Aqueous dispersion composition, method for producing the same, and acid-modified ethylene-α-olefin copolymer

Abstract

The object of the present invention is to obtain an aqueous dispersion having further improved dispersibility of an acid-modified ethylene·α-olefin copolymer and excellent coating properties on a substrate. The present invention relates to an aqueous dispersion composition, characterized in that it contains an acid-modified ethylene·α-olefin copolymer (B) in a range of 0.01 to 50% by mass, wherein the acid-modified ethylene·α-olefin copolymer (B) is an acid-modified ethylene·α-olefin copolymer (A) that satisfies the following (A1) to (A6) and satisfies the following (B1) to (B5). (A1) The content of ethylene units is in the range of 30 to 85 mol%. (A2) The kinematic viscosity at 100°C is in the range of 10 to 5,000 mm 2 / s. (A3) The weight average molecular weight obtained by gel permeation chromatography (GPC) and converted to polystyrene is in the range of 1,000 to 50,000. (A4) The molecular weight distribution (Mw / Mn) of the molecular weight obtained by gel permeation chromatography (GPC) and converted to polystyrene is 2.5 or less. (A5) The B value represented by the following formula [1] is 1.1 or more. [In formula [1], P E Indicates the molar fraction of ethylene units, P O represents the molar fraction of α-olefin units, P OE represents the molar fraction of ethylene·α-olefin chains in all binary chains. ](A6) Using 1 The amount of unsaturated bonds as measured by H-NMR is less than 0.5 per 1000 carbon atoms. (B1) The acid value is in the range of 1 to 300 mgKOH / g. (B2) The apparent viscosity at 150°C is in the range of 1 to 1,000 cPs. (B3) The weight average molecular weight as measured by gel permeation chromatography (GPC) and converted to polystyrene is in the range of 1,000 to 50,000. (B4) The molecular weight distribution (Mw / Mn) of the molecular weights as measured by gel permeation chromatography (GPC) and converted to polystyrene is 2.5 or less. (B5) The weight fraction of unreacted molecules as measured by high performance liquid chromatography (HPLC) is 59% or less.

Description

Technical Field

[0001] The present invention relates to an aqueous dispersion composition having good dispersibility, a method for producing the aqueous dispersion composition, and an acid-modified product of an ethylene-α-olefin copolymer. Background Art

[0002] Conventionally, in various industrial fields, it is known to bond substrates such as plastic films, vapor-deposited films, metal foils, paper, and non-woven fabrics to each other or to another adherend using heat and pressure (i.e., heat sealing). Heat sealing typically involves directly bonding the substrates to each other or to the adherend. However, to improve the heat-sealability between the substrate and the adherend, methods have also been used in which a heat sealant (adhesive) layer is pre-formed on the substrate and the substrates are bonded to each other or to the adherend via the adhesive layer.

[0003] As an adhesive used in such a heat sealant, for example, an aqueous dispersion containing at least one high-crystallinity polyolefin having a crystallinity of more than 50%, at least one dispersant, and water has been proposed (for example, see Patent Document 1).

[0004] The present applicant has discovered that the dispersibility of the acid-modified product (B) and the like in an aqueous dispersion composition containing at least one selected from a specific ethylene / α-olefin copolymer (A) and an acid-modified product (B) of the aforementioned (A) in an amount of 0.01 to 50% by mass is improved, and this has been proposed in Japanese Patent Application Laid-Open No. 2016-102157 (Patent Document 2). However, depending on the application, there is a demand for aqueous dispersions with even better dispersibility and excellent coating properties on substrates and the like.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-52124

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2016-102157 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] An object of the present invention is to obtain an aqueous dispersion of an acid-modified ethylene / α-olefin copolymer having further improved dispersibility and excellent coating properties on substrates and the like.

[0011] Means for solving problems

[0012] The inventors of the present application have conducted various studies to obtain an aqueous dispersion with further improved dispersibility. As a result, they have discovered that the above-mentioned purpose can be achieved by using an acid-modified product obtained by modifying an ethylene-α-olefin copolymer with an unsaturated carboxylic acid and its derivatives, particularly an acid-modified product with a high modification rate, in other words, a low content of unreacted molecules, as the ethylene-α-olefin copolymer forming the aqueous dispersion.

[0013] That is, the present invention relates to an aqueous dispersion composition characterized in that it contains an acid-modified ethylene / α-olefin copolymer (B) in a range of 0.01 to 50% by mass, wherein the acid-modified ethylene / α-olefin copolymer (B) is an acid-modified ethylene / α-olefin copolymer (A) that satisfies the following (A1) to (A6) and also satisfies the following (B1) to (B5).

[0014] The content of the (A1) ethylene unit is within a range of 30 to 85 mol%.

[0015] (A2) Kinematic viscosity at 100°C is 10-5,000 mm 2 / s range.

[0016] (A3) The weight average molecular weight as measured by gel permeation chromatography (GPC) and calculated as polystyrene is within the range of 1,000 to 50,000.

[0017] (A4) The molecular weight distribution (Mw / Mn) of the molecular weight calculated as polystyrene as measured by gel permeation chromatography (GPC) is 2.5 or less.

[0018] (A5) The B value represented by the following formula [1] is 1.1 or more.

[0019] [Mathematical formula 1]

[0020]

[0021] [In formula [1], P E Indicates the molar fraction of ethylene units, P O represents the molar fraction of α-olefin units, P OE Indicates the molar fraction of ethylene·α-olefin chains in all binary chains.]

[0022] (A6) Utilization 1 The amount of unsaturated bonds measured by H-NMR was less than 0.5 per 1000 carbon atoms.

[0023] (B1) The acid value is within the range of 1 to 300 mgKOH / g.

[0024] (B2) The apparent viscosity at 150°C is within the range of 1 to 1,000 cPs.

[0025] (B3) The weight average molecular weight as measured by gel permeation chromatography (GPC) and calculated as polystyrene is within the range of 1,000 to 50,000.

[0026] (B4) The molecular weight distribution (Mw / Mn) of the molecular weight calculated as polystyrene as measured by gel permeation chromatography (GPC) is 2.5 or less.

[0027] (B5) The weight fraction of unreacted molecules measured by high performance liquid chromatography (HPLC) is 59% or less.

[0028] Effects of the Invention

[0029] In the aqueous dispersion of the present invention, the particle size of the acid-modified ethylene / α-olefin copolymer (B) forming the aqueous dispersion is reduced, and the dispersibility is further improved, so the emulsion becomes less likely to separate, thereby improving long-term stability. In addition, the interaction between the particles is increased, and the viscosity is increased, thereby improving the adhesion to the substrate. In addition, liquid suspension is also suppressed, thereby improving the coating properties on the substrate, etc. DETAILED DESCRIPTION

[0030] Hereinafter, the aqueous dispersion composition, the method for producing the aqueous dispersion composition, and the acid-modified ethylene / α-olefin copolymer of the present invention will be described in detail.

[0031] The aqueous dispersion composition of the present invention contains the acid-modified product (B) of the ethylene-α-olefin copolymer (A) described below. hereinafter, these components are also referred to as "component (A)" and "component (B)", respectively.

[0032] In this specification, a structural unit derived from a monomer is also referred to as a "monomer unit".

[0033] [Ethylene-α-olefin copolymer (A)]

[0034] The ethylene / α-olefin copolymer (A) serving as a raw material for the acid-modified ethylene / α-olefin copolymer (B) forming the aqueous dispersion of the present invention satisfies the following (A1) to (A6).

[0035] The content of the (A1) ethylene unit is within a range of 30 to 85 mol%.

[0036] The ethylene unit content in component (A) is within the range of 30 to 85 mol%, preferably 40 to 70 mol%, and particularly preferably 45 to 65 mol%. If the content exceeds this range, the copolymer will develop crystallinity, resulting in an increase in viscosity or a solidification of the copolymer, which will impair its dispersibility in water. Furthermore, if the content exceeds 85 mol%, the number of tertiary carbon atoms in the main chain, which are susceptible to decomposition reactions, will decrease. This is not preferred when the aqueous dispersion composition of the present invention is used as a mold release agent for die casting, for example, because thermally generated oxidative degradation products tend to accumulate on the mold surface.

[0037] The content of ethylene units in component (A) can be determined by the method described in "Polymer Analysis Guide" (first edition published by Asakura Bookstore in 2008, pages 184 to 211). 13 C-NMR is measured. Alternatively, the sample calculated using this method can be used as a known sample and measured using Fourier transform infrared spectroscopy (FT-IR). It should be noted that the total content of all monomer units is set to 100 mol%.

[0038] (A2) Kinematic viscosity at 100°C is 10-5,000 mm 2 / s range.

[0039] The kinematic viscosity of the component (A) is a value measured by the method described in JIS K2283. The kinematic viscosity of the component (A) at 100°C is 10 to 5,000 mm 2 / s, preferably in the range of 10 to 2,500 mm 2 / s, more preferably 15 to 2,500 mm 2 / s, particularly preferably 15 to 500 mm 2 / s. If the kinematic viscosity is too low, the volatile components are high, which can easily ignite and deteriorate the storage stability. Alternatively, the evaporation loss in the aqueous dispersion increases, and for example, when used as a mold release agent for molding, the high molecular weight components that tend to adhere to the mold are reduced, which is not preferred. If the kinematic viscosity exceeds the above range, the viscosity of the copolymer increases, making it difficult to disperse evenly in water.

[0040] (A3) The weight average molecular weight is within the range of 1,000 to 50,000.

