Resin composition, pellet, and molded article

Abstract

A resin composition containing a liquid crystal polyester containing a first monometric unit having a fused aromatic ring and a second monometric unit having a benzene ring, and a styrene-based resin having a dielectric loss tangent of 0.001 or less at 10 GHz, the liquid crystal polyester containing a first monometric unit having a fused aromatic ring and a second monometric unit having a benzene ring, the content of the styrene-based resin is 0.5-20 parts by mass with respect to 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin, and the content of the inorganic filler is 20% by mass or less.

Description

Technical Field

[0001] This disclosure relates to resin compositions and molded articles thereof. Background Technology

[0002] Liquid crystal polyesters have excellent flowability, heat resistance, and dimensional accuracy, making them suitable for a wide range of applications.

[0003] Liquid crystal polyesters are sometimes used as liquid crystal polyester compositions containing filler materials, for example, Patent Document 1 describes a liquid crystal polymer composition containing 20% ​​by mass or more of a specific flat glass fiber and a specific plate-shaped filler.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2003-268252 Summary of the Invention

[0005] The problem that the invention aims to solve However, resin compositions with a high proportion of inorganic fillers can lead to limitations in the shape of the molded product, and the exposure of the inorganic filler to the surface of the molded product can affect its surface properties and appearance.

[0006] The present disclosure aims to provide a resin composition having a sufficiently low amount of inorganic filler, which combines good melt flowability, good electrical properties of the molded article, and good softness of the molded article. Another objective of the present disclosure is to provide a molded article formed from a resin composition having a sufficiently low amount of inorganic filler, excellent moldability, and good electrical properties and good softness.

[0007] Methods for solving problems This disclosure provides, for example, the following. [1] A resin composition comprising a liquid crystal polyester and a styrene-based resin, The aforementioned liquid crystal polyester contains a first monomeric unit having a fused aromatic ring and a second monomeric unit having a benzene ring. The dielectric loss tangent of the aforementioned styrene-based resin at 10 GHz is below 0.001. The content of the above-mentioned styrene-based resin is 0.5 to 20 parts by weight relative to the total of 100 parts by weight of the above-mentioned liquid crystal polyester and the above-mentioned styrene-based resin. The content of inorganic filler material is less than 20% by mass. [2] According to the resin composition described in [1], wherein the styrene-based resin is polystyrene. [3] According to the resin composition described in [1] or [2], wherein the fused aromatic ring is a naphthalene ring. [4] The resin composition according to any one of [1] to [3], wherein the content of the first monolithic unit is 50 mol% or more relative to the total of all monolithic units constituting the liquid crystal polyester. [5] The resin composition according to any one of [1] to [4], wherein the dielectric loss tangent at 10 GHz is less than 0.001. [6] A granule comprising any one of the resin compositions described in [1] to [5]. [7] A molded article comprising any one of the resin compositions described in [1] to [5], The molded products include connectors, sockets, relay components, coil frames, optical pickups, oscillators, semiconductor packages, IC trays, wafer carriers, household electrical appliance components, lighting fixture components, audio product components, optical cable sheaths, telephone components, fax components, modem components, release claws, heater brackets, impellers, fan gears, gears, bearings, motor components, motor housings, engine components, engine compartment components, electrical components, automotive interior components, microwave cooking pots, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing materials, aircraft components, spacecraft components, space equipment components, nuclear reactors, marine facility components, cleaning fixtures, optical equipment components, valves, pipes, nozzles, filters, membranes, medical equipment components, medical materials, sensor components, hygiene supplies, and sporting or leisure products.

[0015] Invention Effects According to this disclosure, a resin composition can be provided that has a sufficiently small amount of inorganic filler, and possesses good melt flowability, good electrical properties of the molded article, and good softness of the molded article. Furthermore, according to this disclosure, a molded article formed from a resin composition with a sufficiently small amount of inorganic filler and excellent moldability can be provided, and possesses good electrical properties and good softness. Detailed Implementation

[0016] The preferred embodiments of this disclosure will now be described in detail.

[0017] The resin composition of this embodiment (hereinafter also simply referred to as the "resin composition") comprises a liquid crystal polyester and a styrene-based resin. The liquid crystal polyester contains a first monolithic unit having a fused aromatic ring and a second monolithic unit having a benzene ring. The styrene-based resin has a dielectric loss tangent of 0.001 or less at 10 GHz. The content of the styrene-based resin is 0.5 to 20 parts by mass relative to 100 parts by mass of the total liquid crystal polyester and styrene-based resin. In addition, in this embodiment, the resin composition may or may not contain inorganic filler, and the content of inorganic filler is 20% by mass or less.

[0018] The resin composition of this embodiment is a resin composition with a sufficiently small amount of inorganic filler, and it also has good flowability when melted, good electrical properties of the molded article, and good softness of the molded article.

[0019] In this embodiment, the liquid crystal polyester and the styrene-based resin have similar structures in that they contain a large number of aromatic rings. Furthermore, the liquid crystal polyester has a small dielectric loss tangent due to the presence of fused aromatic rings. Therefore, the molecular chain mobility of the liquid crystal polyester and the styrene-based resin is similar in that they have small dielectric loss tangents. From these points of view, it is believed that in this embodiment, the dispersion and interaction of the liquid crystal polyester and the styrene-based resin are good, exhibiting high flexibility. In addition, the liquid crystal polyester forms liquid crystal regions through its liquid crystallization. The liquid crystal polyester and liquid crystal regions easily align in the flow direction, but the expansion of the liquid crystal regions is small in the direction perpendicular to the flow direction, thus resulting in weak interaction relative to the direction perpendicular to the flow direction. On the other hand, the molecular chains of the styrene-based resin also easily expand in the direction perpendicular to the flow direction, thus resulting in strong interaction relative to the direction perpendicular to the flow direction. Therefore, it is believed that with a small amount of styrene-based resin, the liquid crystal polyesters and the liquid crystal regions easily interact with each other in the direction perpendicular to the flow direction, making the liquid crystal polyester easy to orient and further improving its flowability.

