Polyolefin copolymers, resin pellets, modifiers for engineering plastics, engineering plastic compositions, and resin molded articles

Abstract

To provide a polyolefin copolymer that is used as a modifier for engineering plastic to yield an engineering plastic composition with low dielectric constants and low dielectric loss tangents.SOLUTION: A polyolefin copolymer has a main chain containing a monomer unit A derived from a C2-8 olefin monomer and a monomer unit B having a glycidyl group. The main chain may also contain a monomer unit C derived from a (meth)acrylic acid ester or vinyl ether. Based on the mass of the olefin copolymer, the proportion of the monomer unit A is 94 mass% or more and the total proportion of the monomer unit B and the monomer unit C is less than 6 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polyolefin copolymers, resin pellets, modifiers for engineering plastics, engineering plastic compositions, and resin molded articles. [Background technology]

[0002] Conventionally, modifiers have been known that are compounded into engineering plastics to improve or modify various properties of engineering plastics. For example, Patent Document 1 describes a resin composition comprising: (A) 5 to 95 parts by mass of a polyphenylene ether resin, or a mixture of the resin and a polystyrene resin; (B) 95 to 5 parts by mass of saturated polyester; (C) 100 parts of (a) a polyolefin resin; (b) 0.1 to 30 parts of a modifying agent consisting of a compound represented by a predetermined formula, or the compound and glycidyl methacrylate, or glycidyl methacrylate; (c) 0.1 to 500 parts of a vinyl monomer; and (d) a radical polymerization initiator, in an aqueous suspension of 0.001 to 10 parts per 100 parts of the total amount of (b) and (c); a graft-modified polyolefin resin obtained by impregnating (a) with (b) and (c) in the aqueous suspension and polymerizing it, in an aqueous suspension of 1 to 100 parts per 100 parts of (A) and (B). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 8-259798 [Overview of the project] [Problems that the invention aims to solve]

[0004] One aspect of the present invention relates to a polyolefin copolymer that, when used as a modifier for engineering plastics, can produce engineering plastic compositions having a low dielectric constant and a low dielectric loss tangent. [Means for solving the problem]

[0005] In some aspects of the present invention, the following [1] to

[14] are provided. [1] Having a main chain comprising monomer unit A derived from an olefin monomer having 2 to 8 carbon atoms and monomer unit B having a glycidyl group, The main chain may further contain monomer units C derived from (meth)acrylic acid esters or vinyl ethers. Based on the mass of the polyolefin copolymer, the proportion of monomer unit A is 94% by mass or more, and the total proportion of monomer units B and C is less than 6% by mass. Polyolefin copolymer. [2] The polyolefin copolymer according to [1], wherein monomer unit A is a monomer unit derived from ethylene, a monomer unit derived from α-olefin, or a combination thereof. [3] The polyolefin copolymer according to [1], wherein monomer unit A is a monomer unit derived from ethylene. [4] The polyolefin copolymer according to any one of [1] to [3], wherein monomer unit B is a monomer unit derived from an unsaturated carboxylic acid glycidyl ester, a monomer unit derived from a glycidyl ether having an unsaturated group, or a combination thereof. [5] A polyolefin copolymer according to any one of [1] to [3], wherein monomer unit B is a monomer unit derived from glycidyl (meth)acrylate. [6] The polyolefin copolymer according to any one of [1] to [5], wherein the proportion of monomer unit B is 1% by mass or more, based on the mass of the polyolefin copolymer. [7] The polyolefin copolymer according to any one of [1] to [5], wherein the proportion of monomer units C is less than 1% by mass, based on the mass of the polyolefin copolymer. [8] A resin pellet containing a polyolefin copolymer as described in any of [1] to [7]. [9] A modifier for engineering plastics, comprising the polyolefin copolymer according to any one of [1] to [7].

[10] The polyolefin copolymer according to any one of [1] to [7], and engineering plastics, and An engineering plastic composition comprising the same.

[11] The engineering plastic composition according to

[10] , substantially free of polyethylene terephthalate resin.

[12] A resin molded body comprising the engineering plastic composition according to

[10] or

[11] .

[13] The resin molded body according to

[12] , which is a member of an automotive part.