[0041] The weight average molecular weight (Mw) of component (A) is a value obtained by measuring by gel permeation chromatography (GPC) according to the method described below and converted to standard polystyrene. The weight average molecular weight (Mw) of component (A) is in the range of 1,000 to 50,000, preferably in the range of 1,500 to 30,000, more preferably in the range of 1,500 to 20,000, and particularly preferably in the range of 1,500 to 7,000. If the Mw is too low below the above range, the volatile components are high, which makes it easy to ignite and the storage properties deteriorate, or the evaporation loss in the aqueous dispersion increases, for example, when used as a mold release agent for molding, the high molecular weight components that easily adhere to the mold are reduced, etc., which is not preferred. If the Mw exceeds the above range, the viscosity of the copolymer increases, making it difficult to disperse evenly in water.

[0042] (A4) The molecular weight distribution is 2.5 or less.

[0043] The molecular weight distribution of component (A) can be calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by measuring the molecular weight distribution according to the method described later and converting the molecular weight distribution according to standard polystyrene using gel permeation chromatography (GPC). The Mw / Mn of component (A) is 2.5 or less, preferably 2.3 or less, and more preferably 2.0 or less. The so-called molecular weight distribution exceeds the above range excessively, which means that the copolymer contains a large amount of low molecular weight components and high molecular weight components. When the copolymer contains a large amount of low molecular weight components, there are many volatile components, so it is easy to ignite and the preservation property deteriorates, or the evaporation loss in the aqueous dispersion increases. When the copolymer contains a large amount of high molecular weight components, the viscosity of the copolymer rises, and it is difficult to be evenly dispersed in water.

[0044] (A5) The B value is 1.1 or more.

[0045] The B value of component (A) represented by the following formula [1] is 1.1 or more, preferably 1.2 or more. The upper limit of the B value is not particularly limited, but is usually 2.0 or less.

[0046] [Mathematical formula 1]

[0047]

[0048] In formula [1], P E Indicates the molar fraction of ethylene units, P O represents the molar fraction of α-olefin units, P OE It represents the molar fraction of ethylene·α-olefin chains in all binary chains.

[0049] The B value is an index indicating the randomness of the comonomer chain distribution in the copolymer. E 、P O and POE In terms of 13 The C-NMR spectrum was obtained based on reports by JC Randall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], and known literature such as "Polymer Analysis Guide" (first edition published by Asakura Bookstore in 2008, pages 184-211).

[0050] As the B value increases, the chain structure of the ethylene units and α-olefin units decreases, the distribution of the ethylene units and α-olefin units becomes more uniform, and the copolymer has a narrower composition distribution. As a result, as the B value increases, component (A) becomes less likely to crystallize, the viscosity of component (A) does not increase, or component (A) does not become solid, and its dispersibility in water is less likely to deteriorate.

[0051] The specific measurement conditions of the B value are as described in the Examples.

[0052] (A6) Utilization 1 The amount of unsaturated bonds measured by H-NMR was less than 0.5 per 1000 carbon atoms.

[0053] The molecules of component (A) have 1 The total number of double bonds derived from vinyl, vinylidene, disubstituted olefins, and trisubstituted olefins, as measured by H-NMR (hereinafter referred to as "unsaturated bond content") is less than 0.5, preferably less than 0.3, more preferably less than 0.2, and particularly preferably less than 0.1, per 1000 carbon atoms. When the unsaturated bond content is within this range, the heat resistance of component (A) is improved. Specific conditions for measuring the unsaturated bond content are described in the Examples.

[0054] Component (A) preferably further satisfies the following (A7).

[0055] (A7) No melting point was observed.

[0056] Component (A) preferably has no observable melting point in differential scanning calorimetry (DSC). Here, "no observable melting point (Tm)" means that substantially no heat of fusion (ΔH) (unit: J / g) is measured by differential scanning calorimetry (DSC). "Substantially no heat of fusion (ΔH)" means that no peak is observed in differential scanning calorimetry (DSC), or that the observed heat of fusion is 1 J / g or less.

[0057] The melting point (Tm) and heat of fusion (ΔH) of component (A) can be determined by differential scanning calorimetry (DSC) by analyzing the DSC curve after cooling to -100°C and then heating to 150°C at a rate of 10°C / minute, in accordance with JIS K7121. If no melting point is observed, this indicates that component (A) has low crystallinity, the viscosity of component (A) does not increase, or component (A) does not become solid, and its dispersibility in water is excellent.

[0058] Examples of the α-olefins forming component (A) include linear or branched α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0059] The α-olefin is preferably a linear or branched α-olefin having 3 to 10 carbon atoms, more preferably at least one selected from propylene, 1-butene, 1-hexene, and 1-octene. From the viewpoint of the fluidity of the aqueous dispersion composition using the resulting copolymer, propylene is most preferred.

[0060] The α-olefins may be used alone or in combination of two or more.

[0061] Alternatively, at least one other monomer selected from a polar group-containing monomer, an aromatic vinyl compound, an alicyclic vinyl compound, and a cyclic olefin may be coexisted with the α-olefin in the reaction system for polymerization to obtain component (A). The other monomer may be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, relative to 100 parts by mass of the total of ethylene and the α-olefin.

[0062] Examples of the polar group-containing monomer include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, and metal salts thereof such as sodium salts; α,β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, methyl methacrylate, and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; and unsaturated glycidyl groups such as glycidyl acrylate and glycidyl methacrylate.

[0063] Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene, α-methylstyrene, and allylbenzene.

[0064] Examples of the alicyclic vinyl compound include vinylcyclohexane and the like.

[0065] Examples of the cyclic olefin include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.

[0066] Component (A) may be used alone or in combination of two or more. For example, two or more components (A) having different molecular weights and / or different monomer compositions may be used in combination.

[0067] The method for producing component (A) is not particularly limited, and examples thereof include methods using a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound, such as those described in Japanese Patent Publication No. 2-1163 and Japanese Patent Publication No. 2-7998. Furthermore, as a method for producing a copolymer with high polymerization activity, methods using a metallocene-based catalyst comprising a metallocene compound (e.g., zirconocene) and an organoaluminum oxy-compound (e.g., aluminoxane), such as those described in Japanese Patent Application Laid-Open No. 61-221207, Japanese Patent Publication No. 7-121969, Japanese Patent No. 2796376, and Japanese Patent No. 4367687, can be utilized. However, methods using a metallocene-based catalyst are more preferred because they can reduce the chlorine content of the resulting copolymer and the amount of 2,1-insertion of propylene.

[0068] In the method using a vanadium-based catalyst, a larger amount of a chlorine compound is used as a co-catalyst compared to the method using a metallocene-based catalyst. Therefore, there is a possibility that a small amount of chlorine remains in the obtained component (A).

[0069] On the other hand, methods using metallocene catalysts essentially eliminate residual chlorine, eliminating the need to consider the possibility of the aqueous dispersion promoting corrosion of metal components such as storage containers. The chlorine content in the copolymer is preferably 100 wtppm or less, more preferably 50 wtppm or less, even more preferably 20 wtppm or less, and particularly preferably 5 wtppm or less. Chlorine content can be quantified using various known methods. Specific determination methods in the present invention are described in the Examples.

[0070] In addition, the reduction of the 2,1-insertion amount of propylene in component (A) can further reduce the number of ethylene chains in the copolymer molecule and suppress the intramolecular crystallinity of ethylene. Therefore, such a copolymer has excellent dispersibility in water. The 2,1-insertion amount of propylene can be reduced by the method described in Japanese Patent Application Laid-Open No. 7-145212. 13It is determined by analysis of C-NMR measurement and is preferably less than 1%, more preferably 0 to 0.5%, and even more preferably 0 to 0.1%. It is particularly preferred that no peak be observed in the range of 15.0 to 17.5 ppm.

[0071] In particular, by utilizing the following method, a component (A) having a good balance of properties in terms of molecular weight control, molecular weight distribution, amorphousness, and B value can be obtained.

[0072] Component (A) can be produced by copolymerizing ethylene and an α-olefin in the presence of an olefin polymerization catalyst comprising a bridged metallocene compound (a) represented by the following general formula [I] and at least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxy-compound (b-2), and a compound (b-3) capable of reacting with the bridged metallocene compound (a) to form an ion pair.

[0073] [Chemical Formula 1]

[0074]

[0075] <Bridged Metallocene Compound (a)>

[0076] The bridged metallocene compound (a) is represented by the above-mentioned formula [I].

[0077] The following is for Y, M, R in formula [I] 1 ~R 14 , Q, n and j are explained.

[0078] (Y, M, R 1 ~R 14 , Q, n and j)

[0079] Y is a Group 14 atom, and examples thereof include a carbon atom, a silicon atom, a germanium atom, and a tin atom. It is preferably a carbon atom or a silicon atom, and more preferably a carbon atom.

[0080] M is a titanium atom, a zirconium atom or a hafnium atom, and is preferably a zirconium atom.

[0081] R 1 ~R 12 is an atom or substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and each of them may be the same or different. 1 to R 12 Adjacent substituents may or may not be bonded to each other to form a ring.

[0082] Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms.

[0083] Examples of the alkyl group having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and branched saturated hydrocarbon groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, and cyclopropylmethyl. The alkyl group preferably has 1 to 6 carbon atoms.

[0084] Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include unsubstituted cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, 1-adamantyl, and 2-adamantyl; and unsubstituted cyclic saturated hydrocarbon groups in which one or two or more hydrogen atoms are replaced with hydrocarbon groups having 1 to 17 carbon atoms such as 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, and 4-phenylcyclohexyl. The cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.

[0085] Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), and 1-methylvinyl (isopropenyl); and alkynyl groups such as ethynyl, 1-propynyl, and 2-propynyl (propargyl). The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

[0086] Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include cyclopentadienyl, norbornenyl, phenyl, naphthyl, indenyl, azulenyl, phenanthrenyl, anthracenyl, and the like, which are unsubstituted cyclic unsaturated hydrocarbon groups; 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, biphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl (mesityl), and the like, which are groups in which one or two or more hydrogen atoms contained in an unsubstituted cyclic unsaturated hydrocarbon group are substituted with a hydrocarbon group having 1 to 15 carbon atoms; and benzyl and cumyl, which are groups in which one or two or more hydrogen atoms contained in a linear or branched saturated hydrocarbon group are substituted with an unsubstituted or substituted cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms. The cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.

