Ethylene-α-olefin copolymer having α1-substituted epoxy groups at its terminus and method for producing the same

Abstract

The objective is to provide an ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its termini. Furthermore, the objective is to provide a resin composition using this olefin resin that improves the mechanical strength of the epoxy resin. [Solution] The present invention relates to an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, having a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and satisfying the following requirements (Y1) and (Y2), and also to a resin composition comprising the copolymer (Y) and an epoxy resin. (Y1) 1 Excluding saturated ends determined by 1H-NMR, more than 60% of all ends contain α1-substituted epoxy groups; (Y2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin copolymer having an α1-substituted epoxy group at its terminus, and a method for producing the ethylene-α-olefin copolymer. [Background technology]

[0002] Epoxy resins, a type of thermosetting resin, are widely used as sealing materials, adhesives, paints, and other coating materials due to their excellent heat resistance, water resistance, and chemical resistance. On the other hand, their low impact resistance and toughness can cause defects such as delamination during heat treatment processes such as reflow in semiconductor manufacturing. Various modifiers have been added to epoxy resins to improve their impact resistance and toughness. In particular, it has been described that by blending an acid-modified ethylene-α-olefin copolymer, a polymer with a low glass transition temperature, with epoxy resin, impact resistance can be improved while maintaining the characteristics of the epoxy resin (Patent Document 1). It has also been described that various acid-modified polyolefin resins other than ethylene-α-olefin copolymers can modify epoxy resins (Patent Document 2). These patent documents describe how maleic anhydride groups are grafted onto low-polarity polyolefins to make them compatible with epoxy resins, which have higher polarity than polyolefins. However, since the reactivity of epoxy groups and maleic anhydride groups to amines differs, there is considered to be room for further development in terms of compatibility. Furthermore, since ester bonds are formed through the reaction of maleic anhydride groups, improvements are needed in terms of long-term stability.

[0003] On the other hand, it has been reported that the mechanical properties of epoxy resins can be improved by introducing epoxy groups into polyolefins. For example, impact resistance can be improved by copolymers of ethylene and glycidyl ether, but problems arise with compatibility and viscosity due to the high molecular weight and glass transition temperature (Patent Document 3). Furthermore, there are reported cases of introducing epoxy groups into ethylene-α-olefin copolymers, but depending on the precursor, ethylene-α-olefin copolymers having vinylidene groups at the ends are used, and only terminal α2-substituted epoxy groups are present. Further improvements are needed from the standpoint of reactivity with epoxy resins (Patent Document 4). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] WO87 / 007900 [Patent Document 2] WO2018 / 131571 [Patent Document 3] Japanese Patent Application Publication No. 51-551 [Patent Document 4] Japanese Patent Publication No. 2006-8840 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide an ethylene-α-olefin copolymer having α1-substituted epoxy groups at its termini. Furthermore, the object of the present invention is to provide a resin composition using this olefin resin that improves the mechanical strength of the epoxy resin. [Means for solving the problem]

[0006] As a result of diligent research to solve the above problems, the inventors of the present invention have completed the present invention by producing an ethylene-α-olefin copolymer having α1-substituted epoxy groups at its termini through an epoxidation reaction using an ethylene-α-olefin copolymer with vinyl groups controlled at its termini. The various aspects of the present invention are described below.

[0007] [1] It has a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from α-olefins having 3 to 10 carbon atoms, Ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, satisfying the following requirements (Y1) and (Y2); (Y1) 1 Excluding saturated ends determined by 1H-NMR, more than 60% of all ends contain α1-substituted epoxy groups; (Y2) The melting point measured by differential scanning calorimetry (DSC) is not observed. [2] An ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, as described in [1] above, further satisfying the following requirements (Y3) to (Y5); (Y3) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%; (Y4) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10000; (Y5) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is between 1.5 and 5.5. [3] An epoxy resin composition comprising an epoxy resin and an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, as described in either [1] or [2] above. [4] The epoxy resin composition according to [3] above, wherein when the total amount of epoxy resin and ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its termini is 100 parts by mass, the epoxy resin content is 50 to 95 parts by mass. [5] A method for producing an ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its termini, satisfying the following requirements (Y1) and (Y2), by reacting an ethylene-α-olefin copolymer (A), which has a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, with a peroxide; (Y1) 1 Excluding saturated ends determined by H-NMR, the content of ends containing α1-substituted epoxy groups is 60% or more; (Y2) The melting point measured by differential scanning calorimetry (DSC) is not observed. [6] A method for producing an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, as described in [5] above, wherein the ethylene-α-olefin copolymer (A) satisfies the following requirements (A1) to (A3); (A1) The content of component (i) is 30 to 70 mol% and the content of component (ii) is 30 to 70 mol% with respect to a total of 100 mol% of the content of component (i) and component (ii); (A2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is between 300 and 10000; (A3) 1 The vinyl group end accounts for more than 70% of the total integrated intensity of the signals of vinyl group end-terminators, vinylidene group end-terminators, disubstituted olefin end-terminators, and trisubstituted olefin end-terminators, as determined by 1H-NMR.

