dry-mixing them; or by feeding inorganic filler (B) and optional components separately from the feed point of the extruder (different from the feed point of thermoplastic resin (A) into the extruder), then melt-mixing them in the extruder, extruding the filament, and cutting the filament. Furthermore, by feeding the granules into various forming machines and thermoforming them using the methods described later, the molded articles described later can be easily manufactured.

[0223] On the other hand, the molded article can also be obtained without going through the granular form. For example, by adding thermoplastic resin (A), inorganic filler (B), and various other arbitrary components as needed, and dry mixing them, the mixture is put into a mold and compressed by heating and pressing to obtain the molded article directly.

[0224] From the viewpoint of producing granules and performing compression molding, the thermoplastic resin composition used in this invention is preferably solvent-free. 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.

[0225] It should be noted that the thermoplastic resin composition used in this invention can also be used for purposes other than the components of this invention. Specifically, examples include gears, bearings, watch cases, jigs for semiconductor manufacturing machinery, conveying components, optical connectors, components for 3D printers, and components for aerospace applications.

[0226] [Method for manufacturing components]

[0227] The present invention also provides a method for manufacturing a probe card component or a printed circuit board inspection fixture component of the present invention, which sequentially comprises the following steps (I) and (II).

[0228] Step (I) is a step in which the following thermoplastic resin composition is molded by thermoforming to obtain a molded body having a plate-like portion.

[0229] The thermoplastic resin composition contains:

[0230] Component (A): at least one thermoplastic resin selected from the group consisting of a crystalline thermoplastic resin (a1) with a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) with a glass transition temperature of 200°C or higher, and...

[0231] Component (B): Inorganic filler material containing zirconium oxide (b1),

[0232] 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).

[0233] Step (II) is a step in which multiple through holes are formed in the plate-shaped portion of the formed body by cutting or laser processing.

[0234] <Process (I)>

[0235] Step (I) involves forming the thermoplastic resin composition by thermoforming to obtain a molded body having a plate-like portion.

[0236] The thermoplastic resin composition and its preferred method are the same as described above.

[0237] The molded body obtained in step (I) has a plate-like portion. This is for forming a through hole in the thickness direction of the plate-like portion of the molded body in step (II) described later. The molded body having the plate-like portion can be at least partially plate-shaped, or it can be a flat plate-shaped molded body that is entirely plate-shaped.

[0238] The thickness of the plate-shaped portion varies depending on the type of component being manufactured, and is preferably 0.1 to 20 mm, more preferably 0.5 to 10 mm, and even more preferably in the range of 0.5 to 5 mm.

[0239] A molded body having a plate-like portion can be manufactured by thermoforming the aforementioned thermoplastic resin composition. Examples of thermoforming methods include injection molding, extrusion molding, compression molding, blow molding, blow forming, vacuum forming, pneumatic forming, laser forming, welding, and fusion molding; any forming method involving a hot-melt process can be used. From the viewpoint of thermoforming granules of the aforementioned thermoplastic resin composition and then machining or laser-processing the resulting molded body in step (II) to form a through hole, the thermoforming method is preferably injection molding, extrusion molding, or compression molding. In particular, from the viewpoint of improving production efficiency, injection molding is preferred, and from the viewpoint of obtaining higher dimensional stability, extrusion molding is preferred.

[0240] The thermoforming conditions of 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 includes a step of thermoforming the thermoplastic resin composition at 290-380°C. Thermoforming can also be performed at temperatures greater than 380°C and below 400°C, but from the viewpoint of suppressing the deterioration of the thermoplastic resin (A) and other components, thermoforming at temperatures below 380°C is preferred. Specific steps include, for example, the following methods.

[0241] First, inorganic filler (B) and any other desired components are added to thermoplastic resin (A) and dry-mixed. This mixture is then fed into an extruder, preferably melted at 290–380°C, and melt-mixed and extruded to produce granules. Alternatively, thermoplastic resin (A) can be fed into an extruder, preferably melted at 290–380°C, and inorganic filler (B) and any other desired components can be added to it. This mixture is then melt-mixed with thermoplastic resin (A) in the extruder and extruded to produce the aforementioned granules.