[0087] Examples of silicon-containing groups include alkylsilyl groups such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl, arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and tert-butyldiphenylsilyl, pentamethyldisilyl, and trimethylsilylmethyl, which are groups in which at least one carbon atom in a hydrocarbon group having 1 to 20 carbon atoms is replaced with a silicon atom; alkylsilyl groups such as pentamethyldisilyl and trimethylsilylmethyl. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

[0088] Examples of nitrogen-containing groups include amino groups; dimethylamino groups, diethylamino groups, N-morpholino groups, dimethylaminomethyl groups, cyano groups, pyrrolidinyl groups, piperidinyl groups, pyridyl groups, and nitro groups, which are groups in which at least one =CH- structural unit in the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms or silicon-containing groups is replaced by a nitrogen atom, a group in which at least one -CH2- structural unit is replaced by a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, a group in which at least one -CH3 structural unit is replaced by a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, or a group in which at least one -CH3 structural unit is replaced by a nitrile group. Examples of nitrogen-containing groups include dimethylamino groups and N-morpholino groups.

[0089] Examples of the oxygen-containing group include: a hydroxyl group; a group in which at least one -CH2- structural unit in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group or nitrogen-containing group is replaced by an oxygen atom or a carbonyl group, or a group in which at least one -CH3 structural unit is replaced by an oxygen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a tert-butoxy group, a phenoxy group, a trimethylsilyloxy group, a methoxyethoxy group, a hydroxymethyl group, a methoxymethyl group, an ethoxy group; Methyl, tert-butoxymethyl, 1-hydroxyethyl, 1-methoxyethyl, 1-ethoxyethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-oxa-n-butylene, 2-oxa-n-pentylidene, 3-oxa-n-pentylidene, aldehyde, acetyl, propionyl, benzoyl, trimethylsilylcarbonyl, carbamoyl, methylaminocarbonyl, carboxyl, methoxycarbonyl, carboxymethyl, ethoxycarboxymethyl, carbamoylmethyl, furyl, pyranyl, etc. The oxygen-containing group is preferably a methoxy group.

[0090] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, which are elements of Group 17.

[0091] Examples of the halogen-containing group include trifluoromethyl, tribromomethyl, pentafluoroethyl, pentafluorophenyl, and the like, which are groups in which at least one hydrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, nitrogen-containing group, or oxygen-containing group is substituted with a halogen atom.

[0092] From R 1 to R 12 Adjacent substituents may be bonded to each other to form an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, etc. 1 to R 12 The bonded ring carbons together form a ring.

[0093] Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylene), ethylmethylene, methylethylene, and n-propylene. The alkylene group preferably has 1 to 6 carbon atoms.

[0094] Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene, m-phenylene, p-phenylene, and 4,4'-biphenylene. The arylene group preferably has 6 to 12 carbon atoms.

[0095] Q can be selected from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, and neutral ligands capable of coordination using lone pair electrons, in the form of the same or different combinations.

[0096] The details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, it is preferably a chlorine atom. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.

[0097] Examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy, and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as methanesulfonate and toluenesulfonate.

[0098] Examples of the neutral ligand capable of coordination using a lone pair of electrons include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ether compounds such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0099] j is an integer of 1 to 4, and preferably 2.

[0100] n is an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

[0101] R 13 and R 14 is an atom or substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (excluding the following aryl groups and substituted aryl groups), an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and each of them may be the same or different. 13 and R 14 They may be bonded to each other to form a ring, or they may not be bonded to each other.

[0102] Details of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom, and the halogen-containing group are as described above.

[0103] Examples of the aryl group are partially the same as those of the aforementioned cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, and include phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthrenyl, naphthacene, Examples of the aryl group include phenyl, 2-naphthyl, pyrenyl, indenyl, azulenyl, pyrrolyl, pyridyl, furyl, and thienyl. The aryl group is preferably phenyl or 2-naphthyl.

[0104] Examples of the aromatic compound include benzene, naphthalene, anthracene, phenanthrene, tetracene, Pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, etc.

[0105] The substituted aryl group partially overlaps with the examples of the aforementioned cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, and includes groups in which one or two or more hydrogen atoms possessed by the aforementioned aryl group are substituted with at least one substituent selected from a hydrocarbon group having 1 to 20 carbon atoms (excluding an aryl group), an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group. Specifically, 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 3-ethylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, biphenyl, 4-(trimethylsilyl)phenyl, 4-aminophenyl, 4-(dimethylamino)phenyl, 4-(diethylamino)phenyl, 4-morpholinylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-phenoxyphenyl, 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 3-methyl-4-methoxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3-(trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 5-methylnaphthyl, 2-(6-methyl)pyridyl, and the like.

[0106] R 13 and R 14 They can be bonded to each other to form an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, etc. 13 and R 14 The bonded Y groups together form a ring. Specific examples of the alkylene group and the arylene group are as described above.

[0107] In the bridged metallocene compound (a) represented by the above formula [I], n is preferably 1. Such a bridged metallocene compound is hereinafter also referred to as a "bridged metallocene compound (a-1)".

[0108] Compared with the compound wherein n in the above formula [I] is an integer of 2 to 4, the bridged metallocene compound (a-1) has the following advantages: the production process can be simplified and the production cost can be reduced. Furthermore, by using the bridged metallocene compound (a-1), the production cost of the ethylene / α-olefin copolymer (A) can be reduced.

[0109] In the bridged metallocene compound (a-1), R 1 、R 2 、R 3 and R 4 All of them are hydrogen atoms. Hereinafter, such a bridged metallocene compound is also referred to as a "bridged metallocene compound (a-2)."

[0110] The bridged metallocene compound (a-2) and R in the above formula [I] 1 、R 2 、R 3 and R 4 Compared to a compound in which at least one of the bridged metallocene compounds (a-2) is substituted with a substituent other than a hydrogen atom, the following advantages are achieved: the production process is simplified and the production cost is reduced. Furthermore, by using the bridged metallocene compound (a-2), the production cost of the ethylene / α-olefin copolymer (A) is reduced. Furthermore, it is generally known that the randomness of the ethylene / α-olefin copolymer (A) decreases with high-temperature polymerization. However, when ethylene and an α-olefin are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a-2), the following advantages are achieved: even with high-temperature polymerization, the resulting ethylene / α-olefin copolymer (A) has a high randomness.

[0111] In the bridged metallocene compound (a-2), R 13 and R 14 Any one of them is an aryl group or a substituted aryl group. Hereinafter, such a bridged metallocene compound is also referred to as a "bridged metallocene compound (a-3)". The bridged metallocene compound (a-3) and R 13 and R 14 Compared with the case where all substituents are other than aryl groups and substituted aryl groups, there is an advantage that the amount of double bonds in the produced ethylene / α-olefin copolymer (A) is small.

[0112] Among the bridged metallocene compounds (a-3), R 13 and R 14 Any one of them is an aryl group or a substituted aryl group, and the other is an alkyl group having 1 to 20 carbon atoms, and R is particularly preferred. 13 and R 14Any one of them is an aryl group or a substituted aryl group, and the other is a methyl group. Hereinafter, such a bridged metallocene compound is also referred to as a "bridged metallocene compound (a-4)". The bridged metallocene compound (a-4) and R 13 and R 14 Compared with the case where all of them are aromatic or substituted aromatic groups, the following advantages can be obtained: the balance between the double bond amount and polymerization activity in the produced ethylene·α-olefin copolymer (A) is excellent, and the production cost of the ethylene·α-olefin copolymer (A) can be reduced by using the bridged metallocene compound.

[0113] When polymerization is carried out under certain conditions of total pressure and temperature within the polymerization reactor, the following problem arises: the increase in hydrogen partial pressure due to hydrogen introduction causes a decrease in the partial pressure of the olefins used as polymerization monomers, particularly in regions with high hydrogen partial pressures, which reduces the polymerization rate. The permissible total internal pressure of a polymerization reactor is limited in design. Therefore, if excessive hydrogen introduction is required, particularly when producing low-molecular-weight olefin polymers, the olefin partial pressure decreases significantly, sometimes leading to a decrease in polymerization activity. However, when a bridged metallocene compound (a-4) is used to produce an ethylene / α-olefin copolymer (A), the following advantages are achieved, compared to the use of the bridged metallocene compound (a-3): the amount of hydrogen introduced into the polymerization reactor is reduced, the polymerization activity is improved, and the production cost of the ethylene / α-olefin copolymer (A) is reduced.

[0114] In the bridged metallocene compound (a-4), R 6 and R 11 is an alkyl group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms formed by bonding with adjacent substituents. Such a bridged metallocene compound is hereinafter referred to as a "bridged metallocene compound (a-5)". 6 and R 11 Compared with compounds substituted with substituents other than alkyl groups having 1 to 20 carbon atoms and alkylene groups having 1 to 20 carbon atoms, the following advantages can be obtained: the production process can be simplified and the production cost can be reduced. Furthermore, by using this bridged metallocene compound (a-5), the production cost of the ethylene / α-olefin copolymer (A) can be reduced.

[0115] In the bridged metallocene compounds (a), (a-1), (a-2), (a-3), (a-4), and (a-5), M is more preferably a zirconium atom. When ethylene and an α-olefin are copolymerized in the presence of an olefin polymerization catalyst comprising the bridged metallocene compound in which M is a zirconium atom, advantages such as higher polymerization activity and reduced production costs of the ethylene / α-olefin copolymer (A) are achieved compared to cases in which M is a titanium atom or a hafnium atom.