[0008] The present invention will be described in more detail below. In this invention, "room temperature" means 25°C. In this specification, the "~" symbol indicating a numerical range means a range that includes the numbers before and after it as the lower and upper limits, respectively. In this specification, when "~" indicating a numerical range is used, for example, when expressed as "M~N" (where M and N are numerical values satisfying M < N), unless otherwise specified, it means "M or more and N or less". Also, the unit described after either one of the numerical values before and after "~" is, unless otherwise specified, the unit of both numerical values described before and after "~". Further, when a numerical range is described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, unless otherwise particularly limited, each component in a composition, or each structural unit in a polymer (polymer) such as a copolymer, may be included alone or in combination of two or more.

Advantages of the Invention

[0009] The ethylene·α-olefin copolymer having an α1-substituted epoxy group at the terminal of the present invention is used for blending into synthetic resins as various modifiers. It is also used in paints, primers, coating materials, etc. Among them, by blending into an epoxy resin, a resin composition with improved mechanical strength can be provided.

[0010] Ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its termini The ethylene·α-olefin copolymer (Y) having an α1-substituted epoxy group at the terminal has a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and is a copolymer satisfying the following requirements (Y1) and (Y2). (Y1) 1 The content of the terminal containing an α1-substituted epoxy group in all terminals excluding the saturated terminals determined by 1H-NMR is 60% or more; (Y2) No melting point is observed by differential scanning calorimetry (DSC).

[0011] Furthermore, in a preferred embodiment of the present invention, the ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus is a copolymer that satisfies at least one of the following requirements (Y3) to (Y5), more preferably a copolymer that satisfies at least two of the following requirements (Y3) to (Y5), and even more preferably a copolymer that satisfies all of the following requirements (Y3) to (Y5).

[0012] (Y3) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%; (Y4) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10000; (Y5) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is between 1.5 and 5.5.

[0013] Of these provisions, constituent units (i) and (ii) are explained below. Examples of α-olefins having 3 to 10 carbon atoms in the constituent unit (ii) include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene, preferably α-olefins having 3 to 8 carbon atoms, more preferably α-olefins having 3 to 5 carbon atoms, and even more preferably propylene.

[0014] The content of these constituent units (i) and (ii) is arbitrary. Among these, it is preferable that the content of constituent unit (i) be 30 to 70 mol% (Requirement (Y3)), more preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%, based on a total of 100 mol%, and that the content of constituent unit (ii) be 30 to 70 mol% (Requirement (Y3)), more preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. The combination of the lower and upper limits for the content of constituent unit (i) and constituent unit (ii) is arbitrary. Next, requirements (Y1), (Y2), (Y4), and (Y5) are explained below.

[0015] Regarding (Y1) The present invention provides an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus. 1 This copolymer has a content of 60% or more of terminals containing α1-substituted epoxy groups, excluding saturated terminals determined by 1H-NMR. Of these, the content is more preferably 62% or more, and more preferably 65% ​​or more. The upper limit is preferably 100%, more preferably 95%, and even more preferably 90%.

[0016] (Regarding Y2) The ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus according to the present invention does not exhibit a melting point as measured by differential scanning calorimetry (DSC). Here, "not observing the melting point (Tm)" means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. "Not substantially measuring the heat of fusion (ΔH)" means that no peak is observed in the differential scanning calorimetry (DSC) measurement, or the observed heat of fusion is 1 J / g or less.

[0017] (Y4) The ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its terminus was measured by gel permeation chromatography (GPC), and the number-average molecular weight (Mn) obtained in polystyrene terms was preferably 300 to 10,000, more preferably 400 to 8,000, and more preferably 500 to 7,000. The combination of the lower and upper limits of the number-average molecular weight (Mn) is arbitrary.