[14] The resin molded body according to

[12] , which is a member of an electric / electronic part. [Effect of the Invention]

[0006] According to the present invention, there can be provided a polyolefin copolymer capable of obtaining an engineering plastic composition having a low dielectric constant and a low dielectric tangent when used as a modifier for engineering plastics. [Embodiments for Carrying Out the Invention]

[0007] Hereinafter, some examples of the present invention will be described in detail. However, the present invention is not limited to the following examples.

[0008] An example of the polyolefin copolymer is a copolymer having a main chain containing a monomer unit A derived from an olefin monomer having 2 to 8 carbon atoms and a monomer unit B having a glycidyl group. This polyolefin copolymer may be used as a resin pellet (resin composition) containing the polyolefin copolymer, or may be used as a modifier for engineering plastics or the like.

[0009] The monomer unit A derived from an olefin monomer having 2 to 8 carbon atoms may be a monomer unit derived from ethylene, a monomer unit derived from an α-olefin, or a combination thereof, and may also be a monomer unit derived from ethylene. Examples of α-olefins include linear olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; cyclic olefins such as norbornene, 5-methylnorbornene, and 1-methylnorbornene; and aromatic olefins such as styrene etc. are mentioned.

[0010] The proportion of monomer unit A (or the total proportion of the monomer unit derived from ethylene and the monomer unit derived from α-olefin) is 94% by mass or more, and may be 95% by mass or more, 96% by mass or more, 97% by mass or more, or 97.5% by mass or more, based on the mass of the polyolefin copolymer. The proportion of monomer unit A (or the total proportion of the monomer unit derived from ethylene and the monomer unit derived from α-olefin) may be 99.9% by mass or less, 99% by mass or less, 98.5% by mass or less, or 98% by mass or less, based on the mass of the polyolefin copolymer. The proportion of monomer unit A (or the total proportion of the monomer unit derived from ethylene and the monomer unit derived from α-olefin) may be 94 to 99.9% by mass or 95 to 99% by mass, based on the mass of the polyolefin copolymer.

[0011] The monomer unit B derived from a monomer having a glycidyl group may be a monomer unit derived from an unsaturated carboxylic acid glycidyl ester, a monomer unit derived from a glycidyl ether having an unsaturated group, or a combination thereof, and may also be a monomer unit derived from an unsaturated carboxylic acid glycidyl ester. The monomer unit B is at least present in the main chain of the polyolefin copolymer. The monomer unit B may not be present at the end of the polyolefin copolymer.

[0012] The unsaturated carboxylic acid glycidyl ester that derives monomer unit B may be a compound represented by the following formula (1). In formula (1), R 1 This represents an alkenyl group having 2 to 18 carbon atoms, and the alkenyl group may have one or more substituents. Examples of compounds represented by formula (1) include glycidyl acrylate, glycidyl methacrylate, and glycidyl itaconic acid ester.

[0013] [ka]

[0014] A glycidyl ether having an unsaturated group that derives monomer unit B may be a compound represented by the following formula (2). In formula (2), R 2 This represents an alkenyl group having 2 to 18 carbon atoms, and the alkenyl group may have one or more substituents. X is CH2-O(CH2 is R 2 It represents a (bonded) or oxygen atom. Examples of compounds represented by formula (2) include allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

[0015] [ka]

[0016] The proportion of monomer unit B may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, or 2.2% by mass or more, based on the mass of the polyolefin copolymer. The proportion of monomer unit B may be less than 6% by mass, 5.5% by mass or less, 5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, or 2.3% by mass or less, based on the mass of the polyolefin copolymer. The proportion of monomer unit B may be 0.1% by mass or more and less than 6% by mass or 0.5 to 5.5% by mass, based on the mass of the polyolefin copolymer.

[0017] The mass ratio of monomer unit B to monomer unit A (percentage of monomer unit B / percentage of monomer unit A) may be 0.001 or higher, 0.005 or higher, 0.01 or higher, 0.015 or higher, or 0.02 or higher. The mass ratio of monomer unit B to monomer unit A (percentage of monomer unit B / percentage of monomer unit A) may be 0.06 or lower, 0.05 or lower, 0.04 or lower, 0.03 or lower, or 0.025 or lower. The mass ratio of monomer unit B to monomer unit A (percentage of monomer unit B / percentage of monomer unit A) may be 0.001 to 0.06 or 0.005 to 0.05.