[0242] After the above granules are dried, they are fed into various forming machines, preferably thermoforming at 290~380°C, to produce a molded body with a plate-like part.

[0243] The molded body obtained by the above thermoforming can be further processed by cutting to obtain a desired shape. For example, the thermoplastic resin composition can be used to make an injection molded body, which can then be processed by cutting to obtain a molded body with a desired shape.

[0244] From the viewpoint of further improving the machinability of the molded body and the fine machining properties in process (II), the molded body obtained by the above thermoforming is preferably further subjected to annealing. When the molded body obtained by thermoforming the thermoplastic resin composition and then further annealing has a low surface roughness on the machined surface during machining, and when it is a flat plate, it can produce a flat plate with less warping. Furthermore, multiple through holes can be formed with higher precision using this flat plate.

[0245] The annealing of the molded body described above is preferably performed after the thermoforming in step (I) and before the cutting process. Alternatively, the annealing can be performed after the thermoforming in step (I) and before the cutting process, and then annealed again after the cutting process.

[0246] 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), from the viewpoint of avoiding deformation of the molded body, the annealing temperature is a temperature lower than the melting point of the crystalline thermoplastic resin (a1). From the viewpoint of further improving the machinability and micro-processability 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 set to Tm (°C), the annealing temperature is preferably in the range of Tm-100°C to Tm-20°C. When the thermoplastic resin (A) is an amorphous thermoplastic resin (a2), from the viewpoint of avoiding deformation of the molded body, the annealing temperature is a temperature lower than the glass transition temperature of the amorphous thermoplastic resin (a2). From the viewpoint of further improving the machinability and micro-processability 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 set to Tg (°C), the annealing temperature is preferably in the range of Tg-100°C to Tg-20°C.

[0247] Regarding specific examples of annealing temperatures, when the thermoplastic resin (A) contains the polyimide resin (a1-1), from the viewpoint of further improving the machinability and micro-processability of the molded article, and from the viewpoint of avoiding deformation of the molded article, a range of 200~360°C is preferred, more preferably 220~340°C, even more preferably 240~330°C, and even more preferably 250~320°C is preferred.

[0248] There is no particular limitation on the annealing time, but from the viewpoint of further improving the machinability and micro-machinability of the formed article, as well as the viewpoint of improving manufacturing efficiency, it is preferably 1 to 180 minutes, and more preferably in the range of 5 to 150 minutes.

[0249] Annealing of the molded body can be performed using known heating devices.

[0250] After annealing, from the viewpoint of suppressing warping of the molded body caused by residual stress, it is preferable to slowly cool until the temperature reaches below 100°C.

[0251] From the viewpoint of improving the micro-machinability in process (II), the surface roughness of the plate-shaped portion of the molded article is preferably low. 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.

[0252] The arithmetic mean roughness (Ra) of the plate-shaped surface is obtained, for example, by measuring the arithmetic mean roughness of a continuous area with a length of 20 mm using a 3D shape measuring device (KEYENCE Co., Ltd. "VR-6000").

[0253] <Process (II)>

[0254] In step (II), multiple through holes are formed in the plate-shaped portion of the formed body obtained in step (I) by cutting or laser processing. According to the manufacturing method of the component of the present invention, even when multiple through holes are formed with a narrow spacing in step (II), high-precision micro-machining can be performed.

[0255] In process (II), when forming a through hole by cutting, an electric drill or similar tool can be used. Alternatively, when forming a through hole by laser processing, a laser processing machine or similar tool can be used.

[0256] From the viewpoint of achieving higher precision micro-machining, the processing method in step (II) is preferably laser processing. There are no particular limitations on the laser processing conditions; for example, lasers with wavelengths of 266–1066 nm can be used for micro-machining. In particular, UV lasers around 355 nm and deep ultraviolet lasers around 266 nm are preferred due to the high absorption rate of polyimide-based materials.