[0018] (Y5) The ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its terminus was measured by gel permeation chromatography (GPC), and the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained on a polystyrene basis (Mw / Mn) was preferably 1.5 to 5.5, more preferably 1.55 to 5.2, even more preferably 1.57 to 5.0, and among these, 1.60 to 4.8 was preferred. (Mw / Mn) could be determined by the method described in the examples. Note that the combination of the lower and upper limits of Mw / Mn is arbitrary.

[0019] Method for producing an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus The ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus according to the present invention is produced by introducing an α1-substituted epoxy group at the terminus of an ethylene-α-olefin copolymer (A) having constituent units (i) and (ii). A preferred method involves converting the vinyl group ends of the ethylene-α-olefin copolymer (A) into epoxy-containing groups.

[0020] The raw material is ethylene-α-olefin copolymer (A) The method for producing the ethylene-α-olefin copolymer (A) is not particularly limited, but for example, it can be produced by copolymerizing ethylene with at least one α-olefin having 3 to 10 carbon atoms in the presence of an olefin polymerization catalyst. Preferably, the method includes a step of polymerizing the olefin at a temperature of 20 to 130°C in the presence of an activator and at least one metallocene compound.

[0021] The polymerization temperature is preferably 25 to 130°C, more preferably 30 to 125°C, and most preferably 40 to 120°C. A polymerization temperature within this range is preferable because it allows the molecular weight of the resulting polymer to be controlled within the range specified in requirement (A2). Examples of activators include at least one compound (b) selected from organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds that react with metallocene compounds to form ion pairs (b-3). Examples of organometallic compounds (b-1) (excluding organoaluminum oxy compounds (b-2)) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, as well as organoaluminum compounds such as tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride. Examples of organoaluminum oxy compounds (b-2) include conventionally known aluminoxanes. Examples of compounds (b-3) that react with metallocene compounds to form ion pairs include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, U.S. Patent No. 5321106, International Publication No. 2015 / 122415, etc. The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 8 MPa gauge pressure, and copolymerization can be carried out by batch, semi-continuous, or continuous methods. The reaction time (or average residence time if the copolymerization reaction is carried out continuously) varies depending on conditions such as catalyst concentration and polymerization temperature, and can be selected as appropriate, but is usually 1 minute to 3 hours, preferably 5 minutes to 2.5 hours. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting ethylene-α-olefin copolymer (A) can also be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. It can also be adjusted by the amount of catalyst component used. When hydrogen is added to the polymerization system, an appropriate amount is approximately 0.001 to 5,000 NL per 1 kg of the resulting ethylene-α-olefin copolymer. The amount of terminal unsaturation in the resulting ethylene-α-olefin copolymer (A) can be increased by minimizing the amount of hydrogenation.

[0022] The raw material ethylene-α-olefin copolymer (A) may contain biomass-derived monomers (ethylene, α-olefin). The monomers constituting the polymer may consist solely of biomass-derived monomers, or it may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are monomers derived from any renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, which are plant-derived or animal-derived, and which contain 10¹⁴C isotopes as carbon. -12 It contains a certain proportion, and the biomass carbon concentration (pMC) measured according to ASTM D 6866 is approximately 100 pMC. Biomass-derived monomers are obtained by conventionally known methods.

[0023] The raw material ethylene-α-olefin copolymer (A) may contain monomers derived from chemical recycling (ethylene, α-olefin). The monomers constituting the polymer may consist solely of monomers derived from chemical recycling, or they may contain monomers derived from chemical recycling, monomers derived from fossil fuels, and / or monomers derived from biomass. Monomers derived from chemical recycling can be obtained by conventionally known methods.

[0024] The raw material, ethylene-α-olefin copolymer (A), is not particularly limited, but among them, those that satisfy the following requirements (A1) to (A3) are preferred. (A1) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%. Preferably, the content of constituent unit (i) is 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%, and preferably the content of constituent unit (ii) is 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. Constituent unit (ii) is preferably an α-olefin having 3 to 8 carbon atoms, more preferably an α-olefin having 3 to 5 carbon atoms, and even more preferably propylene. The combination of the lower and upper limits of the content of constituent unit (i) and constituent unit (ii) is arbitrary. (A2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000, preferably 400 to 8,000, and more preferably 500 to 7,000. The combination of the lower and upper limits of the number-average molecular weight (Mn) is arbitrary. (A3) 1 The sum of the integrated intensities of the vinyl group endpoint and vinylidene group endpoint is greater than 70%, preferably greater than 75%, and more preferably greater than 80%, relative to 100% of the sum of the integrated intensities of the vinyl group endpoint, vinylidene group endpoint, disubstituted olefin endpoint, and trisubstituted olefin endpoint as determined by 1H-NMR. The upper limit is 100%, preferably 99%, and more preferably 98%.