[0018] The main chain of the polyolefin copolymer may or may not further contain monomer unit C (excluding those corresponding to monomer unit B) derived from (meth)acrylic acid ester or vinyl ether. "(meth)acrylate" means acrylate or methacrylate, and this is also true for similar compounds.

[0019] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, and phenyl vinyl ether.

[0020] The proportion of monomer unit C may be 3% by mass or less, 2% by mass or less, 1% by mass or less, less than 1% by mass, 0.5% by mass or less, or 0.1% by mass or less, based on the mass of the polyolefin copolymer. The proportion of monomer unit C may also be 0% by mass, based on the mass of the polyolefin copolymer.

[0021] The total ratio of monomer unit B to monomer unit C is less than 6% by mass, based on the mass of the polyolefin copolymer, and may be 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.7% by mass or less, 2.5% by mass or less, or 2.3% by mass or less. The total ratio of monomer unit B to monomer unit C is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 1.8% by mass or more, 2% by mass or more, or 2.2% by mass or more, based on the mass of the polyolefin copolymer. The total ratio of monomer unit B to monomer unit C is 0.1% by mass or more and less than 6% by mass, or 0.5 to 5.5% by mass, based on the mass of the polyolefin copolymer.

[0022] The mass ratio of monomer units C to monomer units B (ratio of monomer units C / ratio of monomer units B) may be 0.1 or less, 0.05 or less, or 0.01 or less. The mass ratio of monomer units C to monomer units B (ratio of monomer units C / ratio of monomer units B) may also be 0.

[0023] Examples of polyolefin copolymers include ethylene-glycidyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-methyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-ethyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-n-propyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-isopropyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-n-butyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-isobutyl (meth)acrylate copolymer, and ethylene-glycidyl (meth)acrylate-vinyl ether copolymer. The polyolefin copolymer may also be an ethylene-glycidyl (meth)acrylate copolymer.

[0024] Polyolefin copolymers can be synthesized by various methods. For example, polyolefin copolymers can be produced by bulk polymerization using free radical initiators, emulsion polymerization, or solution polymerization. One typical polymerization method for synthesizing polyolefin copolymers involves polymerization at a polymerization pressure of 500 kg / cm² in the presence of a free radical-generating polymerization initiator. 2 The above describes a copolymerization method using olefin monomers having 2 to 8 carbon atoms, monomers having a glycidyl group, and optionally (meth)acrylic acid esters or vinyl ethers, under polymerization temperature conditions of 40 to 300°C. The polymerization pressure is 1000 kg / cm². 2 It may be greater than or equal to 2000 kg / cm². 2 The following is also possible: The polymerization temperature may be 100-250°C or 150-200°C. Since olefin monomers having 2-8 carbon atoms, monomers having a glycidyl group, and (meth)acrylic acid esters or vinyl ethers are randomly copolymerized, olefin monomers having 2-8 carbon atoms and monomers having a glycidyl group are present in the main chain at least.

[0025] The melt flow rate (MFR) of the polyolefin copolymer may be 0.2 g / 10 min or more, 0.5 g / 10 min or more, 1 g / 10 min or more, 1.5 g / min or more, 2 g / 10 min or more, 2.5 g / 10 min or more, or 3 g / 10 min or more. The melt flow rate (MFR) of the polyolefin copolymer may be 300 g / 10 min or less, 250 g / 10 min or less, 220 g / 10 min or less, or 200 g / 10 min or less. The MFR of the polyolefin copolymer can be measured in accordance with JIS K7210 under conditions of a temperature of 190°C and a load of 2.16 kgf.

[0026] The dielectric constant of the polyolefin copolymer may be 2.55 or less, 2.50 or less, 2.47 or less, 2.45 or less, or 2.43 or less, from the viewpoint of easily obtaining an engineering plastic composition with a low dielectric constant. The dielectric constant of the polyolefin copolymer may be 2.0 or more, 2.2 or more, or 2.3 or more. The dielectric constant of the polyolefin copolymer can be measured by the method described in the examples below.

[0027] The dielectric loss tangent of the polyolefin copolymer may be 0.012 or less, 0.010 or less, 0.0095 or less, 0.0080 or less, 0.0070 or less, 0.0060 or less, or 0.0055 or less, from the viewpoint of easily obtaining engineering plastic compositions with particularly low dielectric loss tangents. The dielectric loss tangent of the copolymer may be 0.001 or more, 0.002 or more, 0.003 or more, or 0.004 or more. The dielectric loss tangent of the polyolefin copolymer can be measured by the method described in the examples below.