[0257] Example

[0258] Next, examples will be provided to illustrate the invention in more detail, but the invention is not limited thereto. Furthermore, various measurements and evaluations were performed in each manufacturing example and example.

[0259] <Infrared Spectroscopy Analysis (IR Measurement)>

[0260] The IR measurements of the polyimide resin were performed using a JIR-WINSPEC50 instrument manufactured by Nippon Electronics Co., Ltd.

[0261] <Logarithmic viscosity µ>

[0262] A polyimide resin solution obtained by drying the polyimide resin at 190-200°C for 2 hours and then dissolving 0.100 g of the polyimide resin in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Ltd.) was used as the test sample, and the viscosity was measured at 30°C using a Canon-Fensk viscometer. The logarithmic viscosity µ was calculated using the following formula.

[0263] µ=ln(ts / t0) / C

[0264] t0: Flow time of concentrated sulfuric acid

[0265] ts: Flow time of the polyimide resin solution

[0266] C: 0.5g / dL

[0267] Melting point, glass transition temperature, crystallization temperature, heat of fusion, heat of crystallization

[0268] The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, heat of fusion Hm, and heat of crystallization Hc of polyimide resin were determined using a differential scanning calorimeter (TA Instruments "DSC-25").

[0269] The following thermal process was applied to the test sample under a nitrogen atmosphere (nitrogen gas flow rate 50 mL / min). The thermal process consisted of a first heating (heating rate 10 °C / min), followed by cooling (cooling rate 20 °C / min), and then a second heating (heating rate 10 °C / min).

[0270] The melting point Tm is determined by reading the peak value of the endothermic peak observed during the second heating. The glass transition temperature Tg is determined by reading the value observed during the second heating. The crystallization temperature Tc is determined by reading the peak value of the exothermic peak observed during cooling. It should be noted that for Tm, Tg, and Tc, if multiple peaks are observed, the peak value of each peak should be read.

[0271] The heat of fusion Hm (mJ / mg) is calculated from the area of ​​the endothermic peak observed near the melting point when the sample is heated to a temperature above its melting point at a heating rate of 10°C / min, cooled at a cooling rate of 20°C / min, and then heated again at a heating rate of 10°C / min. Conversely, the heat of crystallization Hc (mJ / mg) is calculated from the area of ​​the exothermic peak observed when the sample is heated to a temperature above its melting point at a heating rate of 10°C / min, cooled at a cooling rate of 20°C / min.

[0272] <Semi-crystallization time>

[0273] The semi-crystallization time of the polyimide resin was determined using a differential scanning calorimeter (DSC-6220, manufactured by SII NanoTechnology Co., Ltd.).

[0274] Under a nitrogen atmosphere and at 420°C for 10 minutes to allow the polyimide resin to completely melt, a rapid cooling operation at a cooling rate of 70°C / min is performed. Calculate the time taken from the appearance of the observed crystallization peak to the peak being reached. It should be noted that in Table 1, cases with a semi-crystallization time of less than 20 seconds are denoted as "<20".

[0275] <Weight-average molecular weight>

[0276] The weight-average molecular weight (Mw) of the polyimide resin was determined using a gel filtration chromatography (GPC) apparatus, “Shodex GPC-101”, manufactured by Showa Denko Corporation, under the following conditions.