[0116] Examples of such bridged metallocene compounds (a) include:

[0117] [Dimethylmethylene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [dimethylmethylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [dimethylmethylene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [dimethylmethylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dimethylmethylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0118] [Cyclohexylidene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [Cyclohexylidene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [Cyclohexylidene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [Cyclohexylidene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [Cyclohexylidene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0119] [Diphenylmethylene (η5-cyclopentadienyl) (η5-fluorenyl)] zirconium dichloride, [diphenylmethylene (η5-cyclopentadienyl) (η5-2,7-di-tert-butylfluorenyl)] zirconium dichloride, [diphenylmethylene (η5-2-methyl-4-tert-butylcyclopentadienyl) (η5-2,7-di-tert-butylfluorenyl)] zirconium dichloride, [diphenylmethylene (η5-cyclopentadienyl) (η5-3,6 -di-tert-butylfluorenyl)]zirconium dichloride, [diphenylmethylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylmethylene{η5-(2-methyl-4-isopropylcyclopentadienyl)}(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylmethylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0120] [Methylphenylmethylene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [methylphenylmethylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methylphenylmethylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0121] [Methyl(3-methylphenyl)methylene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [Methyl(3-methylphenyl)methylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [Methyl(3-methylphenyl)methylene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [Methyl(3-methylphenyl)methylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [Methyl(3-methylphenyl)methylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0122] [Diphenylsilylene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [Diphenylsilylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [Diphenylsilylene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [Diphenylsilylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [Diphenylsilylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0123] [Bis(3-methylphenyl)silylene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0124] [Dicyclohexylsilylene(η5-cyclopentadienyl)(η5-fluorenyl)]zirconium dichloride, [Dicyclohexylsilylene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [Dicyclohexylsilylene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [Dicyclohexylsilylene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [Dicyclohexylsilylene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0125] Ethylidene(η5-cyclopentadienyl)(η5-fluorenyl)zirconium dichloride, ethylidene(η5-cyclopentadienyl)(η5-2,7-di-tert-butylfluorenyl)zirconium dichloride, ethylidene(η5-cyclopentadienyl)(η5-3,6-di-tert-butylfluorenyl)zirconium dichloride, ethylidene(η5-cyclopentadienyl)(η5-octamethyloctahydrodibenzofluorenyl)zirconium dichloride, ethylidene(η5-cyclopentadienyl)(η5-tetramethyloctahydrodibenzofluorenyl)zirconium dichloride,

[0126] and so on.

[0127] Examples include compounds obtained by replacing the zirconium atom of these compounds with a hafnium atom or compounds obtained by replacing the chlorine ligand with a methyl group, etc., but the bridged metallocene compound (a) is not limited to these examples. It should be noted that, respectively, the η5-tetramethyloctahydrodibenzofluorenyl, which is a constituent part of the exemplified bridged metallocene compound (a), represents 4,4,7,7-tetramethyl-(5a,5b,11a,12,12a-η5)-1,2,3,4,7,8,9,10-octahydrodibenz[b,H]fluorene group, and the η5-octamethyloctahydrodibenzofluorenyl represents 1,1,4,4,7,7,10,10-octamethyl-(5a,5b,11a,12,12a-η5)-1,2,3,4,7,8,9,10-octahydrodibenz[b,H]fluorene group.

[0128] <Compound (b)>

[0129] The polymerization catalyst preferably used in the present invention comprises a bridged metallocene compound (a) and at least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxide compound (b-2), and a compound (b-3) capable of reacting with the aforementioned bridged metallocene compound (a) to form an ion pair.

[0130] As the organometallic compound (b-1), specifically, organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table as described below can be used.

[0131] (b-1a) An organoaluminum compound represented by the general formula R a mAl(OR b )nHpXq.

[0132] (In the formula, R a and R b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number of 0 < m ≤ 3, n is a number of 0 ≤ n < 3, p is a number of 0 ≤ p < 3, q is a number of 0 ≤ q < 3, and m + n + p + q = 3)

[0133] Examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tris(4-methylphenyl)aluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; and compounds of the general formula (i-C4H9). x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers, z ≤ 2x.) Alkenyl aluminum such as isoprenyl aluminum, alkyl aluminum alkoxides such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide, alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, and aluminum sesquialkoxides having the general formula R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminums having an average composition represented by , etc., alkylaryl aluminum oxides such as diethylaluminum phenoxide and diethyl(2,6-di-tert-butyl-4-methylphenol)aluminum, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide, partially halogenated alkylaluminums such as ethylaluminum dichloride, dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride, and other partially hydrogenated alkylaluminums, partially alkoxylated and halogenated alkylaluminums such as ethylethoxyaluminum chloride, butylbutoxyaluminum chloride and ethylethoxyaluminum bromide, and the like.

[0134] Alternatively, the above general formula R may be used a mAl(OR b )nHpXq compounds similar to the compound represented by, for example, two or more aluminum compounds bonded via a nitrogen atom organic aluminum compound. As such a compound, specifically, (C2H5)2AlN(C2H5)Al(C2H5)2 etc. can be mentioned.

[0135] (b-1b) General formula M 2 AYR a 4(where M 2 Indicates Li, Na or K, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. ) is a complex alkyl compound of a metal of Group 1 of the Periodic Table and aluminum.

[0136] Examples of such compounds include LiAl(C2H5)4, LiAl(C7H 15 )4, etc.

[0137] (b-1c) General formula R a R b M 3 (Where R a and R b They may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, 3 A dialkyl compound of a metal of Group 2 or Group 12 of the Periodic Table represented by Mg, Zn or Cd.

[0138] As the organoaluminum oxy-compound (b-2), a conventionally known aluminoxane can be used as it is. Specifically, there can be mentioned compounds represented by the following general formula [II] and compounds represented by the following general formula [III].

[0139] [Chemical Formula 2]

[0140]

[0141] In formulae [II] and [III], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or greater.

[0142] In particular, methylaluminoxane can be used, in which R is a methyl group and n is 3 or more, preferably 10 or more. Some organoaluminum compounds may be mixed with these aluminoxanes.

[0143] When copolymerizing ethylene and α-olefins at high temperatures, benzene-insoluble organoaluminum oxy-compounds such as those exemplified in Japanese Patent Application Laid-Open No. 2-78687 can also be used. Furthermore, organoaluminum oxy-compounds described in Japanese Patent Application Laid-Open No. 2-167305 and aluminoxanes having two or more alkyl groups described in Japanese Patent Application Laid-Open No. 2-24701 and Japanese Patent Application Laid-Open No. 3-103407 can also be preferably used. It should be noted that the "benzene-insoluble organoaluminum oxy-compound" that may be used in the present invention refers to a compound that is insoluble or poorly soluble in benzene and has an Al content, calculated as Al atoms, of generally 10% or less, preferably 5% or less, and particularly preferably 2% or less, when dissolved in benzene at 60°C.

[0144] In addition, examples of the organoaluminum oxy-compound (b-2) include modified methylaluminoxane represented by the following general formula [IV].

[0145] [Chemical Formula 3]

[0146]

[0147] In formula [IV], Me represents a methyl group, R represents a hydrocarbon group having 2 to 10 carbon atoms, and m and n each independently represent an integer of 2 or greater.

[0148] This modified methylaluminoxane is prepared using trimethylaluminum and an aluminum alkyl other than trimethylaluminum. Such compounds are generally referred to as MMAO. Such MMAO can be prepared using the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584. Furthermore, compounds prepared using trimethylaluminum and triisobutylaluminum, where R is an isobutyl group, are commercially available from Tosoh Finechem Corporation and others under the names MMAO and TMAO. Such MMAO is an aluminoxane with improved solubility and storage stability in various solvents. Specifically, unlike the compounds represented by formula [II] and formula [III], which are insoluble or poorly soluble in benzene, MMAO is soluble in aliphatic and alicyclic hydrocarbons.

[0149] In addition, examples of the organoaluminum oxy-compound (b-2) include boron-containing organoaluminum oxy-compounds represented by the following general formula [V].

[0150] [Chemical Formula 4]

[0151]

[0152] In formula [V], R c represents a hydrocarbon group having 1 to 10 carbon atoms. d They may be the same as or different from each other and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0153] Examples of the compound (b-3) capable of reacting with the bridged metallocene compound (a) to form an ion pair (hereinafter sometimes referred to as "ionized ionic compound" or simply "ionic compound") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106. Examples include heteropoly compounds and isopoly compounds.

[0154] The ionizing ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VI].

[0155] [Chemical Formula 5]

[0156]

[0157] In formula [VI], R e+ , for example, H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation with transition metal, etc. f ~R i They may be the same as or different from each other and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and are preferably substituted aryl groups.

[0158] Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(4-methylphenyl)carbonium cation, and tri(3,5-dimethylphenyl)carbonium cation.

[0159] Specific examples of the ammonium cation include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0160] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(4-methylphenyl)phosphonium cation, and tri(3,5-dimethylphenyl)phosphonium cation.

[0161] In the above specific example, as R e+ , preferably a carbonium cation, an ammonium cation, etc., and particularly preferably a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation.

[0162] Among the ionizing ionic compounds preferably used in the present invention, compounds containing a carbonium cation include triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis{3,5-di-(trifluoromethyl)phenyl}borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, and tri(4-methylphenyl)carbonium tetrakis(pentafluorophenyl)borate.

[0163] Among the ionizing ionic compounds preferably used in the present invention, examples of compounds containing trialkyl-substituted ammonium cations include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(4-methylphenyl)borate, trimethylammonium tetrakis(2-methylphenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(4-(trifluoromethyl)phenyl)borate, and tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate. tri(n-butyl)ammonium tetrakis{3,5-bis(trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis(2-methylphenyl)borate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis{4-(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium tetrakis{3,5-bis(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium and the like.