[0025] In other words, the raw material, ethylene-α-olefin copolymer (A), has saturated and unsaturated ends, and the unsaturated ends include vinyl group ends, vinylidene group ends, disubstituted olefin ends, and trisubstituted olefin ends. Of these unsaturated ends, vinyl group ends and vinylidene group ends account for more than 70% of the total unsaturated ends (calculation is 1 If an ethylene-α-olefin copolymer (A) (as determined by H-NMR) is used as a raw material, it is preferable because by introducing vinyl group ends, if the reaction proceeds quantitatively, α1-substituted epoxy groups can be introduced to more than 70% of all ends excluding the saturated end. The ethylene-α-olefin copolymer (A) is preferably one that satisfies the following requirement (A4). (A4) The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn), measured by gel permeation chromatography (GPC) and obtained in polystyrene equivalent, is preferably 1.5 to 5.5, more preferably 1.55 to 5.2, even more preferably 1.57 to 5.0, and among these, 1.60 to 4.8 is preferred. (Mw / Mn) can be determined by the method described in the examples. Note that the combination of the lower and upper limits of Mw / Mn is arbitrary.

[0026] The method for converting the vinyl group, which is a terminal unsaturated group of the ethylene-α-olefin copolymer (A), to an α1-substituted epoxy group is not particularly limited, but the following methods can be given as examples. (1) Oxidation by peroxides such as performic acid, peracetic acid, and perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide (4) Oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Oxidation with Salen complex such as manganese Salen and hydrogen peroxide or hypochlorite (6) Oxidation with manganese-triazacyclononane (TACN) complex and other TACN complexes and hydrogen peroxide (7) Oxidation by hydrogen peroxide in the presence of a group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst. Of the methods (1) to (7) described above, method (1) is particularly preferred in terms of activity.

[0027] In the oxidation by peracid described in (1) above, it is preferable to use bis(monoperoxyphthalate)magnesium hexahydrate (MMPP) and / or m-chloroperbenzoic acid (mCPBA) as the peracid.

[0028] Purpose The ethylene-α-olefin copolymer (Z) having α1-substituted epoxy groups at its termini according to the present invention has many applications. For example, it is used as a modifier in synthetic resins. It is used in paints, primers, coatings, etc., and is also used as a modifier for these materials. It is used in various types of paints, including lacquer-based, urethane-based, acrylic-based, alkyd-based, epoxy-based, and polyester-based paints. As a primer, it is used as a compounding agent for synthetic resins, such as thermoplastic resins and thermosetting resins. Examples of modifiers include lubricating oil modifiers and surface modifiers. Examples of coating materials include fluorine-based and silicone-based materials.

[0029] Thermoplastic resins include (meth)acrylic resins, polycarbonate resins, polyester resins, fluorinated aromatic polymer resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyamide-imide resins, polystyrene resins, polyamide resins, polyimide resins, polyacetal, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, and ethylene-(meth)acrylic acid ester copolymer resins.

[0030] Thermosetting resins include epoxy resins, amino resins, phenolic resins, thermosetting urethane resins, thermosetting polyimide resins, amino alkyd resins, urea resins, benzooxanzine resins, silicon resins, and unsaturated polyester resins.