[0020] In this embodiment, it is believed that by using 20 parts by mass or less of styrene-based resin, the aforementioned effects can be obtained without hindering the good mechanical properties of the liquid crystal polyester. Furthermore, in this embodiment, it is believed that by keeping the content of inorganic filler material at 20% by mass or less, the interaction between the liquid crystal polyester and the styrene-based resin is less likely to be hindered, as well as the orientation of the liquid crystal polyesters via a small amount of styrene-based resin, thus significantly achieving the aforementioned effects.

[0021] Liquid crystal polyesters are any polyesters that exhibit liquid crystal properties in the molten state. The resin composition may contain only one type of liquid crystal polyester or two or more types.

[0022] The flow initiation temperature of the liquid crystal polyester can be, for example, above 250°C or above 270°C. Alternatively, the flow initiation temperature of the liquid crystal polyester can be, for example, below 400°C, below 360°C, or below 340°C.

[0023] That is, the flow start temperature of the liquid crystal polyester can be, for example, above 250°C and below 400°C, above 250°C and below 360°C, above 250°C and below 340°C, above 270°C and below 400°C, above 270°C and below 360°C, or above 270°C and below 340°C.

[0024] In this specification, the flow initiation temperature of the liquid crystal polyester is determined using a flow tester, with the liquid crystal polyester subjected to a flow test at 9.8 MPa (100 kg / cm²). 2 Under a load of 4℃ / min, the liquid crystal polyester is heated and melted, and extruded from a nozzle with an inner diameter of 1mm and a length of 10mm. The viscosity is 4800Pa·s (48000 poise) at the temperature.

[0025] Liquid crystal polyesters have constituent units (also called monomeric units) derived from raw material monomers. In liquid crystal polyesters, the main monomeric units (e.g., monomeric units comprising 90 mol% or more, 95 mol% or more, or 99 mol% or more of all monomeric units, preferably all monomeric units) can be monomeric units derived from aromatic compounds. Liquid crystal polyesters in which all monomeric units are monomeric units derived from aromatic compounds are also called fully aromatic liquid crystal polyesters.

[0026] The liquid crystal polyester has a first monomeric unit having a fused aromatic ring and a monomeric unit having a benzene ring. The liquid crystal polyester may have one or more first monomeric units. Additionally, the liquid crystal polyester may have one or more second monomeric units. The second monomeric unit may be a monomeric unit having a benzene ring but not a fused aromatic ring.

[0027] The first monomer unit can be a monomer unit from an aromatic compound (1) having a fused aromatic ring. In addition, the second monomer unit can be a monomer unit from an aromatic compound (2) having a benzene ring.

[0028] It should be noted that, in this specification, "from" refers to a change in the chemical structure of the functional groups that facilitate polymerization of the raw material monomers within the monolithic unit of the liquid crystal polyester formed by the polymerization of the raw material monomers, while no other structural changes occur. Here, "from" also includes the concept of polymerizable derivatives of the raw material monomers (e.g., compounds formed by converting the polymerization-contributing functional groups of the raw material monomers into other polymerizable groups).

[0029] Examples of first monomeric units include, for instance, monomeric units derived from aromatic hydroxycarboxylic acids (1-1) having fused aromatic rings (hereinafter also referred to as monomeric units (1-1)); monomeric units derived from aromatic dicarboxylic acids (1-2) having fused aromatic rings (hereinafter also referred to as monomeric units (1-2)); and monomeric units derived from aromatic diols (1-3) having fused aromatic rings (hereinafter also referred to as monomeric units (1-3)).

[0030] Examples of second monomeric units include, for instance, monomeric units derived from aromatic hydroxycarboxylic acids (2-1) (hereinafter also referred to as monomeric units (2-1)), monomeric units derived from aromatic dicarboxylic acids (2-2) (hereinafter also referred to as monomeric units (2-2)), and monomeric units derived from aromatic diols (2-3) (hereinafter also referred to as monomeric units (2-3)).

[0031] Examples of fused aromatic rings that can be used as the first monomeric unit include naphthalene rings, anthracene rings, phenanthrene rings, tetraphenyl rings, pyrene rings, benzo[a]phenanthrene rings, perylene rings, and fluorene rings. Among these, naphthalene rings are preferred from the viewpoint of availability and price.

[0032] Examples of monolithic units in liquid crystal polyesters include, for example, the monolithic unit shown in formula (I) below (hereinafter also referred to as monolithic unit (I))., the monolithic unit shown in formula (II) below (hereinafter also referred to as monolithic unit (II))., and the monolithic unit shown in formula (III) below (hereinafter also referred to as monolithic unit (III)).

[0033] -O-Ar 1 -CO- (I) -CO-Ar 2 -CO- (II) -X-Ar 3 -Y- (III) [In the formula, Ar] 1 Ar 2 and Ar 3 Each of these groups independently represents a phenylene group, a biphenylene group, a fused polycyclic aromatic hydrocarbon group, or a group represented by formula (IV). Ar 1 Ar 2 and Ar 3 Some or all of the hydrogen atoms can be substituted with halogen atoms, alkyl groups, or aryl groups. X and Y independently represent an oxygen atom or an imino group (-NH-), respectively. -Ar 4 -Z-Ar 5 - (IV) [In the formula, Ar]4 and Ar 5 Each group independently represents a phenylene group or a fused polycyclic aromatic hydrocarbon group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkyl diene group. The phenylene oxide can be 1,4-phenylene oxide or 1,3-phenylene oxide, preferably 1,4-phenylene oxide.

[0034] The biphenylene oxide can be 4,4'-biphenylene oxide.

[0035] A fused polycyclic aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from a fused polycyclic aromatic hydrocarbon. Examples of fused polycyclic aromatic hydrocarbons include naphthalene, anthracene, phenanthrene, benzo[a]phenylene, pyrene, benzo[a]phenanthrene, perylene, and fluorene. Among these, naphthalene is preferred from the viewpoint of availability and price.