[0164] Among the ionizing ionic compounds preferably used in the present invention, compounds containing N,N-dialkylanilinium cations include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis{3,5-bis(trifluoromethyl)phenyl}borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis{3,5-bis(trifluoromethyl)phenyl}borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, and N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

[0165] Among the ionizing ionic compounds preferably used in the present invention, compounds containing a dialkylammonium cation include di-n-propylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0166] Furthermore, the ionic compounds exemplified in Japanese Patent Application Laid-Open No. 2004-51676 can also be used without limitation.

[0167] The above-mentioned ionic compound (b-3) may be used alone or in combination of two or more.

[0168] As the organometallic compound (b-1), trimethylaluminum, triethylaluminum, and triisobutylaluminum, which are easily available as commercial products, are preferred. Among them, triisobutylaluminum is particularly preferred because it is easy to handle.

[0169] The organoaluminum oxy-compound (b-2) is preferably methylaluminoxane, which is readily available as a commercial product, or MMAO prepared using trimethylaluminum and triisobutylaluminum. Among these, MMAO having improved solubility in various solvents and storage stability is particularly preferred.

[0170] As the ionic compound (b-3), triphenylcarbonium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are preferred because they are readily available as commercial products and contribute significantly to improving polymerization activity.

[0171] As compound (b), a combination of triisobutylaluminum and triphenylcarbonium tetrakis(pentafluorophenyl)borate and a combination of triisobutylaluminum and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are particularly preferred because they significantly improve polymerization activity.

[0172] <Carrier (c)>

[0173] In the present invention, a support (c) may be used as a component of the olefin polymerization catalyst as needed.

[0174] The support (c) that can be used in the present invention is an inorganic or organic compound in the form of a granular or microparticle solid. Among them, the inorganic compound is preferably a porous oxide, an inorganic chloride, clay, a clay mineral, or an ion-exchange layered compound.

[0175] As porous oxides, specifically, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or composites or mixtures thereof, such as natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. can be used. Among them, porous oxides with SiO2 and / or Al2O3 as main components are preferred. For such porous oxides, their properties vary depending on the type and preparation method. The particle size of the carrier preferably used in the present invention is 0.5 to 300 μm, preferably 1.0 to 200 μm, and the specific surface area is 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and the pore volume is 0.3~3.0cm 3 Such a support can be used after being calcined at 100 to 1000°C, preferably 150 to 700°C, as needed.

[0176] As the inorganic chloride, MgCl2, MgBr2, MnCl2, MnBr2, etc. can be used. The inorganic chloride can be used directly or after being pulverized using a ball mill or a vibration mill. Alternatively, a substance obtained by dissolving the inorganic chloride in a solvent such as alcohol and then precipitating it in particulate form using a precipitating agent can be used.

[0177] Clay is usually composed of clay minerals as the main component. In addition, ion-exchange layered compounds are compounds having the following crystal structure and the ions contained therein can be exchanged, and the crystal structure is a crystal structure in which the composed surfaces are stacked parallel to each other with weak binding forces using ionic bonds, etc. Most clay minerals are ion-exchange layered compounds. In addition, as these clays, clay minerals, and ion-exchange layered compounds, they are not limited to natural products, and artificial synthesis products can also be used. In addition, as clays, clay minerals or ion-exchange layered compounds, clays, clay minerals, and ionic crystalline compounds with layered crystal structures such as hexagonal closest packing type, antimony type, CdCl2 type, CdI2 type, etc. can be exemplified. Examples of such clays and clay minerals include kaolin, bentonite, Kibuki clay, wamosin clay, allophane, ferrositite, pyrophyllite, micas, montmorillonites, vermiculite, chlorites, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchange layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O. The clays and clay minerals used in the present invention are preferably subjected to chemical treatment. As chemical treatment, any surface treatment to remove impurities adhering to the surface, treatment to affect the crystal structure of clay, etc. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.

[0178] Ion-exchange layered compounds can be layered compounds that utilize ion exchangeability to exchange interlayer exchangeable ions with other bulky ions, thereby expanding the interlayer. Such bulky ions play the role of pillars supporting the layered structure and are generally referred to as pillars. In addition, the introduction of other substances (guest compounds) between the layers of the layered compound as described above is called intercalation. Examples of guest compounds include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (R is a hydrocarbon group, etc.), [Al 13O4(OH) 24 ] 7+ 、[Zr4(OH) 14 ] 2+ 、[Fe3O(OCOCH3)6] + Such metal hydroxide ions, etc. These compounds can be used alone or in combination of two or more. In addition, when inserting these compounds, polymers obtained by hydrolysis and polycondensation of metal alkoxides such as Si(OR)4, Al(OR)3, Ge(OR)4 (R is a hydrocarbon group, etc.), colloidal inorganic compounds such as SiO2, etc. can also coexist. In addition, as pillars, oxides generated by inserting the above-mentioned metal hydroxide ions between layers and then heating and dehydrating them can be mentioned.

[0179] Among them, clay or clay minerals are preferred, and montmorillonite, vermiculite, phillipsite, taeniamite, and synthetic mica are particularly preferred.

[0180] The organic compound as the support (c) may be a granular or particulate solid having a particle size in the range of 0.5 to 300 μm. Specifically, (co)polymers mainly composed of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers mainly composed of vinylcyclohexane or styrene, and modified forms thereof may be exemplified.

[0181] By using a polymerization method that uses an olefin polymerization catalyst that can produce an ethylene·α-olefin copolymer (A) with high randomness, high-temperature polymerization can be performed. That is, by using this olefin polymerization catalyst, it is possible to suppress the reduction in the randomness of the produced ethylene·α-olefin copolymer (A) during high-temperature polymerization. In solution polymerization, the viscosity of the polymerization solution containing the produced ethylene·α-olefin copolymer (A) decreases at high temperatures. Therefore, compared with low-temperature polymerization, the concentration of the ethylene·α-olefin copolymer (A) in the polymerizer can be increased, and as a result, the productivity per polymerizer is improved. The copolymerization of ethylene and α-olefin in the present invention can be carried out by any method of liquid phase polymerization such as solution polymerization, suspension polymerization (slurry polymerization), or gas phase polymerization. As mentioned above, solution polymerization is particularly preferred from the perspective of maximizing the effects of the present invention.

[0182] The method of using and order of adding the components of the olefin polymerization catalyst can be arbitrarily selected. In addition, at least two or more components of the catalyst may be brought into contact with each other in advance.

[0183] The bridged metallocene compound (a) (hereinafter also referred to as "component (a)") is usually 10 -9 ~10 -1 mole, preferably 10-8 ~10 -2 Molar amounts are used.

[0184] The organometallic compound (b-1) (hereinafter also referred to as "component (b-1)") is used in such an amount that the molar ratio of component (b-1) to the transition metal atom (M) in component (a) [(b-1) / M] is usually 0.01 to 50,000, preferably 0.05 to 10,000.

[0185] The organic aluminum oxy-compound (b-2) (hereinafter also referred to as "component (b-2)") is used in such an amount that the molar ratio of the aluminum atoms in component (b-2) to the transition metal atoms (M) in component (a) [(b-2) / M] is usually 10 to 5,000, preferably 20 to 2,000.

[0186] The ionic compound (b-3) (hereinafter also referred to as "component (b-3)") is used in such an amount that the molar ratio of component (b-3) to the transition metal atom (M) in component (a) [(b-3) / M] is usually 1 to 10,000, preferably 1 to 5,000.

[0187] The polymerization temperature is generally -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, and even more preferably 130°C to 200°C. Within the aforementioned polymerization temperature range, the viscosity of the solution decreases as the temperature increases during polymerization, making it easier to remove the heat of polymerization. The polymerization pressure is generally normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.

[0188] The polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out continuously using two or more polymerizers with different reaction conditions.

[0189] The molecular weight of the resulting copolymer can be adjusted by varying the hydrogen concentration in the polymerization system and the polymerization temperature. Alternatively, it can be adjusted by the amount of compound (b) used. When hydrogen is added, the appropriate amount of hydrogen is approximately 0.001 to 5,000 NL per kg of the resulting copolymer.

[0190] The polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure. As the polymerization solvent, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane can be mentioned, and particularly preferred are hexane, heptane, octane, decane, and cyclohexane. The α-olefin itself as the polymerization object can also be used as the polymerization solvent. It should be noted that aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents, but from the perspective of reducing the burden on the environment and minimizing the impact on human health, it is not ideal to use these substances.

[0191] The kinematic viscosity of the ethylene-α-olefin copolymer (A) at 100°C depends on the molecular weight of the copolymer. That is, if it is a high molecular weight, it becomes high viscosity, and if it is a low molecular weight, it becomes low viscosity. Therefore, the kinematic viscosity at 100°C is adjusted by adjusting the molecular weight. In addition, the low molecular weight components of the obtained copolymer can be removed by a conventional method such as vacuum distillation, thereby adjusting the molecular weight distribution (Mw / Mn) of the obtained copolymer. In addition, the obtained copolymer can also be hydrogenated (hereinafter also referred to as "hydrogenation") by a conventional method. If the amount of unsaturated bonds in the copolymer obtained by hydrogenation is reduced, the oxidation stability and heat resistance are improved.

[0192] [Acid-modified ethylene-α-olefin copolymer (B)]

[0193] The acid-modified ethylene / α-olefin copolymer (B) forming the aqueous dispersion of the present invention is an acid-modified product of the above-mentioned ethylene / α-olefin copolymer (A). This acid-modified product (B) is also referred to as "component (B)" or "acid-modified ethylene / α-olefin copolymer (B)."

[0194] The acid-modified product (B) of the present invention is obtained by modifying the ethylene / α-olefin copolymer (A) with a compound selected from unsaturated carboxylic acids and their derivatives, and is preferably obtained by graft-modifying the ethylene / α-olefin copolymer with the compound.