[0028] The polyolefin copolymer content may be 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more, based on the total mass of the resin pellets. The polyolefin copolymer content may also be 100% by mass, based on the total mass of the resin pellets.

[0029] The resin pellets may further contain additives such as compatibilizers, antioxidants, heat stabilizers, ultraviolet absorbers, color inhibitors, plasticizers, flame retardants, mold release agents, antistatic agents, and colorants.

[0030] Resin pellets can be obtained, for example, by a method that includes melt-kneading a mixture containing a polyolefin copolymer and additives as needed.

[0031] Melt mixing can be carried out using, for example, a twin-screw mixer or a laboplast mill. Examples of twin-screw mixers include a co-directional twin-screw extruder.

[0032] The maximum temperature of the mixture being melted and kneaded may be 50-350°C, 80-320°C, 100-300°C, 120-280°C, or 150-250°C.

[0033] The mixing time for melt mixing may be 1 to 1800 seconds, 10 to 1200 seconds, or 30 to 600 seconds.

[0034] Resin pellets can be used, for example, as modifiers for engineering plastics to improve various properties of engineering plastics (e.g., impact resistance). Engineering plastic compositions comprising engineering plastics and polyolefin copolymers (or modifiers) can be obtained, for example, by a method comprising melt-kneading a mixture containing a polyolefin copolymer (or modifier) ​​and an engineering plastic. An engineering plastic composition may comprise a continuous phase containing an engineering plastic and particles containing a polyolefin copolymer dispersed in the continuous phase.

[0035] Engineering plastics refer to plastics that have a temperature deflection under load of 100°C or higher as measured by ASTM D648, a tensile strength of 50 MPa as measured by ASTM D638, and a flexural modulus of 2.4 GPa or higher as measured by ASTM D790. Plastics with a heat resistance of 150°C or higher are called special engineering plastics or super engineering plastics, but in this specification, special engineering plastics and super engineering plastics are also included in engineering plastics.

[0036] Examples of engineering plastics include polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polycarbonate, polyethylene terephthalate, liquid crystalline polymers, polyethersulfone, polyamide, polyphthalamide, polyketone, polyetherketone, polyetheretherketone, polyacetal, and polysulfone. The engineering plastic composition does not have to contain substantially any polyethylene terephthalate resin, and the polyethylene terephthalate content may be less than 1% by mass, based on the mass of engineering plastics in the engineering plastic composition. The polyethylene terephthalate resin referred to here also includes modified products in which some of the monomer units derived from terephthalic acid are replaced with monomer units derived from dicarboxylic acids or the like other than terephthalic acid.

[0037] The engineering plastic composition may further contain other components added separately from the polyolefin copolymer (or modifier), such as resin components (excluding those corresponding to the polyolefin copolymer mentioned above), fillers, antioxidants, heat stabilizers, ultraviolet absorbers, color inhibitors, plasticizers, flame retardants, mold release agents, antistatic agents, and colorants.

[0038] The resin component may be an olefin copolymer that does not have epoxy groups. This olefin copolymer may be an ethylene-α-olefin copolymer having monomer units derived from ethylene and monomer units derived from α-olefin. Examples of olefin copolymers that do not have epoxy groups include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, and ethylene-(3-methyl-1-butene) copolymer.

[0039] The MFR of the resin component at a temperature of 190°C and a load of 2.16 kgf may be 0.1 g / 10 min or more, 0.5 g / 10 min or more, or 1 g / 10 min or more, or it may be 50 g / 10 min or less, 20 g / 10 min or less, or 10 g / 10 min or less.

[0040] The density of the resin component is 0.85 g / cm 3 or more, 0.87 g / cm 3 or more, or 0.89 g / cm 3 or more, and may be 0.95 g / cm 3 or less, 0.92 g / cm 3 or less, or 0.90 g / cm 3 or less.

[0041] The dielectric constant of the engineering plastic composition may be 2.96 or less, 2.95 or less, 2.94 or less, 2.93 or less, or 2.92 or less. The dielectric constant of the engineering plastic composition may be 2.0 or more, 2.5 or more, or 2.8 or more. The dielectric constant of the engineering plastic composition can be measured by the method described in the examples below.