[0277] Column: Shodex HFIP-806M

[0278] Mobile phase solvent: HFIP containing 2 mM sodium trifluoroacetate

[0279] Column temperature: 40℃

[0280] Mobile phase flow rate: 1.0 mL / min

[0281] Sample concentration: approximately 0.1% by mass

[0282] Detector: IR detector

[0283] Injection volume: 100µm

[0284] Standard curve: Standard PMMA

[0285] Manufacturing Example 1 (Manufacturing of Crystalline Thermoplastic Polyimide Resin 1)

[0286] 500 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Emulsifier Co., Ltd.) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced into a 2L 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 form a homogeneous 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. The mixed diamine solution was slowly added using a plunger pump. The addition caused heat generation, but the internal temperature was adjusted to 40-80°C. Nitrogen gas was used throughout the addition of the mixed diamine solution, and the stirrer was rotated at 250 rpm. After the addition was complete, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.01 mol) of n-octylamine (manufactured by Kanto Chemical Co., Ltd.) as a capping agent were added, and the mixture was stirred further. At this stage, a pale yellow polyamic acid solution was obtained. Next, the stirring speed was set to 200 rpm, and the polyamic acid solution in the 2 L separable flask was heated to 190°C. During the heating process, precipitation of polyimide resin powder and dehydration accompanied by imidization were observed at a liquid temperature between 120-140°C. After maintaining the temperature at 190°C for 30 minutes, the mixture was allowed to cool naturally to room temperature and then filtered. The obtained polyimide resin powder was washed and filtered with 300g of 2-(2-methoxyethoxy)ethanol and 300g of methanol, and then dried at 180℃ for 10 hours to obtain 317g of crystalline thermoplastic polyimide resin 1 (hereinafter also referred to as "polyimide resin 1") powder.

[0287] The IR spectrum of polyimide resin 1 was measured, and the results were at ν(C=O) 1768 and 1697 (cm). -1 The characteristic absorption of the imide ring was confirmed. The logarithmic viscosity is 1.30 dL / g, Tm is 323℃, Tg is 184℃, Tc is 266℃, heat of fusion is 21.0 mJ / mg, heat of crystallization is 20.3 mJ / mg, semi-crystallization time is less than 20 seconds, and Mw is 55,000.

[0288] The composition and property evaluation results of the polyimide resin 1 obtained in Manufacturing Example 1 are shown in Table 1. It should be noted that the molar percentages of the tetracarboxylic acid and diamine components in Table 1 are values ​​calculated from the input amounts of each component during the manufacturing of the polyimide resin.

[0289] [Table 1]

[0290]

[0291] The abbreviations in Table 1 are as follows.

[0292] PMDA: Pyromellitic dianhydride

[0293] ·1,3-BAC: 1,3-bis(aminomethyl)cyclohexane

[0294] ·OMDA: 1,8-Octamethylenediamine

[0295] n-OcA: n-Ocylamine

[0296] Example 1

[0297] [Preparation of thermoplastic resin compositions]

[0298] The components (A) and (B) shown in Table 2 were thoroughly mixed by dry mixing. The resulting mixed powder was then extruded into wire with a diameter of 2-3 mm using a co-rotating twin-screw compounding extruder (Parker Corporation "HK-25D-41D", screw diameter: 25 mm) at a barrel temperature of 360°C and a screw speed of 120 rpm.

[0299] The extruded wire material is cooled by air and then granulated using a granulator ("FanCutter FC-Mini-4 / N" manufactured by Hoshi Plastic Co., Ltd.).

[0300] [Process (I): Fabrication of the flat, molded body]

[0301] The granules (thermoplastic resin composition) obtained by the above method were dried at 150°C for 10 hours, and then injection molded to produce a flat molded body by the following method. Using an injection molding machine (FANUC Corporation "Roboshot αoS30iA"), 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 with a diameter of 40 mm Φ and a thickness of 4 mm. This body was then heated at 300°C for 60 minutes in a hot air dryer and annealed.

[0302] Next, on one side of the resulting injection-molded body 100, on Figure 1 The indicated location is drilled to create a 5mm×5mm×3mm deep recess, forming a 200-shaped body.

[0303] Here, Figure 1This is a plan view of the molded body 200 produced in the above process (I) of Example 1, where 201 and 202 are the recesses.