[0195] Examples of unsaturated carboxylic acids and their derivatives include unsaturated carboxylic acids having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, and derivatives of the aforementioned unsaturated carboxylic acids. Examples of unsaturated carboxylic acid derivatives include anhydrides, esters, amides, and imides of unsaturated carboxylic acids.

[0196] Since component (A), which is the starting material of component (B), has a small amount of unsaturated bonds as described above, component (B) is presumed to have a structure in which the graft component is randomly graft-bonded to the main chain skeleton of component (A).

[0197] Examples of the unsaturated carboxylic acid include monobasic acids such as acrylic acid and methacrylic acid; and dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and 5-norbornene-2,3-dicarboxylic acid.

[0198] Examples of the anhydride of the unsaturated carboxylic acid include anhydrides of dibasic acids such as maleic acid, itaconic acid, citraconic acid, and 5-norbornene-2,3-dicarboxylic acid.

[0199] Examples of the esters of the unsaturated carboxylic acid include esters and half-esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate, and diethyl itaconate.

[0200] Examples of the amides of the unsaturated carboxylic acids include acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, and fumaric acid-N,N-dibutylamide.

[0201] Examples of the imide of the unsaturated carboxylic acid include maleimide, N-butylmaleimide, and N-phenylmaleimide.

[0202] Among them, at least one selected from maleic acid and maleic anhydride is preferred because they have high polarity as a single monomer and are less likely to form by-products such as homopolymers in a modification reaction using a peroxide.

[0203] The graft component may be used alone or in combination of two or more.

[0204] The grafting reaction can be carried out, for example, by the method described in Japanese Patent Application Laid-Open No. 61-126120, typically by adding a grafting component to the ethylene / α-olefin copolymer (A) in the presence of a free radical initiator such as di-tert-butyl peroxide. The reaction temperature is typically 150 to 200°C, preferably 160 to 180°C, and the reaction time is typically 1 to 50 hours, preferably 1 to 10 hours. The grafting component is preferably used in an amount such that the acid value of the resulting component (B) falls within the following range.

[0205] The acid-modified ethylene / α-olefin copolymer (B) of the present invention is an acid-modified ethylene / α-olefin copolymer (A) satisfying the above-mentioned (A1) to (A6) and further satisfying the following (B1) to (B5).

[0206] (B1) The acid value is within the range of 1 to 300 mgKOH / g.

[0207] The acid value can be used as an indicator of the grafting amount of the graft component. The acid value of component (B) is preferably in the range of 1 to 300 mgKOH / g, more preferably in the range of 5 to 200 mgKOH / g, and even more preferably in the range of 10 to 150 mgKOH / g. If the acid value is below the above range, the polarity of the copolymer may decrease and the stability of the aqueous dispersion may decrease. If the acid value exceeds the above range, hydrogen bonds between the graft components may occur, the viscosity of the copolymer may increase, and as a result, the dispersibility in water may decrease.

[0208] The acid value of component (B) can be adjusted by adjusting the graft amount of the graft component to component (A). For example, in order to increase the acid value of component (B), it is preferable to increase the graft amount.

[0209] The acid value of the component (B) represents the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the polymer, and can be measured by a method in accordance with JIS K 0070. Specifically, it is as described in the Examples.

[0210] (B2) The apparent viscosity at 150°C is within the range of 1 to 1,000 cPs.

[0211] The apparent viscosity (Brookfield viscosity) of component (B) at 150°C is a value measured by the method described in JIS K7117-1. The apparent viscosity of component (B) at 150°C is preferably in the range of 1 to 1,000 cPs, more preferably in the range of 5 to 800 cPs, and particularly preferably in the range of 5 to 90 cPs. When the apparent viscosity is within this range, the composition exhibits an excellent balance between low volatility, handleability, and dispersibility in water.

[0212] (B3) The weight average molecular weight as measured by gel permeation chromatography (GPC) and calculated as polystyrene is within the range of 1,000 to 50,000.

[0213] The weight average molecular weight (Mw) of component (B) is a value obtained by measuring the weight average molecular weight (Mw) of component (B) in accordance with the method described below using gel permeation chromatography (GPC) and converted to standard polystyrene. The weight average molecular weight (Mw) of component (B) is preferably in the range of 1,000 to 50,000, more preferably in the range of 1,000 to 30,000, further preferably in the range of 1,500 to 30,000, particularly preferably in the range of 2,000 to 7,000, and most preferably in the range of 5,000 to 6,000. If Mw is excessively below the above range, the amount of volatile components is high, and therefore, it may be easy to ignite and the storage properties may deteriorate, or the evaporation loss in the aqueous dispersion may increase. If Mw exceeds the above range excessively, the viscosity of the copolymer may increase, making it difficult to disperse evenly in water.

[0214] (B4) The molecular weight distribution (Mw / Mn) of the molecular weight calculated as polystyrene as measured by gel permeation chromatography (GPC) is 2.5 or less.

[0215] The molecular weight distribution of component (B) can be calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and measuring according to the method described later and converted by standard polystyrene. The Mw / Mn of component (B) is preferably less than 2.5, more preferably less than 2.3, and further preferably less than 2.0. The so-called molecular weight distribution exceeds the above range excessively, which means that the copolymer includes a large amount of low molecular weight components and high molecular weight components. When the copolymer includes a large amount of low molecular weight components, there are many volatile components, so it is easy to ignite and the preservation property is deteriorated, or the evaporation loss in the aqueous dispersion increases. When the copolymer includes a large amount of high molecular weight components, the viscosity of the copolymer sometimes rises, and it is difficult to be evenly dispersed in water.

[0216] (B5) The weight fraction of unreacted molecules measured by high performance liquid chromatography (HPLC) is 59% or less.

[0217] When the weight fraction of unreacted molecules is within the above range, the proportion of molecules of acid-modified products modified with unsaturated carboxylic acids and their derivatives having excellent affinity for water contained in component (B) increases, and component (B) is easily dispersed uniformly in water, which is preferred.

[0218] The component (B) according to the present invention preferably further satisfies the following (B6).

[0219] (B6) Among the unreacted molecules contained in the acid-modified product (B), the weight fraction of unreacted molecules having a molecular weight higher than the weight average molecular weight of the acid-modified product (B) measured by gel permeation chromatography (GPC) and calculated as polystyrene is 20% or less.

[0220] When the weight fraction of unreacted molecules having a molecular weight higher than the weight average molecular weight of the acid-modified product (B) is within the above range, the proportion of high-molecular-weight unreacted molecules having poor dispersibility in water among the unreacted molecules is reduced, and the component (B) is easily dispersed uniformly in water, which is preferred.

[0221] The component (B) according to the present invention preferably further satisfies the following (B7).

[0222] (B7) No melting point was observed.

[0223] Component (B) preferably has no observable melting point in differential scanning calorimetry (DSC). Here, "no observable melting point (Tm)" means that substantially no heat of fusion (ΔH) (unit: J / g) is measured by differential scanning calorimetry (DSC). "Substantially no heat of fusion (ΔH)" means that no peak is observed in differential scanning calorimetry (DSC), or that the observed heat of fusion is 1 J / g or less.

[0224] The melting point (Tm) and heat of fusion (ΔH) of component (B) can be determined by differential scanning calorimetry (DSC) by analyzing the DSC curve after cooling to -100°C and then heating to 150°C at a rate of 10°C / minute, in accordance with JIS K7121. If no melting point is observed, this indicates that component (B) has low crystallinity, the viscosity of component (B) does not increase, or component (B) does not become solid, and its dispersibility in water is excellent.

[0225] Component (B) may be used alone or in combination of two or more.

[0226] <Aqueous Dispersion Composition>

[0227] The aqueous dispersion composition of the present invention contains the acid-modified ethylene / α-olefin copolymer (B) in an amount of 0.01 to 50% by mass, preferably 0.05 to 30% by mass.

[0228] The aqueous dispersion composition of the present invention preferably has a viscosity of 15 mPa·s or greater, more preferably 20 to 200 mPa·s, even more preferably 30 to 200 mPa·s, particularly preferably 60 to 200 mPa·s, and most preferably 100 to 200 mPa·s. A viscosity within this range is preferred because the aqueous dispersion composition spreads well onto the substrate surface during application and coating, and is less likely to cause liquid dripping, resulting in excellent substrate coating properties.

[0229] For the aqueous dispersion composition of the present invention, the average particle size of the dispersed particles of the above-mentioned ethylene·α-olefin copolymer acid-modified product (B) forming the dispersion composition is preferably in the range of 100 nm or less, more preferably in the range of 10 to 95 nm, further preferably in the range of 10 to 60 nm, particularly preferably in the range of 20 to 40 nm, and most preferably in the range of 20 to 30 nm. If the average particle size of the dispersed particles is larger than the above range, the particles tend to separate easily, which is not preferred from the perspective of stability. In addition, if the average particle size of the dispersed particles is smaller than the above range, the interaction between the particles becomes stronger, the viscosity of the aqueous dispersion composition tends to increase, and therefore, it is difficult to spread to the surface of the substrate, which is not preferred. In other words, if the average particle size of the dispersed particles is within the above range, the stability of the aqueous dispersion composition is excellent and the coating properties on the substrate are also excellent, so it is preferred.

[0230] [Method for measuring average particle size]

[0231] The average particle size in the present invention refers to the diameter of the particles at 50% of the cumulative volume, with the total volume being 100%. This can be measured using a dynamic light scattering particle size distribution analyzer or a Nanotrac particle size distribution analyzer. In the present invention, the average particle size of the particles in the dispersion is measured using a Nanotrac WAVE2-EX150 (manufactured by Microtrac BEL).

[0232] Furthermore, the phrase "the water dispersion composition of the present invention has excellent stability" means that the dispersion state of the water dispersion composition is good when stored at room temperature.