[0042] The dielectric loss tangent of the engineering plastic composition may be 0.0060 or less, 0.0058 or less, 0.0057 or less, 0.0056 or less, or 0.0055 or less. The dielectric loss tangent of the engineering plastic composition may be 0.001 or more, 0.002 or more, 0.003 or more, 0.004 or more, or 0.005 or more. The dielectric loss tangent of the engineering plastic composition can be measured by the method described in the examples below.

[0043] The MFR retention rate of the engineering plastic composition may be 50% or more, 70% or more, or 90% or more. The MFR retention rate of the engineering plastic composition may be 150% or less, 130% or less, or 110% or less. The MFR retention rate of the engineering plastic composition means the change rate of the MFR of the engineering plastic composition after storage for 1 to 6 months in a room temperature environment with respect to the MFR of the engineering plastic composition immediately after production (MFR of the engineering plastic composition after storage / MFR of the engineering plastic composition before storage), and can be measured by the method described in the examples below.

[0044] The Izod impact strength of the engineering plastic composition at -30°C is 3.0 kJ / m². 2 Above or above, or 3.1 kJ / m 2 The above is also acceptable. The Izod impact strength of the engineering plastic composition at -30°C is 5.0 kJ / m². 2 Below, 4.0kJ / m 2 The following, or 3.5 kJ / m³ 2 The following may also apply. The Izod impact strength of the engineering plastic composition at -30°C can be measured by the method described in the examples below.

[0045] The flexural strength of the engineering plastic composition may be 74 MPa or higher or 75 MPa or higher. The flexural strength of the engineering plastic composition may be 90 MPa or lower or 80 MPa or lower. The flexural strength of the engineering plastic composition can be measured by the method described in the examples below.

[0046] The flexural modulus of the engineering plastic composition may be 2050 MPa or higher or 2100 MPa or higher. The flexural modulus of the engineering plastic composition may be 2300 MPa or lower or 2200 MPa or lower. The flexural modulus of the engineering plastic composition can be measured by the method described in the examples below.

[0047] The HDT (heat distortion temperature) of the engineering plastic composition may be 59.5°C or higher or 60°C or higher. The HDT of the engineering plastic composition may be 80°C or lower or 70°C or lower. The HDT of the engineering plastic composition can be measured by the method described in the examples below.

[0048] The content of the polyolefin copolymer may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, based on the total mass of the engineering plastic composition. The content of the polyolefin copolymer may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less, based on the total mass of the engineering plastic composition. The content of the polyolefin copolymer may be 1 to 50% by mass, based on the total mass of the engineering plastic composition.

[0049] The engineering plastic content may be 50% or more by mass, 60% or more by mass, 70% or more by mass, or 80% or more by mass, based on the total mass of the engineering plastic composition. The engineering plastic content may be 95% or less by mass or 90% or less by mass, based on the total mass of the engineering plastic composition. The engineering plastic content may be 50 to 95% by mass, based on the total mass of the engineering plastic composition.

[0050] An engineering plastic composition can be molded by any molding method, such as injection molding, extrusion molding, vacuum forming, and hollow molding, to obtain a resin molded article of the engineering plastic composition. The resulting resin molded article has a low dielectric constant and a low dielectric loss tangent, and may be used, for example, as a component for an automobile part or a component for an electrical or electronic part. [Examples]