[0304] [Process (II): Formation and evaluation of through holes]

[0305] Next, multiple through holes are formed on a portion (central part) of the bottom surface of the recesses 201 and 202 of the shaped body 200 produced in step (I) by laser processing.

[0306] Specifically, in the center of the bottom surface of the recess 201, 1,000 through holes with a diameter of 25µmΦ and a circular shape are formed at a spacing of 32µm and a partition wall of 7µm. In addition, in the center of the bottom surface of the recess 202, 1,000 through holes with a side length of 30µm and a square shape are formed with a partition wall of 7µm.

[0307] Laser processing is performed using a laser processing machine manufactured by Kataoka Manufacturing Co., Ltd.

[0308] The shape of the formed through hole was evaluated as follows. The evaluation results are shown in Table 2.

[0309] (Microfabrication Evaluation-1)

[0310] The through-holes formed by the method described were observed using a digital microscope (KEYENCE VHX-7000, 150x magnification). The micro-machining condition was evaluated based on the following items and criteria.

[0311] <Appearance (presence or absence of broken or charred partitions)>

[0312] A: No fractures or charring were observed in the partition wall.

[0313] C: The partition wall was observed to be broken or charred.

[0314] <The state of burrs>

[0315] A: No burrs were observed at all.

[0316] B: Burrs are present, but can be removed by air jetting.

[0317] C: It contains a large number of burrs, which are difficult to remove by air blowing.

[0318] (Microfabrication Evaluation-2)

[0319] The shape of the opening of the through hole formed by the method is observed and measured using a high-precision image size measuring instrument (KEYENCE Co., Ltd. "LM series"), and evaluated based on the following items and criteria.

[0320] <Roundness>

[0321] A: For all through holes with a circular opening shape, the diameter of the opening is within the range of 25.0±0.5µm.

[0322] C: Regarding through holes with a circular opening shape, there are those with an opening diameter exceeding 25.0±0.5µm.

[0323] <right angle>

[0324] For all through holes with a square opening shape, the curvature of the right-angle portion of the opening is measured, and the average value of this curvature is taken as the radius R (µm) and shown in Table 2. The smaller the value of R, the closer it is to a right angle, indicating that high-precision machining has been performed.

[0325] Example 2

[0326] In step (I) of Example 1, the forming method of the flat molded body was changed to extrusion molding, and the annealing temperature was changed to the temperature recorded in the table. Otherwise, the molding body was produced, step (II) was performed, and various evaluations were conducted using the same method as in Example 1. The evaluation results are shown in Table 2. Specifically, step (I) was performed by the following method.

[0327] [Process (I)]

[0328] After drying the granules (thermoplastic resin composition) obtained by the same method as in Example 1 at 150°C for 10 hours, the granules were extruded by the following method to produce a flat molded body.

[0329] The thermoplastic resin composition was extruded using an extrusion molding machine (FS30 manufactured by Ikegai Co., Ltd.) at an extrusion temperature of 360°C. Next, machining was performed to produce a flat extruded body 110 with a diameter of 40 mm and a thickness of 4 mm. This body was then heated in a hot air dryer at 260°C for 120 minutes and annealed. On one side of the resulting extruded body 110, two 5 mm × 5 mm × 3 mm depth recesses were etched at two locations using the same method as in Example 1, forming a molded body 210.

[0330] It should be noted that injection molded body 100 and extruded molded body 110, as well as molded bodies 200 and 210, have the same shape.

[0331] [Table 2]

[0332]

[0333] The details of each component shown in Table 2 are as follows.

[0334] <Thermoplastic Resin (A)>

[0335] (a1-1) Polyimide resin 1 obtained in Manufacturing Example 1

[0336] <Inorganic Filler Materials (B)>

[0337] (b1) Zirconia, high-purity zirconia "KZ-0Y-LSF" manufactured by Kyoritsu Materials Co., Ltd., spherical particles, D50: 0.2µm

[0338] (b2) Talc, "NanoAce D-800" manufactured by Japan Talc Co., Ltd., in plate form, D50: 0.8µm

[0339] As shown in Table 2, even when multiple fine through holes are formed with a narrow spacing, the components of this embodiment exhibit fewer burrs, less breakage and scorching of the partition walls, and less deviation in the shape of the through hole openings. Furthermore, it is evident that when the opening shape is square, the shape reproducibility is high, indicating high-precision micro-machining.