[0036] The fused polycyclic aromatic hydrocarbon group can be naphthylene. The naphthylene can be 2,6-naphthylene or 2,7-naphthylene, preferably 2,6-naphthylene.

[0037] Halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine.

[0038] The alkyl group used as a substituent can be straight-chain, branched, or cyclic. For example, the alkyl group can have 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, and n-decyl.

[0039] The aryl group used as a substituent can be monocyclic or fused-ring. For example, aryl groups can have 6 to 20 carbon atoms. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl. An aryl group can be a group where the hydrogen atoms of the aromatic ring are replaced by alkyl groups, such as tolyl.

[0040] Ar 1 Ar 2 and Ar 3 The number of substituents can be, for example, 0 to 2, or 0 or 1, or even 0.

[0041] X and Y are preferably oxygen atoms.

[0042] The alkyl diene in Z can be straight-chain or branched. The alkyl diene can be an alkyl diene with 1 to 10 carbon atoms. Examples of alkyl dienes include methylene, ethane diene, propane diene (e.g., propane-2,2-diyl), butane diene, and octane diene (e.g., octane-3,3-diyl).

[0043] Z is preferably an oxygen atom, a sulfur atom, a methylene group, an ethanediyl group, or a propanediyl group, and more preferably an oxygen atom.

[0044] The first monolithic unit can be the monolithic unit (Ar) shown in equation (I). 1 It is a fused polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 At least one of them is a group of formula (IV) that is a fused polycyclic aromatic hydrocarbon group, or it can be a monolithic unit of formula (II) (Ar 2 It is a fused polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 At least one of them is a group of formula (IV) that is a fused polycyclic aromatic hydrocarbon group, or it can be a monolithic unit of formula (III) (Ar 2 It is a fused polycyclic aromatic hydrocarbon group, or Ar 4 and Ar 5 At least one of them is a group of formula (IV) that is a fused polycyclic aromatic hydrocarbon group.

[0045] The first monomeric unit can be a monomeric unit from an aromatic compound (1) having a fused aromatic ring. Examples of aromatic compounds (1) include, for example, 2-hydroxy-6-naphthoic acid, 2,6-naphthoic acid, 2,6-dihydroxynaphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, 2,7-naphthodiol, etc.

[0046] The second monolithic unit can be the monolithic unit (Ar) shown in equation (I). 1 It is phenylene, biphenylene, or Ar 4 and Ar 5 (The group represented by formula (IV) is a phenylene group), or it can be a monolithic unit represented by formula (II) (Ar) 2 It is phenylene, biphenylene, or Ar 4 and Ar 5 (The group represented by formula (IV) of the phenylene group), or it can be the monotypic unit represented by formula (III) (Ar 3 It is phenylene, biphenylene, or Ar 4 and Ar 5 (The group is a phenylene group represented by formula (IV)).

[0047] The second monounit can be a monounit that does not have a fused aromatic ring and comes from an aromatic compound (2) having a benzene ring. Examples of aromatic compounds (2) include p-hydroxybenzoic acid, terephthalic acid, hydroquinone, isophthalic acid, 4,4'-biphenol, etc.

[0048] In liquid crystal polyesters, the content of the first monomeric unit, relative to the total number of monomeric units constituting the liquid crystal polyester, can be, for example, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more. A higher content of the first monomeric unit tends to further improve the dielectric properties. Furthermore, relative to the total number of monomeric units constituting the liquid crystal polyester, the content of the first monomeric unit can be, for example, 90 mol% or less, 85 mol% or less, or 80 mol% or less. This tends to improve moldability and processability at low temperatures.

[0049] That is, relative to the total number of all monomer units constituting the liquid crystal polyester, the content of the first monomer unit can be, for example, 20 mol% or more and 90 mol% or less, 20 mol% or more and 85 mol% or less, 20 mol% or more and 80 mol% or less, 30 mol% or more and 90 mol% or less, 30 mol% or more and 85 mol% or less, 30 mol% or more and 80 mol% or less, 40 mol% or more and 90 mol% or less, 40 mol% or more and 85 mol% or less, 40 mol% or more and 80 mol% or less, 50 mol% or more and 90 mol% or less, 50 mol% or more and 85 mol% or less, 50 mol% or more and 80 mol% or less, 60 mol% or more and 90 mol% or less, 60 mol% or more and 85 mol% or less, 60 mol% or more and 80 mol% or less, 70 mol% or more and 90 mol% or less, 70 mol% or more and 85 mol% or less, or 70 mol% or more and 80 mol% or less.

[0050] In the liquid crystal polyester, the content of the second monomeric unit, relative to the total number of monomeric units constituting the liquid crystal polyester, can be, for example, 10 mol% or more, 15 mol% or more, or 20 mol% or more. Furthermore, the content of the second monomeric unit, relative to the total number of monomeric units constituting the liquid crystal polyester, can be, for example, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less.

[0051] That is, the content of the second monomeric unit can be, for example, 10 mol% or more and 80 mol% or less, 10 mol% or more and 70 mol% or less, 10 mol% or more and 60 mol% or less, 10 mol% or more and 50 mol% or less, 10 mol% or more and 40 mol% or less, 10 mol% or more and 30 mol% or less, 15 mol% or more and 80 mol% or less, 15 mol% or more and 70 mol% or less, 15 mol% or more and 60 mol% or less, 15 mol% or more and 50 mol% or less, 15 mol% or more and 40 mol% or less, 15 mol% or more and 30 mol% or less, 20 mol% or more and 80 mol% or less, 20 mol% or more and 70 mol% or less, 20 mol% or more and 60 mol% or less, 20 mol% or more and 50 mol% or more, 20 mol% or more and 40 mol% or less, or 20 mol% or more and 30 mol% or less.