[0051] The invention will be described in detail below based on the following examples. However, the present invention is not limited to the following examples. 1. Raw materials The following raw materials were prepared for the preparation of the polybutylene terephthalate resin composition: polyolefin copolymers, engineering plastics, and other resin components were each prepared as resin pellets. (A) Polyolefin copolymer • BF-2C (product name, manufactured by Sumitomo Chemical Co., Ltd., random copolymer of 94 parts by mass of ethylene and 6 parts by mass of glycidyl methacrylate, MFR = 3 g / 10 min, polymerization pressure: 1346 kg / cm²) 2 , polymerization temperature: 194℃) • BF-7L (product name, manufactured by Sumitomo Chemical Co., Ltd., random copolymer of 70 parts by mass of ethylene, 3 parts by mass of glycidyl methacrylate, and 27 parts by mass of methyl acrylate, MFR = 7 g / 10 min, polymerization pressure: 1804 kg / cm²) 2 , polymerization temperature: 191℃) EGMA-1 (random copolymer of 97.8 parts by mass of ethylene and 2.2 parts by mass of glycidyl methacrylate, MFR = 3 g / 10 min, polymerization pressure: 1356 kg / cm²) 2 , polymerization temperature: 196℃) EGMA-2 (random copolymer of 97.7 parts by mass of ethylene and 2.3 parts by mass of glycidyl methacrylate, MFR = 43 g / 10 min, polymerization pressure: 1356 kg / cm²) 2 , polymerization temperature: 195℃) EGMA-3 (random copolymer of 97.7 parts by mass of ethylene and 2.3 parts by mass of glycidyl methacrylate, MFR = 85 g / 10 min, polymerization pressure: 1356 kg / cm²) 2 , polymerization temperature: 195℃) EGMA-4 (random copolymer of 97.7 parts by mass of ethylene and 2.3 parts by mass of glycidyl methacrylate, MFR = 190 g / 10 min, polymerization pressure: 1356 kg / cm²) 2 , polymerization temperature: 195℃) EGMA-5 (random copolymer of 94.7 parts by mass of ethylene and 5.3 parts by mass of glycidyl methacrylate, MFR = 3 g / 10 min, polymerization pressure: 1346 kg / cm²) 2 , polymerization temperature: 195℃) (B) Engineering plastics • Polybutylene terephthalate (PBT): Trecon 1401 X06 (product name, manufactured by Toray Industries, Inc., intrinsic viscosity: 1.74) (C) Other resin components • EHR:FX201 (product name, manufactured by Sumitomo Chemical Co., Ltd., ethylene-hexene copolymer, MFR = 2g / 10min, density: 0.898g / cm³) 3 )

[0052] 2. Fabrication of molded body A (Example 1) A sheet-like molded body A with a thickness of 1.0 mm was produced by heating EGMA-1 at 190°C for 10 minutes using a vacuum press (Imoto Seisakusho Co., Ltd., IMC-19E6 model), and then cooling it at 30°C for 5 minutes.

[0053] (Example 2) Molded body A was prepared in the same manner as in Example 1, except that EGMA-2 was used instead of EGMA-1.

[0054] (Example 3) Molded body A was prepared in the same manner as in Example 1, except that EGMA-3 was used instead of EGMA-1.

[0055] (Example 4) Molded body A was prepared in the same manner as in Example 1, except that EGMA-4 was used instead of EGMA-1.

[0056] (Example 5) Molded body A was prepared in the same manner as in Example 1, except that EGMA-5 was used instead of EGMA-1.

[0057] (Comparative Example 1) Molded body A was prepared in the same manner as in Example 1, except that BF-2C was used instead of EGMA-1.

[0058] (Comparative Example 2) Molded body A was prepared in the same manner as in Example 1, except that BF-7L was used instead of EGMA-1.

[0059] 3. Preparation of engineering plastic compositions and molded articles B to D (Example 6) 90% by mass of polybutylene terephthalate (PBT) was fed from the main feeder into the hopper opening of barrel C1 of a twin-screw compounding extruder (KZW20TW, manufactured by Technovel Co., Ltd.), and 10% by mass of EGMA-1 was fed from the secondary feeder. The nozzle head temperature was set to 260°C and the screw rotation speed to 300 rpm, and the PBT and EGMA-1 were melt-mixed. The melt-mixed material was discharged from the twin-screw extruder at a discharge rate of 5 kg / hour, and the melt-mixed material was cut with a pelletizer to obtain resin pellets of an engineering plastic composition containing PBT. These resin pellets were injection-molded using an injection molding machine (Sumitomo Heavy Industries, SE100EV) under the conditions of a mold temperature of 80°C, a cylinder temperature of 260°C, and an injection speed of 15 mm / second to produce sheet-like molded body B with a thickness of 3.2 mm and sheet-like molded body C with a thickness of 6.4 mm. Furthermore, a sheet-like molded body D with a thickness of 1.0 mm was produced by heating and pressurizing the resin pellets in a vacuum press at 260°C for 10 minutes, and then cooling them at 30°C for 5 minutes.

[0060] (Example 7) Molded bodies B to D were prepared in the same manner as in Example 6, except that EGMA-2 was used instead of EGMA-1.