[0031] The ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus is preferably used in a composition with epoxy resins among synthetic resins. The composition of the present invention between an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus and a synthetic resin may optionally contain a curing agent. Examples of curing agents include alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, and 1,4-diaminobutane; polyalkyl polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-bisaminopropylallylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine, N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, and N,N-(bisaminopropyl) This includes (nopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N-bisaminopropylpentylamine, N,N-bisaminopropylhexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine; N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, N'-ethyl-N,N-dibenzylaminopropylamine, N,N-bisaminopropylbenzylamine, etc. Here, the epoxy compound typically has two or more epoxy groups. In one preferred and exemplary embodiment of the present invention, the curing agent is an amine compound. The hardening agent may be used individually or in combination of multiple types. In the composition containing a synthetic resin, an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at the terminal, and a curing agent as an optional component, the blending ratio of each component is not particularly limited, but a composition having the following blending ratio is preferred. When the total amount of the synthetic resin, the ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at the terminal, and the curing agent as an optional component is 100% by mass, the amount of the synthetic resin is 50% by mass or more and 95% by mass or less, the amount of the ethylene-α-olefin copolymer having an α1-substituted epoxy group at the terminal is 0.1% by mass or more and 50% by mass or less, and the amount of the curing agent is preferably 0% by mass or more and 10% by mass or less. Among them, the amount of the synthetic resin is more preferably 55% by mass or more and 90% by mass or less, the amount of the ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at the terminal is 0.5% by mass or more and 44.5% by mass or less, and the amount of the curing agent is more preferably 0.5% by mass or more and 9% by mass or less.

[0032] [Additive] The epoxy resin composition containing the epoxy resin of the present invention and the ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at the terminal may contain at least one selected from an organic solvent, an antistatic agent, a silane coupling agent, an ultraviolet absorber, an antioxidant, a tackifying resin, a plasticizer, an antifoaming agent, a filler, a stabilizer, a softening agent, and a wettability adjuster as an additive within a range not impairing the effects of the present invention.

[0033] Examples [[ID=**14**]]Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples at all. The physical property values were as follows.

[0034] [GPC measurement] The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the following copolymers used in the examples were determined by the following method. Ethylene-propylene copolymer (Y-a) having an α1-substituted epoxy group at the terminal, Terminal unsaturated ethylene-propylene copolymer (EPR-1), Terminal unsaturated ethylene-propylene copolymer (EPR-2), and Ethylene-propylene copolymer having an α2-substituted epoxy group at the terminal (EPR-3)

[0035] 〔Pretreatment of sample〕 After dissolving 10 mg of the copolymer synthesized in the example in 10 ml of THF at room temperature, the solution was filtered through a 0.45 μm hydrophilic PTFE membrane filter cartridge to obtain an analytical sample.

[0036] 〔GPC analysis〕 Using gel permeation chromatography (GPC), the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and a molecular weight distribution curve was obtained. The molecular weight distribution (Mw / Mn) was calculated from the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

[0037] 〔Measurement conditions〕 Measuring device: KP-22-13S dual pump (From), 717plus automatic injector (Waters Japan), RI-101 differential refractive index detector (Shodex) Analytical device: Data processing software Empower2 (registered trademark of Waters) Column: PLgel 5μ MIXED-D, 7.5 x 300 mm (Agilent Technologies) x 2 Column temperature: 40 °C Mobile phase: THF (containing stabilizer) Flow rate: 1 mL / min Injection volume: 0.1 mL Column calibration: Monodisperse polystyrene

[0038] < 1 H-NMR> 〔Measurement conditions〕 Measuring device: JEOL ECX400P nuclear magnetic resonance apparatus Measured nucleus: 1 H (400 MHz) Measurement mode: Single pulse Pulse width: 45° (5.25 μsec) Points: 32k Measurement range: 20 ppm (-4 to 16 ppm) Repeat time: 7.0 seconds Total number of times: 64 Measurement solvent: Deuterated chloroform Sample concentration: approx. 20 mg / 0.6 mL Measurement temperature: 25℃ Window function: exponential (BF: 0.12Hz) Chemical shift standard: Chloroform (7.26 ppm).

[0039] [Spectrum of ethylene-propylene copolymer (Ya) with α1-substituted epoxy groups at its termini] the above 1 The spectra obtained by 1H-NMR measurements show ethylene and propylene units in the main chain, terminal α1-substituted epoxy groups, α2-substituted epoxy groups, and unsaturated bonding groups (vinyl and vinylidene groups). The ethylene and propylene content and the content of terminals with α1-substituted epoxy groups were calculated from the integrated intensity of each signal. Furthermore, since disubstituted olefin terminals and trisubstituted olefin terminals in the unsaturated bonds of the ethylene-propylene copolymer (A-1) used as a raw material were hardly observed, these structures and the epoxy-containing terminals generated from these structures were not considered in the calculation formula.