[0052] In liquid crystal polyester, the total amount of the first monolithic unit and the second monolithic unit relative to the total amount of all monolithic units constituting the liquid crystal polyester can be, for example, 90 mol% or more, 95 mol% or more, 99 mol% or more, or 100 mol%.

[0053] Liquid crystal polyester can be a polymer having two or more monolithic units (I), or a polymer having monolithic units (I), monolithic units (II) and monolithic units (III).

[0054] When the liquid crystal polyester has monolithic units (I), monolithic units (II), and monolithic units (III), the content of monolithic unit (I) relative to the total number of monolithic units in the liquid crystal polyester can be, for example, 30 mol% or more, 40 mol% or more, 45 mol% or more, 50 mol% or more, or 55 mol% or more. Furthermore, when the liquid crystal polyester has monolithic units (I), monolithic units (II), and monolithic units (III), the content of monolithic unit (I) relative to the total number of monolithic units in the liquid crystal polyester can be, for example, 80% or less, or 70% or less.

[0055] That is, when the liquid crystal polyester has monolithic units (I), monolithic units (II) and monolithic units (III), the content of monolithic unit (I) relative to the total of all monolithic units of the liquid crystal polyester can be, for example, 30 mol% or more and 80 mol% or less, 30 mol% or more and 70 mol% or less, 40 mol% or more and 80 mol% or less, 40 mol% or more and 70 mol% or less, 45 mol% or more and 80 mol% or less, 45 mol% or more and 70 mol% or less, 50 mol% or more and 80 mol% or less, 50 mol% or more and 70 mol% or less, 55 mol% or more and 80 mol% or less, or 55 mol% or more and 70 mol% or less.

[0056] When the liquid crystal polyester has monolithic units (I), monolithic units (II), and monolithic units (III), the content of monolithic unit (II) and the content of monolithic unit (III) relative to the total number of monolithic units in the liquid crystal polyester can, for example, be 35 mol% or less, or 30 mol% or less. Furthermore, when the liquid crystal polyester has monolithic units (I), monolithic units (II), and monolithic units (III), the content of monolithic unit (II) and the content of monolithic unit (III) relative to the total number of monolithic units in the liquid crystal polyester can, for example, be 5 mol% or more, 10 mol% or more, or 15 mol% or more.

[0057] That is, when the liquid crystal polyester has monolithic units (I), monolithic units (II) and monolithic units (III), the content of monolithic unit (II) and the content of monolithic unit (III) relative to the total of all monolithic units of the liquid crystal polyester can be, for example, 5 mol% or more and 35 mol% or less, 5 mol% or more and 30 mol% or less, 10 mol% or more and 35 mol% or less, 10 mol% or more and 30 mol% or less, 15 mol% or more and 35 mol% or less, or 15 mol% or more and 30 mol% or less.

[0058] The liquid crystal polyester may have monolithic units other than monolithic units (I), monolithic units (II) and monolithic units (III), and the number of monolithic units relative to the total number of monolithic units of the liquid crystal polyester may be less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, or less than 0 mol%.

[0059] In this specification, the number of each monomer unit in the liquid crystal polyester is determined using the analytical method described in Japanese Patent Application Publication No. 2000-19168. Specifically, the liquid crystal polyester is depolymerized by reacting it with a lower alcohol in a supercritical state, and the depolymerization products (monomers from which each monomer unit is derived) are quantified by liquid chromatography, thereby allowing the calculation of the number of each monomer unit relative to the total number of monomer units.

[0060] Liquid crystal polyesters can be manufactured by polymerizing raw material monomers corresponding to the monomer units constituting them. For example, they can be manufactured according to the method described in Japanese Patent No. 6439027.

[0061] The dielectric loss tangent of the liquid crystal polyester at 10 GHz can be, for example, 0.002 or less, preferably 0.0015 or less, and more preferably 0.001 or less. Therefore, the resin composition having an appropriate dielectric loss tangent, as described later, can be readily obtained.

[0062] The relative permittivity of the liquid crystal polyester at 10 GHz can be, for example, 4.0 or less, or 3.8 or less. Alternatively, the relative permittivity of the liquid crystal polyester at 10 GHz can be, for example, 2.8 or more, or 3.0 or more.

[0063] In this specification, the dielectric loss tangent and relative permittivity of the liquid crystal polyester at 10 GHz are determined by the following method.

[0064] Using an injection molding machine (FANUC, ROBOSHOT S-2000i 30B), liquid crystal polyester granules were used as the molding material at a barrel temperature of 330°C, a mold temperature of 130°C, and an injection speed of 100 mm / s to obtain test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm. For the obtained test pieces, the relative permittivity and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (Keysight Technologies, N5290A) and a split cylindrical resonator (EM Lab, CR710). It should be noted that the measurement environment was set at 23°C and 50% RH.

[0065] Styrene-based resins are polymers containing monolithic units derived from styrene.

[0066] Styrene-based resins can contain monomer units derived from monomers other than styrene. Examples of monomers other than styrene include acrylonitrile, butadiene, and ethylene.

[0067] Styrene-based resins can be, for example, polystyrene, modified polystyrene, etc. From the viewpoint of obtaining the above-mentioned effects more significantly, polystyrene is preferred.

[0068] Polystyrene can be isotactic polystyrene, syndiotactic polystyrene, or atactic polystyrene.

[0069] The dielectric loss tangent of styrene-based resins at 10 GHz is below 0.001, or even below 0.0008.

[0070] The relative permittivity of styrene-based resins at 10 GHz can be, for example, 3 or less, or 2.6 or less. Alternatively, the relative permittivity of styrene-based resins at 10 GHz can be, for example, 2 or more, or 2.2 or more.

[0071] In this specification, the dielectric loss tangent and relative permittivity of styrene-based resins at 10 GHz are determined by the following method.