[0061] (Example 8) Molded bodies B to D were prepared in the same manner as in Example 6, except that EGMA-3 was used instead of EGMA-1.

[0062] (Example 9) Molded bodies B to D were prepared in the same manner as in Example 6, except that EGMA-4 was used instead of EGMA-1.

[0063] (Example 10) Molded bodies B to D were prepared in the same manner as in Example 6, except that EGMA-5 was used instead of EGMA-1.

[0064] (Comparative Example 3) Molded bodies B to D were prepared in the same manner as in Example 6, except that BF-2C was used instead of EGMA-1.

[0065] (Comparative Example 4) Molded bodies B to D were prepared in the same manner as in Example 6, except that BF-7L was used instead of EGMA-1.

[0066] (Comparative Example 5) Molded bodies B to D were prepared in the same manner as in Example 6, except that 93.3% by mass of polybutylene terephthalate (PBT) was introduced from the main feeder and 6.7% by mass of BF-2C was introduced from the secondary feeder.

[0067] (Comparative Example 6) Molded bodies B to D were prepared in the same manner as in Example 6, except that 97.5% by mass of polybutylene terephthalate (PBT) was introduced from the main feeder and 2.5% by mass of BF-2C was introduced from the secondary feeder.

[0068] (Comparative Example 7) Molded bodies B to D were prepared in the same manner as in Example 6, except that 99% by mass of polybutylene terephthalate (PBT) was introduced from the main feeder and 1% by mass of BF-2C was introduced from the secondary feeder.

[0069] (Example 11) The temperatures of the nine barrels C1 to C9, located along the extrusion direction from the hopper side of the twin-screw compounding extruder, were set as follows: C1: 100℃ C2: 200℃ C3~C9: 260℃ 80% by mass of PBT is fed from the main feeder into the hopper opening of barrel C1 of the twin-screw compounding extruder (KZW20TW, manufactured by Technovel Co., Ltd.), and 5% by mass of EGMA-1 and 15% by mass of FX201 (trade name, manufactured by Sumitomo Chemical Co., Ltd., ethylene-hexene copolymer (EHR), MFR=2g / 10min, density: 0.898g / cm³) are fed from the secondary feeder. 3PBT, EGMA-1, and EHR were added. The nozzle head temperature was set to 260°C and the screw rotation speed to 300 rpm, and the PBT, EGMA-1, and EHR were melt-kneaded. The melt-kneaded material was discharged from a twin-screw extruder at a discharge rate of 5 kg / hour, and the melt-kneaded material was cut with a pelletizer to obtain resin pellets of an engineering plastic composition containing PBT and EHR. These resin pellets were injection-molded using an injection molding machine (Sumitomo Heavy Industries, SE100EV) under the conditions of a mold temperature of 80°C, a cylinder temperature of 260°C, and an injection speed of 30 mm / second to produce a sheet-like molded body E with a thickness of 2.0 mm.

[0070] (Example 12) Molded body E was prepared in the same manner as in Example 11, except that EGMA-2 was used instead of EGMA-1.

[0071] (Example 13) Molded body E was prepared in the same manner as in Example 11, except that EGMA-3 was used instead of EGMA-1.

[0072] (Example 14) Molded body E was prepared in the same manner as in Example 11, except that EGMA-4 was used instead of EGMA-1.

[0073] (Comparative Example 8) Molded body E was prepared in the same manner as in Example 11, except that BF-2C was used instead of EGMA-1, the content of BF-2C was changed to 1.7 mass%, and the content of EHR was changed to 18.3 mass%.

[0074] (Comparative Example 9) Molded body E was prepared in the same manner as in Example 11, except that BF-7L was used instead of EGMA-1.

[0075] 4. Evaluation [Evaluation of dielectric constant and dielectric loss tangent] Test specimens measuring 64 mm in length, 64 mm in width, and 1.0 mm in thickness were prepared from molded bodies A and D. The dielectric constant and dielectric loss tangent at 1 GHz were measured using the capacitance method in a 23°C atmosphere.