[0340] It should be noted that, in Figures 2-5 The image shown is an image of the through hole formed in step (II) of Examples 1 and 2, viewed from above using the digital microscope (magnification: 150x). Figure 2 This is an observation image of the through hole with a circular opening shape fabricated in Example 1. Figure 3 This is an observation image of the through hole with a square opening shape fabricated in Example 1. Figure 4 This is an observation image of the through hole with a circular opening shape made in Example 2. Figure 5 This is an observation image of the through hole with a square opening shape made in Example 2.

[0341] Industrial availability

[0342] According to the present invention, a probe card component or a printed circuit board inspection fixture component, which has achieved high-precision micro-machining, is provided, particularly when laser processing is used to form fine through holes, resulting in less burr generation and a high degree of precision. A method for manufacturing the same is also provided.

[0343] Explanation of reference numerals in the attached figures

[0344] 200 Molded body produced in process (I) of Example 1

[0345] 201, 202 dents

Claims

1. A component, which is a component for a probe card or a component for a printed circuit board inspection fixture, The component is composed of a thermoplastic resin composition, the thermoplastic resin composition containing: Component A: At least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resin a1 with a melting point above 270°C and amorphous thermoplastic resin a2 with a glass transition temperature above 200°C, and Component B: An inorganic filler material containing zirconium oxide (b1). 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.

2. The component according to claim 1, wherein, The component a1 comprises polyimide resin a1-1, which comprises repeating structural units shown in formula (1) and repeating structural units shown in formula (2). The content of repeating structural units in formula (1) is 20 to 70 mol% relative to the total of repeating structural units in formula (1) and repeating structural units in formula (2). R1 is a divalent group with 6 to 22 carbons containing at least one alicyclic hydrocarbon structure, R2 is a divalent chain aliphatic group with 5 to 16 carbons, and X1 and X2 are each independently a tetravalent group with 6 to 22 carbons containing at least one aromatic ring.

3. The component according to claim 1 or 2, wherein, The volume median particle size D50 of the zirconium oxide b1 is less than 1µm.

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

5. The component according to any one of claims 1 to 4, wherein, The component B further includes an inorganic filler material b2 other than component b1, wherein the inorganic filler material b2 comprises 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 component according to claim 5, wherein, The content of the inorganic filler material b2 is 1 to 40 parts by mass relative to 100 parts by mass of component A in the thermoplastic resin composition.

7. The component according to any one of claims 1 to 6, wherein, The component has a plate-shaped portion, and the plate-shaped portion has a plurality of through holes that are approximately circular with an opening diameter of less than 400µm or approximately square with one side of the opening having a length of less than 400µm.

8. The component according to any one of claims 1 to 7, wherein, The component is a probe holding component or a probe guiding component.

9. A method for manufacturing a probe card component or a printed circuit board inspection fixture component according to any one of claims 1 to 8, the method comprising the following steps I and II in sequence. Step I is a step in which the following thermoplastic resin composition is molded by thermoforming to obtain a molded body having a plate-like portion. The thermoplastic resin composition contains: Component A: At least one thermoplastic resin selected from the group consisting of crystalline thermoplastic resin a1 with a melting point above 270°C and amorphous thermoplastic resin a2 with a glass transition temperature above 200°C, and Component B: An inorganic filler material containing zirconium oxide (b1). 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 is a step in which multiple through holes are formed in the plate-shaped portion of the formed body by cutting or laser processing.

10. The manufacturing method according to claim 9, wherein, The thermoforming method in process I is injection molding, extrusion molding, or compression molding.

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

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