[0072] Using an injection molding machine (FANUC, ROBOSHOT S-2000i 30B), styrene-based resin granules were used as molding materials at barrel temperatures of 290°C (XAREC 300ZC) and 300°C (XAREC 90ZC), a mold temperature of 130°C, and an injection speed of 100 mm / s to obtain test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm. The barrel temperature was set to a temperature at which the resin was fully plasticized and resin decomposition did not progress significantly. For the obtained test pieces, the relative permittivity and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (Keysight Technologies, N5290A) and a split cylindrical resonator (EM Lab, CR710). It should be noted that the measurement environment was set at 23°C and 50% RH.

[0073] The number average molecular weight (Mn) of styrene-based resins can be, for example, 10,000 or more, or 20,000 or more, 30,000 or more, or 40,000 or more. Alternatively, the number average molecular weight (Mn) of styrene-based resins can be, for example, 200,000 or less, or 150,000 or less, 130,000 or less, or 100,000 or less.

[0074] The weight-average molecular weight (Mw) of styrene-based resins can be, for example, 20,000 or more, or 40,000 or more, 60,000 or more, or 800,000 or more. Alternatively, the weight-average molecular weight (Mw) of styrene-based resins can be, for example, 400,000 or less, or 300,000 or less, 250,000 or less, or 200,000 or less.

[0075] The molecular weight distribution (Mw / Mn) of styrene-based resins can be, for example, 1.3 or more, or 1.6 or more, 1.8 or more, or 2 or more. Conversely, the molecular weight distribution (Mw / Mn) of styrene-based resins can be, for example, 8 or less, or 7 or less, 6 or less, or 5 or less.

[0076] In this specification, the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of styrene-based resins are values ​​determined by gel permeation chromatography at 135°C using 1,2,4-trichlorobenzene as solvent.

[0077] The content of styrene resin in the resin composition is 0.5 parts by mass or more, specifically 1 part by mass or more, or 2 parts by mass or more, relative to a total of 100 parts by mass of liquid crystal polyester and styrene resin. This tends to further improve the melt flowability of the resin composition and the softness of the molded article. Furthermore, the content of styrene resin in the resin composition is 20 parts by mass or less, specifically 17 parts by mass or less, 15 parts by mass or less, 13 parts by mass or less, or 10 parts by mass or less, relative to a total of 100 parts by mass of liquid crystal polyester and styrene resin. This tends to further improve the softness and heat resistance of the molded article.

[0078] Relative to a total of 100 parts by weight of liquid crystal polyester and styrene-based resin, the content of styrene-based resin in the resin composition is 0.5 parts by weight or more and 20 parts by weight or less, or 1 part by weight or more and 17 parts by weight or less, or 1 part by weight or more and 15 parts by weight or less, or 1 part by weight or more and 13 parts by weight or less, or 2 parts by weight or more and 10 parts by weight or less.

[0079] In the resin composition, the total amount of liquid crystal polyester and styrene resin can be, for example, 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, or 99% by mass or more, or 100% by mass.

[0080] The resin composition may further include other components besides liquid crystal polyester and styrene-based resin.

[0081] For example, the resin composition may contain one or more resins other than liquid crystal polyester and styrene-based resins. Examples of such resins include polyolefins, cyclic polyolefins, polyvinyl chloride, polysulfone, (meth)acrylic resins, polyphenylene ether resins, polyacetal resins, polyamide resins, imide resins, cellulose resins, polyetheretherketone resins, fluororesins, polycarbonate resins, thermosetting resins, etc.

[0082] In addition, the resin composition may further include inorganic fillers, colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, lubricants, release agents, etc.

[0083] The content of inorganic filler in the resin composition is 20% by mass or less, based on the total amount of the resin composition. The content of inorganic filler in the resin composition, based on the total amount of the resin composition, can be 17% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, or 2% by mass or less, or it can be 0% by mass or more.

[0084] The content of inorganic filler in the resin composition may be, for example, 0.1% by mass or more and 20% by mass or less, 0.1% by mass or more and 17% by mass or less, 0.1% by mass or more and 15% by mass or less, 0.1% by mass or more and 10% by mass or less, 0.1% by mass or more and 5% by mass or less, or 0.1% by mass or more and 2% by mass or less, based on the total amount of the resin composition.

[0085] The resin composition of this embodiment is suitable for use as a molding material due to its excellent flowability upon melting. For example, the resin composition can be used as granules.

[0086] The molded articles of this embodiment comprise the resin composition described above. The molded articles of this embodiment can be connectors, sockets, relay components, coil frames, optical pickups, oscillators, semiconductor packages, IC trays, wafer carriers, household electrical appliance components, lighting fixture components, audio product components, optical cable sheaths, telephone components, fax components, modem components, release claws, heater brackets, impellers, fan gears, gears, bearings, motor components, motor housings, engine components, engine compartment components, electrical components, automotive interior components, microwave cooking pots, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing materials, aircraft components, spacecraft components, space equipment components, nuclear reactors, marine facility components, cleaning fixtures, optical equipment components, valves, pipes, nozzles, filters, membranes, medical equipment components, medical materials, sensor components, hygiene products, sporting goods, or leisure products.

[0087] The molded article of this embodiment can be obtained, for example, by molding the above-described resin composition into a desired shape and performing processing as needed.

[0088] As a molding method for molded products, melt molding is preferred. Examples of melt molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, and compression molding.

[0089] The preferred embodiments of this disclosure have been described above, but this disclosure is not limited to the above embodiments.

[0090] [Example] The following examples illustrate the invention disclosed herein in more detail, but the invention disclosed herein is not limited to these examples. Unless otherwise specified, the percentages and parts of content or usage are used on a mass basis.

[0091] (Example 1-1) (1) Manufacturing of liquid crystal polyester (LCP1) In a reactor equipped with a stirrer, torque meter, nitrogen inlet pipe, thermometer, and reflux cooler, 1035.0 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 378.3 g (1.75 mol) of 2,6-naphthoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.), 83.1 g (0.5 mol) of terephthalic acid, 255.2 g of hydroquinone, 1226.87 g (12 mol) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst were added. After the reactor was fully purged with nitrogen, the temperature was raised to 140°C over a nitrogen flow for 1 hour, maintained at the temperature, and refluxed for 1 hour.