[0233] In the present invention, the stability of the aqueous dispersion composition was evaluated by placing the aqueous dispersion composition in a transparent cylindrical glass container having a length of 120 mm and a diameter of 40 mm and visually evaluating the presence of separation after standing at 23° C. for 15 hours.

[0234] The water dispersion composition of the present invention preferably has a water content of 50 to 99.99% by mass, more preferably 60 to 99.95% by mass.

[0235] The aqueous dispersion composition of the present invention may contain, in addition to the acid-modified ethylene / α-olefin copolymer (B), a surfactant, an anticorrosive agent, an antioxidant, animal or vegetable oils or fatty acid esters thereof, a synthetic lubricating oil, a wax, an inorganic powder, and various other additives. These additives may be used alone or in combination of two or more.

[0236] As the surfactant, various surfactants of anionic, cationic, and nonionic types can be used. For example, alkylene oxide adducts of nonylphenol, alkylene oxide adducts of linear higher alcohols having 12 to 18 carbon atoms, alkylene oxide adducts of higher amines, polyoxyethylene adducts of fatty acids such as castor oil, alkylene oxide adducts of fatty acid amides, alkyl sulfates, Tamol-type, tetraalkylammonium salts, alkyl betaines, etc. can be illustrated. When using a surfactant, its addition amount is preferably 0.1 to 20% by mass in the aqueous dispersion composition, and more preferably 0.5 to 10% by mass.

[0237] Examples of the anticorrosive agent include sodium nitrite, sodium benzoate, triethanolamine salts, etc. When the anticorrosive agent is used, the amount added is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, in the aqueous dispersion composition.

[0238] Examples of the antioxidant include phenolic and amine compounds such as 2,6-di-tert-butyl-4-methylphenol. The amount of the antioxidant added is preferably 0 to 3% by mass in the aqueous dispersion composition.

[0239] Examples of the animal and vegetable oils include mineral oil, rapeseed oil, soybean oil, coconut oil, palm oil, beef tallow, lard, etc. Examples of the synthetic lubricating oils include polyα-olefins, polybutadiene, polyisobutylene, and various ester oils.

[0240] Examples of the wax include synthetic waxes such as polyethylene wax and polypropylene wax, oxides and acid-modified products of these synthetic waxes, and natural waxes such as carnauba wax, montan wax, and beeswax, as long as their dispersibility in water and adhesion to the mold are not deteriorated.

[0241] Examples of the inorganic powder include talc, mica, clay, organoclay, boron nitride, mortar, sericite, calcium carbonate, borate, aluminum oxide, titanium oxide, sodium hydrogen carbonate, zirconium oxide, graphite, carbon black, and diamond powder.

[0242] As other components, silicone compounds such as silicone, dimethyl silicone, alkyl-modified silicone, and alkyl-aralkyl-modified silicone, zinc dialkyldithiophosphate (ZnDTP), molybdenum dialkyldithiophosphate (MoDTP), zinc dithiocarbamate (ZnDTC), molybdenum dithiocarbamate (MoDTC) for reducing friction, extreme pressure additives such as phosphorus-based and sulfur-based additives, defoaming agents, and preservatives may also be used in combination.

[0243] <Method for producing aqueous dispersion composition>

[0244] The aqueous dispersion composition of the present invention may be produced, for example, by emulsifying water, the acid-modified ethylene / α-olefin copolymer (B), and the appropriate additives described above, manually or using a conventional method such as a stirrer, a homomixer, a rubber mill, a line mixer, or a homogenizer. The water temperature during emulsification is preferably 40 to 99°C, more preferably 50 to 99°C.

[0245] When morpholine is used in preparing an aqueous dispersion composition of the acid-modified substance (B), the following effect is achieved: morpholine reacts with the polar groups of the acid-modified substance (B), stabilizing the aqueous dispersion composition. Morpholine can be added during the preparation of the aqueous dispersion composition, or it can be pre-mixed with the acid-modified substance (B) and allowed to react. The amount of morpholine added is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 20 parts by mass, per 100 parts by mass of the acid-modified substance (B).

[0246] In addition, in the present invention, as the above-mentioned ethylene·α-olefin copolymer acid-modified product (B), an ethylene·α-olefin copolymer acid-modified product (B) having any acid value, apparent viscosity at 150°C, weight-average molecular weight, molecular weight distribution, weight fraction of unreacted molecules, and weight fraction of unreacted molecules having a molecular weight higher than the weight-average molecular weight of the ethylene·α-olefin copolymer acid-modified product (B) is used, thereby making it possible to adjust the stability, viscosity, and average particle size of the aqueous dispersion composition without changing the equipment and conditions during emulsification.

[0247] In particular, for a method using an ethylene·α-olefin copolymer acid-modified product (B) having an adjusted weight fraction of unreacted molecules and a weight fraction of unreacted molecules having a molecular weight higher than the weight-average molecular weight of the ethylene·α-olefin copolymer acid-modified product (B), since the stability, viscosity, and average particle size of the aqueous dispersion composition can be adjusted without changing the total amount, molecular weight, and molecular weight distribution of the polar groups in the ethylene·α-olefin copolymer acid-modified product (B), changes in properties when the aqueous dispersion composition is applied or coated and dried can be easily reduced, and this is a preferred method for producing an aqueous dispersion composition having stability, viscosity, and average particle size suitable for various applications.

[0248] <Purpose>

[0249] The aqueous dispersion composition of the present invention can be used for a variety of resin or rubbery polymer modifiers, modifier aids, softeners, gel modifiers, latex modifiers, other water-soluble resin modifiers, emulsifying aids such as emulsion polymerization aids, lubricant additives, adhesives, dispersants, dispersing aids, printing inks, printing pastes, spray paints, inks, coatings for food packaging materials, coatings for flooring materials, coatings for shoes, coatings for automotive products, other water-based coatings, finishes for papermaking, spinning, and textiles, metalworking oils such as cutting oils and drawing oils, various release agents such as mold release agents for die casting, various modifiers and modifier aids, inks, coatings, coating materials, adhesives, and the like, for example, heat sealants and cosmetics. The aqueous dispersion composition of the present invention can ensure good adhesion to substrates when used as a heat sealant and has excellent dispersibility in water, making it particularly suitable for use as a heat sealant.

[0250] Example

[0251] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

[0252] [Evaluation method]

[0253] In the following Examples and Comparative Examples, the physical properties of the ethylene / α-olefin copolymer (A), the acid-modified ethylene / α-olefin copolymer (B), and the aqueous dispersion composition were measured by the following methods.

[0254] 《Physical Properties of Ethylene-α-Olefin Copolymer (A)》

[0255] <Ethylene unit content (mol%) (A1)>

[0256] The wavelength of 721 cm-1 based on the horizontal vibration of long-chain methylene groups was calculated using a Fourier transform infrared spectrophotometer FT / IR-610 or FT / IR-6100 manufactured by JASCO Corporation. -1 The absorption near 1155 cm is related to the skeleton vibration of the propylene group. -1 Absorbance ratio of the absorption near (D1155cm -1 / D721cm -1 ), the ethylene unit content (mass %) was determined from a pre-prepared calibration curve (prepared using standard samples in ASTM D3900). Next, the ethylene unit content (mass %) obtained was used to determine the ethylene unit content (mol %) according to the following formula.

[0257] [Mathematical formula 2]

[0258]

[0259] <Viscosity characteristics (A2)>

[0260] The kinematic viscosity at 100° C. was measured and calculated by the method described in JIS K2283. The apparent viscosity (Brookfield viscosity) at 150° C. was measured and calculated by the method described in JIS K7117-1.

[0261] <Molecular weight (A3) and molecular weight distribution (A4)>

[0262] For molecular weight and molecular weight distribution, HLC-8320GPC manufactured by Tosoh Corporation was used and measured as follows. As a separation column, TSKgel SuperMultiporeHZ-M (4 pieces) was used, the column temperature was set to 40°C, tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the development speed was set to 0.35 ml / min, the sample concentration was set to 5.5 g / L, the sample injection volume was set to 20 microliters, and a differential refractometer was used as the detector. As standard polystyrene, PStQuick MP-M manufactured by Tosoh Corporation was used. According to the universal calibration procedure, the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in a manner converted according to the molecular weight of polystyrene, and the molecular weight distribution (Mw / Mn) was calculated from these values.

[0263] B value (A5)

[0264] The measurement was performed using o-dichlorobenzene / benzene-d6 (4 / 1 [vol / vol%]) as the measurement solvent under the measurement conditions of a measurement temperature of 120°C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 4.7 μsec (45° pulse) (100 MHz, JEOL ECX400P), or a measurement temperature of 120°C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 5.0 μsec (45° pulse) (125 MHz, Bruker BioSpinAVANCEIIIcryo-500). 13 The B value was calculated from the C-NMR spectrum based on the following formula [1]. The peaks were assigned with reference to the aforementioned known literature.

[0265] [Mathematical formula 3]

[0266]

[0267] In formula [1], P E Indicates the molar fraction of ethylene units, P O represents the molar fraction of α-olefin units, P OE It represents the molar fraction of ethylene·α-olefin chains in all binary chains.

[0268] 〈Unsaturated bond amount (A6)〉

[0269] The measurement was performed using o-dichlorobenzene-d4 as the measurement solvent under the measurement conditions of a measurement temperature of 120°C, a spectrum width of 20 ppm, a pulse repetition time of 7.0 seconds, and a pulse width of 6.15 μsec (45° pulse). 1 H-NMR spectrum (400 MHz, JEOL ECX400P). Using the solvent peak (o-dichlorobenzene 7.1 ppm) as a chemical shift standard, the amount of unsaturated bonds per 1000 carbon atoms (numbers / 1000C) was calculated from the ratio of the integrated value of the main peak observed at 0-3 ppm and the peak derived from unsaturated bonds observed at 4-6 ppm.