[0040] [ka]

[0041] In each equation, the dashed lines represent bonds other than those of hydrogen atoms, and show the main chain of the ethylene-propylene copolymer. The peaks for each hydrogen atom (1-5) are observed around the following locations. • Hydrogen atom 1 peak: 0.95 ppm ~ 1.4 ppm • Hydrogen atom 2 peak: 0.95 ppm ~ 1.4 ppm • Hydrogen atom 3 peak: 1.4 ppm ~ 1.7 ppm • Hydrogen atom 4 peak: 3.0 ppm • Hydrogen atom 5 peak: 2.8 ppm • Hydrogen atom 6 peak: 5.9 ppm • Hydrogen atom 7 peak: 4.9 ppm • Hydrogen atom 8 peak: 4.6 ppm

[0042] [Content of α1-substituted epoxy groups at the terminal end of ethylene-propylene copolymer (Ya) having α1-substituted epoxy groups at the terminal end] The content of terminals having α1-substituted epoxy groups is as follows: Furthermore, since it is not possible to distinguish between peaks 7 and 10, the integrated intensity of peak 10 is calculated using peak 6. Concentration of terminals with α1-substituted epoxy groups = 100 × Integrated intensity of signal 4 / (Integrated intensity of signal 4 + Integrated intensity of signal 5 / 2 + Integrated intensity of signal 6 + Integrated intensity of signal 8 / 2)

[0043] [Calculation of ethylene and propylene content in ethylene-propylene copolymer (Ya) having α1-substituted epoxy groups at the terminals] The quantitative formulas for ethylene and propylene content are as follows: Ethylene content (mol%) = 100 × [(Integrated intensity of signal 1 + Integrated intensity of signal 2 - 2 × Integrated intensity of signal 3) / 4] / {[(Integrated intensity of signal 1 + Integrated intensity of signal 2 - 2 × Integrated intensity of signal 3) / 4] + Integrated intensity of signal 3} Propylene content (mol%) = 100 × Integrated intensity of signal 3 / {[(Integrated intensity of signal 1 + Integrated intensity of signal 2 - 2 × Integrated intensity of signal 3) / 4] + Integrated intensity of signal 3}

[0044] [Spectrum of ethylene-propylene copolymer (A-1)] the above 1The spectra obtained by 1H-NMR measurement showed ethylene and propylene units in the main chain, as well as vinyl group ends, vinylidene group ends, disubstituted olefin ends, and trisubstituted olefin ends. The ethylene and propylene content and the content of vinyl group ends in the unsaturated ends were calculated from the integrated intensity of each signal. Furthermore, the spectral assignment was the same as that of the ethylene-propylene copolymer (Ya) having α1-substituted epoxy groups at the ends described above.

[0045] [Calculation of ethylene and propylene content in ethylene-propylene copolymer (A-1)] The ethylene and propylene content was calculated using the same method as for the ethylene-propylene copolymer (Ya) having an α1-substituted epoxy group at its terminus.

[0046] [Content of vinyl group terminals in the unsaturated terminal of ethylene-propylene copolymer (A)] The quantitative formula for the content of vinyl groups at the unsaturated end is as follows. Furthermore, since peaks 7 and 10 cannot be separated, the integrated intensity is calculated using peak 6.

[0047] The content of vinyl groups at the unsaturated end = 100 × integrated intensity of signal 6 / [integrated intensity of signal 6 + (integrated intensity of signal 8 / 2) + (integrated intensity of signal 9 / 2) + (integrated intensity of signal 7 + integrated intensity of signal 10 - integrated intensity of signal 6 × 2)]

[0048] [Spectrum of the product obtained when an ethylene-propylene copolymer (Ya) with α1-substituted epoxy groups at its termini reacts with an amine compound] the above 1The spectra obtained by 1H-NMR measurement show terminal α1-substituted epoxy groups, α2-substituted epoxy groups, unsaturated vinyl and vinylidene groups, amine groups formed by ring-opening of epoxy groups, and hydroxyl groups. The content of terminal epoxy groups formed by ring-opening was calculated from the integrated intensity of each signal. In addition, to calculate the integrated value of hydroxyl groups, the hydroxyl groups were deuterated by adding a drop of heavy water to the measurement sample and stirring vigorously before measurement.