[0092] Then, while distilling off the distillate byproduct acetic acid, the temperature was increased to 310°C over 4 hours and 35 minutes. The reaction was considered complete when the torque was confirmed to be rising, and the contents were removed. The flow start temperature of the obtained solid component was 270°C. The obtained solid component was cooled to room temperature, pulverized with a coarse pulverizer, and then heated from room temperature to 250°C over 1 hour under a nitrogen atmosphere, followed by a further increase from 250°C to 283°C over 5 hours and 30 minutes. The temperature was maintained at 283°C for 6 hours to carry out a polymerization reaction in the solid layer, yielding liquid crystal polyester (LCP1).

[0093] The flow initiation temperature of liquid crystal polyester (LCP1) was determined by the following method, and the result was 306℃.

[0094] <Determination of Flow Onset Temperature> Using a flow testing apparatus (Shimadzu Corporation, CFT-500 model), approximately 2g of liquid crystal polyester granules were filled into a barrel equipped with a nozzle having an inner diameter of 1mm and a length of 10mm, and tested at 9.8MPa (100kg / cm²). 2 The liquid crystal polyester was heated at a rate of 4°C / min under a load of 4°C, and extruded from a nozzle. The temperature (FT) at which the viscosity was measured was 4800 Pa·s (48000 P), and this temperature was taken as the flow initiation temperature. "Approximately 2g" can be estimated as 2g ± 0.1g.

[0095] The relative permittivity of liquid crystal polyester (LCP1) at 10 GHz is 3.6, and the dielectric loss tangent is 0.00091.

[0096] (2) Preparation of styrene-based resin (S1) As a styrene-based resin (S1), syndiotactic polystyrene (manufactured by Idemitsu Kosan Co., Ltd., "XAREC300ZC", weight-average molecular weight (Mw) of 140,000) was prepared.

[0097] The styrene-based resin (S1) has a relative permittivity of 2.6 and a dielectric loss tangent of 0.00038 at 10 GHz.

[0098] (3) Manufacturing of resin composition and granules Liquid crystal polyester (LCP1) and styrene-based resin (S1) were mixed at a mass ratio of 93:7 to obtain a resin composition. Next, the resin composition was granulated using a twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd., PCM-30) at a barrel temperature of 320°C to obtain resin composition granules.

[0099] (4) Evaluation of resin composition and molded article The melt viscosity, elongation, relative permittivity, and dielectric loss tangent were determined using the following method. The results are shown in Table 1.

[0100] <Evaluation of fluidity at melt> Using a capillary rheometer (Toyo Seiki Co., Ltd., Capillograph 1D), a capillary tube with an inner diameter of 0.5 mm and a length of 10 mm was installed at the front end of the barrel. The resin composition granules were melted in the barrel heated to 340°C and extruded from the nozzle. The viscosity of the extruded resin composition was measured at a shear rate of 1000 / s, and this viscosity was used as the melt viscosity of the resin composition for evaluation.

[0101] <Evaluation of Softness> Using an injection molding machine (Nissei Resin Kogyo Co., Ltd., PNX-40-5A), resin composition granules were used as molding material to injection mold ASTM D638 dumbbell-shaped test pieces (2.5 mm thick) at a barrel temperature of 340°C, a mold temperature of 130°C, and an injection speed of 75 mm / s. Five dumbbell test pieces were then subjected to tensile testing using a tensile testing machine (A&D Corporation, Tensilon RTG-1310) at a chuck distance of 50 mm, a crosshead speed of 10 mm / min, and a test temperature of 23°C. The elongation at this point was measured, and the average of the tensile elongation at fracture (%) was calculated from the five samples.

[0102] The elongation at break is calculated using the following formula.

[0103] Elongation at break (%) = (L - Lo) / Lo × 100 Lo: Length of the distance between the chucks before the test (mm) L: The length of the distance between the chucks at the time of fracture (mm) Evaluation of dielectric properties Using an injection molding machine (FANUC, ROBOSHOT S-2000i 30B), with a barrel temperature of 330°C, a mold temperature of 130°C, and an injection speed of 50 mm / s, granules of a resin composition were used as molding materials to obtain test pieces with a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm. For the obtained test pieces, the relative permittivity and dielectric loss tangent at 10 GHz were measured using a vector network analyzer (Keysight Technologies, N5290A) and a split cylindrical resonator (EM Lab, CR710).

[0104] • Measurement environment: 23℃, 50%RH (Examples 1-2) The ratio of liquid crystal polyester (LCP1) to styrene-based resin (S1) was changed from 93:7 to 85:15. Otherwise, the resin composition and granules were prepared in the same manner as in Examples 1-1. Furthermore, the obtained granules were evaluated in the same way as in Examples 1-1, and the results are shown in Table 1.

[0105] (Comparative Example 1-1) Without styrene-based resin (S1), only liquid crystal polyester (LCP1) was used to manufacture the resin composition and granules in the same manner as in Examples 1-1. Furthermore, the obtained granules were evaluated in the same way as in Examples 1-1, and the results are shown in Table 1. Additionally, the molding temperature of the ASTM dumbbells was 320°C, and the molding temperature of the test pieces used for dielectric property evaluation was also 320°C.

[0106] (Comparative Examples 1-2) The ratio of liquid crystal polyester (LCP1) to styrene-based resin (S1) was changed from 93:7 to 70:30. Otherwise, the resin composition and granules were prepared in the same manner as in Examples 1-1. Furthermore, the obtained granules were used for the same evaluation as in Examples 1-1, and the results are shown in Table 1. Additionally, the molding temperature for the ASTM dumbbells was 320°C, and the molding temperature for the test pieces used for dielectric property evaluation was also 320°C.