[0076] [MFR retention rate] The resin pellets prepared in Examples 6-10 or Comparative Examples 3-7 were sealed in aluminum bags and stored at room temperature for at least one month. The resin pellets prepared in Examples 6-9 and Comparative Example 3 were stored for six months, the resin pellets prepared in Example 10 were stored for two months, and the resin pellets prepared in Comparative Examples 4-7 were stored for one month. The MFR of the resin pellets (engineering plastic composition) before and after storage was measured using a melt flow tester under conditions of a temperature of 190°C and a load of 2.16 kgf. From the measured MFR of the engineering plastic composition before and after storage, the rate of change of the MFR of the engineering plastic composition after storage compared to the MFR of the engineering plastic composition before storage was calculated.

[0077] [Izod impact test] A notched test specimen measuring 63.5 mm in length, 12.7 mm in width, and 3.2 mm in thickness was prepared from molded body B. Using this specimen, an Izod impact test was performed in accordance with ASTM D-256 to determine the Izod impact strength (kJ / m²) in an atmosphere of -30°C. 2 ) was measured.

[0078] [Bending test] A test specimen measuring 127 mm in length, 12.7 mm in width, and 3.2 mm in thickness was prepared from molded body B. The bending strength (MPa) and bending modulus (MPa) were measured in a 23°C atmosphere using a double bending tester (RTF-1350-2M, manufactured by A&D Co., Ltd.) in accordance with JIS-K7203 (ASTM-D-790).

[0079] [HDT measurement] A test specimen measuring 127 mm in length, 12.7 mm in width, and 6.4 mm in thickness was prepared from molded body C, and its HDT (°C) was measured in accordance with JIS K7197-1 and 2.

[0080] [Surface peel test] In molded body E, 100 cuts of 2mm x 2mm each were made with a cutter near the resin inlet. Cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.) was applied to the cut areas. The cellophane tape was peeled off quickly, and the number of cells that peeled off out of the 100 (number of peeled cells) was measured. A smaller number of peeled cells indicates a better appearance of the molded body.

[0081] [Table 1]

[0082] [Table 2]

[0083] [Table 3]

[0084] [Table 4]

Claims

1. A modifier for engineering plastics, comprising a polyolefin copolymer, The polyolefin copolymer has a main chain comprising monomer unit A derived from an olefin monomer having 2 to 8 carbon atoms and monomer unit B derived from a monomer having a glycidyl group. The main chain may further contain monomer units C derived from (meth)acrylic acid esters or vinyl ethers. A modifier for engineering plastics, wherein, based on the mass of the polyolefin copolymer, the proportion of monomer unit A is 94% by mass or more, the proportion of monomer unit B is 2.5% by mass or less, and the total proportion of monomer unit B and monomer unit C is less than 6% by mass.

2. An engineering plastic composition comprising a polyolefin copolymer and an engineering plastic, The polyolefin copolymer has a main chain comprising monomer unit A derived from an olefin monomer having 2 to 8 carbon atoms and monomer unit B derived from a monomer having a glycidyl group. The main chain may further contain monomer units C derived from (meth)acrylic acid esters or vinyl ethers. An engineering plastic composition in which, based on the mass of the polyolefin copolymer, the proportion of monomer unit A is 94% by mass or more, the proportion of monomer unit B is 2.5% by mass or less, and the total proportion of monomer unit B and monomer unit C is less than 6% by mass.

3. The engineering plastic composition according to claim 2, wherein monomer unit A is a monomer unit derived from ethylene, a monomer unit derived from α-olefin, or a combination thereof.

4. The engineering plastic composition according to claim 2, wherein monomer unit A is a monomer unit derived from ethylene.

5. The engineering plastic composition according to claim 2, wherein monomer unit B is a monomer unit derived from an unsaturated carboxylic acid glycidyl ester, a monomer unit derived from a glycidyl ether having an unsaturated group, or a combination thereof.

6. The engineering plastic composition according to claim 2, wherein monomer unit B is a monomer unit derived from glycidyl (meth)acrylate.

7. The engineering plastic composition according to claim 2, wherein the proportion of monomer unit B is 1% by mass or more, based on the mass of the polyolefin copolymer.

8. The engineering plastic composition according to claim 2, wherein the proportion of monomer units C is less than 1% by mass, based on the mass of the polyolefin copolymer.

9. The engineering plastic composition according to claim 2, which is substantially free of polyethylene terephthalate resin.

10. A resin molded article comprising the engineering plastic composition according to any one of claims 2 to 9.

11. A resin molded article according to claim 10, which is a component of an automobile part.

12. A resin molded body according to claim 10, which is a component of an electrical or electronic component.

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