[0049] [ka]

[0050] • Hydrogen atom 4 peak: 3.0 ppm • Hydrogen atom 5 peak: 2.8 ppm • Hydrogen atom 6 peak: 5.9 ppm • Hydrogen atom 7 peak: 4.9 ppm • Hydrogen atom 8 peak: 4.6 ppm • Hydrogen atom peaks 9 and 10: 3.5 ppm to 3.9 ppm • Hydrogen atom 11 peak: 2.2~2.9 ppm Concentration of ring-opened epoxy groups at the terminal end = 100 × [(integrated intensity of signal 9 + integrated intensity of signal 10) / 5] / [(integrated intensity of signal 9 + integrated intensity of signal 10) / 5 + integrated intensity of signal 4 + [integrated intensity of signal 5 + integrated intensity of signal 11 - 6 × (integrated intensity of signal 9 + integrated intensity of signal 10) / 5] / 2 + integrated intensity of signal 6 + integrated intensity of signal 8 / 2]

[0051] <Raw materials> <<Terminal unsaturated ethylene-propylene copolymer (EPR-1)>> [Synthesis Example 1] The raw material, ethylene-propylene copolymer (EPR-1), was synthesized by the following method. 500 mL of xylene was added to a 1.0 L glass reactor that had been thoroughly purged with nitrogen. The reactor was then maintained at 110°C, and while stirring the inside of the polymerizer at 600 rpm, ethylene, propylene, and nitrogen were continuously supplied at 78 L / h, 44 L / h, and 52 L / h, respectively, until the liquid and gas phases were saturated. While ethylene and propylene were continuously supplied, 0.10 mL (0.10 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), 2.5 mL (0.005 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride (0.002 mol / L), and then 2.0 mL (0.020 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl) borate (hereinafter also referred to as Ph3CB(C6F5)4) (0.01 mol / L) were added, and polymerization was carried out at 110°C for 16 minutes under atmospheric pressure. Polymerization was stopped by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the solvent of the organic layer obtained by liquid-liquid extraction was removed under reduced pressure to obtain an ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130°C for 10 hours to obtain 8.45 g of ethylene-propylene copolymer. The obtained copolymer (EPR-1) had Mw=7240, Mn=2640, Mw / Mn=2.74, ethylene content=50 mol%, and propylene content=50 mol%. 1 The vinyl group content and vinylidene group content in the unsaturated end, as measured by 1H-NMR, were 81% and 16%, respectively.

[0052] [Synthesis Example 2] The raw material, ethylene-propylene copolymer (EPR-2), was synthesized by the following method. In a 500 mL glass reactor, 300 mL of toluene was added and maintained at 50°C. While stirring the inside of the polymerizer at 600 rpm, ethylene and propylene were continuously supplied at 9.9 L / h and 98.4 L / h, respectively, to saturate the liquid and gas phases. 5.0 mL (5.0 mmol) of a toluene solution (1.00 mol / L) of modified methylaluminoxane (hereinafter also referred to as MMAO) manufactured by Tosoh Fine Chemicals Co., Ltd. was added, followed by 2.5 mL (0.005 mmol) of a toluene solution (0.002 mol / L) of bis(cyclopentadienyl) zirconium(IV) dichloride manufactured by Fujifilm Wako Pure Chemical Corporation. Polymerization was carried out at atmospheric pressure at 50°C for 30 minutes. Except for these steps, purification was carried out in the same manner as in Example 1 to obtain 3.65 g of ethylene-propylene copolymer. The obtained copolymer (EPR-2) had Mw=3540, Mn=2300, Mw / Mn=1.53, ethylene content=49 mol%, and propylene content=51 mol%. 1 The content of vinyl group terminals and vinylidene group terminals in the unsaturated end, as measured by 1H-NMR, was 0% and 99%, respectively.

[0053] <<Ethylene-propylene copolymer with α2-substituted epoxy groups at its termini (EPR-3)>> [Synthesis Example 3] In a 50 mL round-bottom flask containing a stirring bar, 3.1 g of ethylene-propylene copolymer (EPR-2) obtained in Synthesis Example 2 was dissolved in 20 mL of dichloromethane. Then, at room temperature, while stirring with a magnetic stirrer, 0.52 g of mCPBA (water content approximately 30 wt%) was added and the mixture was reacted for 6 hours. After that, a small amount of saturated sodium bicarbonate solution and 25 wt% sodium sulfite aqueous solution were added to stop the reaction. The resulting reaction solution was washed with saturated sodium bicarbonate solution, and the organic layer obtained by liquid-liquid extraction was dried with sodium sulfate. The solvent was then removed by vacuum distillation to obtain 3.2 g of ethylene-propylene copolymer (EPR-3) having α2-substituted epoxy groups at the ends.