[0107] (Comparative Examples 1-3) Granules of styrene-based resin (S1) were used instead of liquid crystal polyester (LCP1). Using these granules, the same evaluation as in Examples 1-1 was performed, and the results are shown in Table 1. It should be noted that the conditions for manufacturing the ASTM dumbbells were set as follows: temperature 290°C, mold temperature 135°C, and injection speed 50 mm / s. Additionally, the conditions for manufacturing the test pieces used to evaluate dielectric properties were set as follows: temperature 290°C, mold temperature 135°C, and injection speed 50 mm / s.

[0108] (Example 2-1) (1) Manufacturing of liquid crystal polyester (LCP2) In a reactor equipped with a stirrer, torque meter, nitrogen inlet pipe, thermometer, and reflux cooler, 1035.0 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 378.3 g (1.75 mol) of 2,6-naphthoic acid, 83.1 g (0.5 mol) of terephthalic acid, 255.2 g of hydroquinone, 1226.87 g (12 mol) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst were added. After the reactor was fully purged with nitrogen, the temperature was raised to 140°C over a nitrogen flow for 1 hour, maintained at the temperature, and refluxed for 1 hour.

[0109] Then, while distilling off the distillate byproduct acetic acid, the temperature was increased to 310°C over 4 hours and 35 minutes. The reaction was considered complete when the torque was confirmed to be rising, and the contents were removed. The flow start temperature of the obtained solid component was 270°C. The obtained solid component was cooled to room temperature, pulverized with a coarse pulverizer, and then heated from room temperature to 250°C over 1 hour under a nitrogen atmosphere, followed by a further increase from 250°C to 286°C over 7 hours and 40 minutes. The temperature was then maintained at 286°C for 6 hours to carry out a polymerization reaction in the solid layer, yielding liquid crystal polyester (LCP2).

[0110] The flow start temperature of liquid crystal polyester (LCP2) was determined using the above method, and the result was 311℃.

[0111] The relative permittivity of liquid crystal polyester (LCP2) at 10 GHz is 3.5, and the dielectric loss tangent is 0.00080°.

[0112] (2) Manufacturing and evaluation of resin compositions and granules Liquid crystal polyester (LCP2) and styrene-based resin (S1) were mixed at a mass ratio of 96:4 to obtain a resin composition. Next, the resin composition was granulated using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) at a barrel temperature of 340°C to obtain resin composition granules. The obtained granules were evaluated in the same manner as in Examples 1-1, and the results are shown in Table 2. Additionally, the molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces used for dielectric property evaluation was 325°C.

[0113] (Example 2-2) The ratio of liquid crystal polyester (LCP2) to styrene-based resin (S1) was changed from 96:4 to 93:7. Otherwise, the resin composition and granules were prepared in the same manner as in Example 2-1 (with the barrel temperature at 320°C). Furthermore, the obtained granules were evaluated in the same way as in Example 1-1, and the results are shown in Table 2. Additionally, the molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test piece used to evaluate the dielectric properties was 325°C.

[0114] (Comparative Example 2-1) Except for the absence of styrene-based resin (S1) and the use of liquid crystal polyester (LCP2), the resin composition and granules were prepared in the same manner as in Example 2-1 (wherein the barrel temperature was 330°C). Furthermore, the obtained granules were evaluated in the same manner as in Example 1-1, and the results are shown in Table 1. Additionally, the molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces used for dielectric property evaluation was 325°C.

[0115] (Example 3-1) (1) Preparation of styrene-based resin (S2) As a styrene-based resin (S2), syndiotactic polystyrene (manufactured by Idemitsu Kosan Co., Ltd., "XAREC90ZC", weight-average molecular weight (Mw) of 200,000) was prepared. The styrene-based resin (S2) has a relative permittivity of 2.6 and a dielectric loss tangent of 0.00037 at 10 GHz.

[0116] (2) Manufacturing and evaluation of resin compositions and granules Liquid crystal polyester (LCP2) and styrene-based resin (S2) were mixed at a mass ratio of 99:1 to obtain a resin composition. Next, the resin composition was granulated using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) at a barrel temperature of 330°C to obtain resin composition granules. The obtained granules were evaluated in the same manner as in Examples 1-1, and the results are shown in Table 3. It should be noted that the molding temperature for the ASTM dumbbells was set to 340°C, and the molding temperature for the test pieces used for dielectric property evaluation was set to 325°C.

[0117] (Example 3-2) The ratio of liquid crystal polyester (LCP2) to styrene-based resin (S2) was changed from 99:1 to 96:4. Otherwise, the resin composition and granules were prepared in the same manner as in Example 3-1 (barrel temperature 330°C). Furthermore, the obtained granules were used for the same evaluation as in Example 1-1, and the results are shown in Table 3. It should be noted that the molding temperature for the ASTM dumbbell was set to 340°C, and the molding temperature for the test piece used for dielectric property evaluation was set to 325°C.

[0118] (Example 3-3) The ratio of liquid crystal polyester (LCP2) to styrene-based resin (S2) was changed from 99:1 to 93:7. Otherwise, the resin composition and granules were prepared in the same manner as in Example 3-1 (barrel temperature 330°C). Furthermore, the obtained granules were used for the same evaluation as in Example 1-1, and the results are shown in Table 3. It should be noted that the molding temperature for the ASTM dumbbell was set to 340°C, and the molding temperature for the test piece used for dielectric property evaluation was set to 325°C.

[0119] (Comparative Example 3-1) Granules of styrene-based resin (S2) were used instead of liquid crystal polyester (LCP2). Using these granules, the same evaluation as in Examples 1-1 was performed, and the results are shown in Table 3. It should be noted that the conditions for manufacturing the ASTM dumbbells were set as follows: temperature 290°C, mold temperature 135°C, and injection speed 50 mm / s. Additionally, the conditions for manufacturing the test pieces used to evaluate dielectric properties were set as follows: temperature 300°C, mold temperature 135°C, and injection speed 50 mm / s.

[0120] (Example 4-1) Liquid crystal polyester (LCP2), styrene-based resin (S1), and glass fiber (manufactured by Nitto Boshoku Co., Ltd., SC3J260S) were mixed at a mass ratio of 88.6:6.7:4.7 to obtain a resin composition. The resin composition was then granulated at a barrel temperature of 330°C to obtain resin composition granules. The obtained granules were used for the same evaluation as in Examples 1-1, and the results are shown in Table 4. Additionally, the molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces used for dielectric property evaluation was 325°C.

[0121] (Comparative Example 4-1) The ratio of liquid crystal polyester (LCP2) to styrene-based resin (S1) to glass fiber was changed to 71.5:5.4:23.1. Otherwise, the resin composition and granules were prepared in the same manner as in Example 4-1. Furthermore, the obtained granules were used for the same evaluation as in Example 1-1, and the results are shown in Table 4. Additionally, the molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test piece used for dielectric property evaluation was 325°C.

[0122] (Comparative Example 5-1) (1) Manufacturing of liquid crystal polyester (LCP3) In a reactor equipped with a stirrer, torque meter, nitrogen inlet pipe, thermometer, and reflux cooler, 994.5 g (7.2 mol) of 4-hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl, 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of isophthalic acid, and 1347.6 g (13.2 mol) of acetic anhydride were added, along with 0.19 g of 1-methylimidazole as a catalyst. After fully purging the reactor with nitrogen, the temperature was raised to 140 °C over a nitrogen flow for 30 minutes, maintained at that temperature, and refluxed for 1 hour. Then, 0.92 g of 1-methylimidazole was added.

[0123] Then, while distilling off the distillate byproduct acetic acid, the temperature was increased to 300°C over 4 hours and 20 minutes. The reaction was considered complete when the torque increased, and the contents were removed. The flow start temperature of the obtained solid component was 245°C. The obtained solid component was cooled to room temperature, pulverized using a coarse pulverizer, and then heated from room temperature to 240°C over 1 hour under a nitrogen atmosphere, followed by a further increase from 240°C to 284°C over 5 hours and 40 minutes. The temperature was maintained at 284°C for 5 hours to carry out a polymerization reaction in the solid layer, yielding liquid crystal polyester (LCP3). The flow start temperature of the obtained liquid crystal polyester (LCP3) was 330°C.

[0124] (2) Manufacturing and evaluation of resin compositions and granules Granules were manufactured using only liquid crystal polyester (LCP3) in the same manner as in Examples 1-1. Furthermore, the resulting granules were evaluated in the same way as in Examples 1-1 (with a barrel temperature of 330°C), and the results are shown in Table 5. Additionally, the molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces used to evaluate the dielectric properties was also 340°C.

[0125] (Comparative Example 5-2) Liquid crystal polystyrene (LCP3) and styrene-based resin (S1) were mixed at a mass ratio of 93:7 to obtain a resin composition. Next, granules were prepared in the same manner as in Examples 1-1. Furthermore, the obtained granules were used for the same evaluation as in Examples 1-1, and the results are shown in Table 5. Additionally, the molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces used for dielectric property evaluation was 340°C.

[0126] (Example 6-1) (1) Preparation of styrene-based resin (S3) As a styrene-based resin (S3), randomized polystyrene (ToyoStyrol GP HRM10N, manufactured by ToyoStyrol Corporation) was prepared. The styrene-based resin (S3) has a relative permittivity of 2.5 and a dielectric loss tangent of 0.00041 at 10 GHz.

[0127] (2) Manufacturing and evaluation of resin compositions and granules Liquid crystal polyester (LCP2) and styrene-based resin (S3) were mixed at a mass ratio of 96:4 to obtain a resin composition. Next, the resin composition was granulated using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) at a barrel temperature of 330°C to obtain resin composition granules. The obtained granules were evaluated in the same manner as in Example 1-1, and the results are shown in Table 6. It should be noted that the molding temperature for the ASTM dumbbells was set to 340°C, and the molding temperature for the test pieces used for dielectric property evaluation was set to 325°C. Table 6 shows a comparison between Example 6-1 and Comparative Example 2-1.

[0128]

Claims

1. A resin composition comprising a liquid crystal polyester and a styrene-based resin, The liquid crystal polyester contains a first monomeric unit having a fused aromatic ring and a second monomeric unit having a benzene ring. The styrene-based resin has a dielectric loss tangent of less than 0.001 at 10 GHz. The content of the styrene-based resin is 0.5 to 20 parts by weight relative to the total of 100 parts by weight of the liquid crystal polyester and the styrene-based resin. The content of inorganic filler material is less than 20% by mass.

2. The resin composition according to claim 1, wherein, The styrene-based resin is polystyrene.

3. The resin composition according to claim 1, wherein, The fused aromatic ring is a naphthalene ring.

4. The resin composition according to claim 1, wherein, The content of the first monolithic unit is 50 mol% or more relative to the total of all monolithic units constituting the liquid crystal polyester.

5. The resin composition according to claim 1, wherein, The dielectric loss tangent at 10 GHz is below 0.

001.

6. A granule comprising the resin composition according to any one of claims 1 to 5.

7. A molded article comprising the resin composition according to any one of claims 1 to 5. The molded products include connectors, sockets, relay components, coil frames, optical pickups, oscillators, semiconductor packages, IC trays, wafer carriers, household electrical appliance components, lighting fixture components, audio product components, optical cable sheaths, telephone components, fax components, modem components, release claws, heater brackets, impellers, fan gears, gears, bearings, motor components, motor housings, engine components, engine compartment components, electrical components, automotive interior components, microwave cooking pots, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing materials, aircraft components, spacecraft components, space equipment components, nuclear reactors, marine facility components, cleaning fixtures, optical equipment components, valves, pipes, nozzles, filters, membranes, medical equipment components, medical materials, sensor components, hygiene supplies, and sporting or leisure products.

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