[0054] [Example 1] In a 300 mL round-bottom flask containing a stirring bar, 5.2 g of EPR-12 obtained in Synthesis Example 1 was dissolved in 150 mL of dichloromethane. Then, at room temperature, while stirring with a magnetic stirrer, 4.2 g of mCPBA (water content approximately 30 wt%) was added and the mixture was reacted for 72 hours. After that, a small amount of saturated sodium bicarbonate solution and 25 wt% sodium sulfite aqueous solution were added to stop the reaction. The resulting reaction solution was washed with saturated sodium bicarbonate solution, and the organic layer obtained by liquid-liquid extraction was dried with sodium sulfate. The solvent was then removed by vacuum distillation to obtain 24.3 g of ethylene-propylene copolymer (Ya) having α1-substituted epoxy groups at the ends. The obtained copolymer had Mw=7280, Mn=2530, Mw / Mn=2.88, ethylene content=50 mol%, propylene content=50 mol%, and a terminal content of 71% containing α1-substituted epoxy groups. 20.0 g of the ethylene-propylene copolymer (Ya) having α1-substituted epoxy groups at its termini was added to a 150 mL Schlenk tube containing a stirring bar. Then, 5.9 g of diethanolamine was added, and the mixture was dried at room temperature for 5 hours. After that, 20 mL of xylene was added, and the mixture was heated in an oil bath to 135 °C and reacted for 8 hours. The reaction solution was cooled to room temperature, and 100 mL of toluene was added. The resulting organic layer was washed with water, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The resulting product had a content of 67% of ring-opened epoxy groups at the termini.

[0055] [Comparative Example 1] 3.0 g of the ethylene-propylene copolymer (EPR-3) having α2-substituted epoxy groups at its termini was added to a 50 mL Schlenk tube containing a stirring bar. Then, 0.89 g of diethanolamine was added, and the mixture was dried at room temperature for 5 hours. After that, 5 mL of xylene was added, and the mixture was heated in an oil bath to 135 °C and reacted for 8 hours. The reaction solution was cooled to room temperature, and 50 mL of toluene was added. The resulting organic layer was washed with water, dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure. The resulting product had a 0% content of ring-opened epoxy groups at the termini.

[0056] [Table 1]

Claims

1. It has a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from α-olefins having 3 to 10 carbon atoms, An ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, satisfying the following requirements (Y1) and (Y2); (Y1) 1 More than 60% of all terminals, excluding the saturated terminal determined by H-NMR, contain an α1-substituted epoxy group; (Y2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

2. An ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, according to claim 1, further satisfying the following requirements (Y3) to (Y5); (Y3) With respect to a total of 100 mol% of the content of constituent unit (i) and constituent unit (ii), the content of constituent unit (i) is 30 to 70 mol%, and the content of constituent unit (ii) is 30 to 70 mol%; (Y4) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10000; (Y5) The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent (Mw / Mn) is between 1.5 and 5.

5.

3. An epoxy resin composition comprising an epoxy resin and an ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its termini, as described in either claim 1 or 2.

4. The epoxy resin composition according to claim 3, wherein when the total amount of epoxy resin and ethylene-α-olefin copolymer (Y) having α1-substituted epoxy groups at its termini is 100 parts by mass, the content of epoxy resin is 50 to 95 parts by mass.

5. A method for producing an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, satisfying the following requirements (Y1) and (Y2), by reacting an ethylene-α-olefin copolymer (A), which has a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, with a peroxide; (Y1) 1 The content of terminals containing an α1-substituted epoxy group is 60% or more of the total terminals excluding the saturated terminals determined by H-NMR; (Y2) The melting point measured by differential scanning calorimetry (DSC) is not observed.

6. A method for producing an ethylene-α-olefin copolymer (Y) having an α1-substituted epoxy group at its terminus, according to claim 5, wherein the ethylene-α-olefin copolymer (A) satisfies the following requirements (A1) to (A3); (A1) The content of component (i) is 30 to 70 mol% and the content of component (ii) is 30 to 70 mol% with respect to a total of 100 mol% of the content of component (i) and component (ii); (A2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is 300 to 10,000; (A3) 1 The vinyl group end content exceeds 70% of the total integrated intensity of the signals for vinyl group end-terminus, vinylidene group end-terminus, disubstituted olefin end-terminus, and trisubstituted olefin end-terminus, as determined by 1H-NMR.

Images