[0270] Melting Point

[0271] Using Seiko Instruments Inc. X-DSC-7000, a sample of about 8 mg of the copolymer was placed in a simple, airtight aluminum sample pan and placed in a DSC unit. Under a nitrogen atmosphere, the DSC unit was heated from room temperature to 150°C at 10°C / min. Then, after holding at 150°C for 5 minutes, the temperature was lowered at 10°C / min and the DSC unit was cooled to -100°C (cooling process). Next, after holding at -100°C for 5 minutes, the temperature was raised at 10°C / min. The temperature at which the enthalpy curve obtained during the heating process showed a maximum value was taken as the melting point (Tm), and the sum of the endothermic heat accompanying the melting was taken as the heat of fusion (ΔH). If no peak was observed or the value of the heat of fusion (ΔH) was less than 1 J / g, it was considered that the melting point (Tm) was not observed. The method for determining the melting point (Tm) and the heat of fusion (ΔH) was based on JIS K7121.

[0272] 《Physical Properties of Acid-Modified Ethylene-α-Olefin Copolymer (B)》

[0273] 〈Acid value (B1)〉

[0274] A precisely weighed sample of the copolymer was dissolved in a mixed solvent of xylene and n-butanol in a mass ratio of 1:1 to obtain a sample solution. This sample solution was then titrated with a pre-standardized N / 10 potassium hydroxide alcohol solution (obtained by adding 5 g of ion-exchanged water to 7 g of special-grade potassium hydroxide, adjusting the volume to 1 L with first-grade ethanol, and standardizing the titer with N / 10 hydrochloric acid and 1% phenolphthalein solution to obtain a titer of F). The neutralization amount was calculated using the following formula.

[0275] Acid value (mgKOH / g)

[0276] =(N / 10KOH titration (ml) × F × 5.61) / (sample (g) × 0.01)

[0277] 〈Apparent viscosity (B2)〉

[0278] The apparent viscosity (Brookfield viscosity) at 150° C. was measured and calculated by the method described in JIS K7117-1.

[0279] <Molecular weight (B3) and molecular weight distribution (B4)>

[0280] For molecular weight and molecular weight distribution, Tosoh Corporation HLC-8320GPC was used and measured as follows. As a separation column, TSKgel SuperMultiporeHZ-M (4 pieces) was used, the column temperature was set to 40°C, tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the development speed was set to 0.35 ml / min, the sample concentration was set to 5.5 g / L, the sample injection volume was set to 20 microliters, and a differential refractometer was used as the detector. As standard polystyrene, Tosoh Corporation PStQuick MP-M was used. According to the universal calibration procedure, the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in a manner converted according to the molecular weight of polystyrene, and the molecular weight distribution (Mw / Mn) was calculated from these values.

[0281] <Weight fraction of unreacted molecules (B5)>

[0282] The weight fraction of unreacted molecules was measured as follows using an HPLC apparatus manufactured by Waters Corporation (Alliancee 2695 Separations Module / 2414RI Detector).

[0283] Mobile phase: hexane

[0284] Flow rate: 1ml / min

[0285] Sample concentration: 1w / v%

[0286] Sample injection volume: 20 μL

[0287] Column: Normal phase column manufactured by Agilent Technologies, Inc.

[0288] Column size: inner diameter 4.6mm, length 250mm

[0289] Column filler: silica particles (particle size 5 μm)

[0290] Detector: Differential refractometer

[0291] In the examples of the present invention, the ethylene-propylene copolymer used in the production of the acid-modified ethylene-α-olefin copolymer (B) was used as a standard, and the peak area (S0) (appearing in the region of 2 to 3.5 minutes) when the standard was measured under the above conditions was compared with the peak area (S0) at the same position in the measurement results of each sample. MD ) is determined using the following formula.

[0292] Weight fraction of unreacted molecules = 100 × S MD / S0

[0293] <Weight fraction (B6) of unreacted molecules having a molecular weight higher than the weight average molecular weight of the acid-modified ethylene / α-olefin copolymer (B) among the unreacted molecules contained in the acid-modified ethylene / α-olefin copolymer (B)>

[0294] The molecular weight of the unreacted molecules contained in the acid-modified ethylene / α-olefin copolymer (B) was determined by fractionating the unreacted molecules using a silica column and measuring the molecular weight using gel permeation chromatography (GPC). The unreacted molecules were fractionated by filling a 50 mm diameter chromatographic tube with crushed silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) to a height of 5 cm and impregnating it with hexane. A solution obtained by dissolving 1 g of the acid-modified ethylene / α-olefin copolymer (B) in 5 mL of hexane and 20 mL of hexane were then added from the top in that order. Approximately 10 mL of the solution eluted from the bottom of the chromatographic tube was collected and dried. The molecular weight of the separated unreacted molecules was measured using a Tosoh HLC-8320GPC as described below, and the weight fraction of unreacted molecules having a molecular weight higher than the weight average molecular weight of the acid-modified ethylene / α-olefin copolymer (B) was calculated. TSKgel SuperMultipore HZ-M (4 columns) were used as separation columns, the column temperature was maintained at 40°C, tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the development rate was set at 0.35 ml / min, the sample concentration was set at 5.5 g / L, the sample injection volume was set at 20 μL, and a differential refractometer was used as the detector. PStQuick MP-M manufactured by Tosoh Corporation was used as the standard polystyrene.

[0295] [Production Example of Ethylene / α-Olefin Copolymer (A)]

[0296] The ethylene·α-olefin copolymer (A) was produced according to the following polymerization example. The obtained ethylene·α-olefin copolymer (A) was subjected to hydrogenation by the following method as needed.

[0297] <Hydrogenation Operation>

[0298] A 1L stainless steel autoclave was charged with 100 mL of a 0.5% by mass Pd / alumina catalyst hexane solution and 500 mL of a 30% by mass ethylene / α-olefin copolymer hexane solution. The autoclave was sealed and purged with nitrogen. The temperature was then raised to 140°C while stirring, and the system was purged with hydrogen. The pressure was then increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.

[0299] <Synthesis of Metallocene Compounds>

[0300] [Synthesis example 1]

[0301] [Methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 Synthesis of [(2,7-di-tert-butylfluorenyl)]zirconium dichloride

[0302] (i) Synthesis of 6-methyl-6-phenylfulvene

[0303] Under a nitrogen atmosphere, 7.3 g (101.6 mmol) of cyclopentadiene lithium and 100 mL of dehydrated tetrahydrofuran were added to a 200 mL three-necked flask and stirred. The solution was cooled in an ice bath and 15.0 g (111.8 mmol) of acetophenone was added dropwise. The mixture was stirred at room temperature for 20 hours and the resulting solution was quenched with a dilute aqueous hydrochloric acid solution. 100 mL of hexane was added to extract the soluble matter. After the organic layer was washed with water and saturated aqueous sodium chloride solution, it was dried over anhydrous magnesium sulfate. The solvent was then distilled off and the resulting viscous liquid was separated by column chromatography (hexane) to obtain the target product (red viscous liquid).

[0304] (ii) Synthesis of methyl(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)(phenyl)methane

[0305] Under a nitrogen atmosphere, 2.01 g (7.20 mmol) of 2,7-di-tert-butylfluorene and 50 mL of dehydrated tert-butyl methyl ether were added to a 100 mL three-necked flask. While cooling in an ice bath, 4.60 mL (7.59 mmol) of a 1.65 M n-butyllithium / hexane solution were slowly added, followed by stirring at room temperature for 16 hours. 1.66 g (9.85 mmol) of 6-methyl-6-phenylfulvene was added, followed by stirring under reflux for 1 hour. While cooling in an ice bath, 50 mL of water was slowly added, and the resulting two-layer solution was transferred to a 200 mL separatory funnel. After adding 50 mL of diethyl ether and shaking several times, the aqueous layer was removed, and the organic layer was washed three times with 50 mL of water and once with 50 mL of saturated brine. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. A small amount of hexane was added, and ultrasonic waves were applied to the resulting solution, resulting in the precipitation of a solid. This solid was collected, washed with a small amount of hexane, and dried under reduced pressure to obtain 2.83 g of methyl(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)(phenyl)methane as a white solid.

[0306] (iii) [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 Synthesis of [(2,7-di-tert-butylfluorenyl)]zirconium dichloride

[0307] Under a nitrogen atmosphere, 1.50 g (3.36 mmol) of methyl(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)(phenyl)methane, 50 mL of dehydrated toluene, and 570 μL (7.03 mmol) of THF (tetrahydrofuran) were added to a 100 mL Schlenk tube in this order. While cooling in an ice bath, 4.20 mL (6.93 mmol) of a 1.65 M n-butyllithium / hexane solution were slowly added, and the mixture was stirred at 45°C for 5 hours. The solvent was distilled off under reduced pressure, and 40 mL of dehydrated ether was added to form a red solution. While cooling in a methanol / dry ice bath, 728 mg (3.12 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 16 hours while slowly warming to room temperature, resulting in an orange-red slurry. The solvent was distilled off under reduced pressure, and the resulting solid was brought into a glove box, washed with hexane, and extracted with dichloromethane. The solvent was distilled off under reduced pressure and the mixture was concentrated. A small amount of hexane was added and the mixture was allowed to stand at -20°C, whereupon an orange-red solid precipitated. The solid was washed with a small amount of hexane and then dried under reduced pressure to obtain [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride 1.20 g.

[0308] [Synthesis example 2]

[0309] [Ethylene (η 5 -cyclopentadienyl)(η 5 Synthesis of [(2,7-di-tert-butylfluorenyl)]zirconium dichloride

[0310] [Ethylene (η 5 -cyclopentadienyl)(η 5 [(2,7-di-tert-butylfluorenyl)] zirconium dichloride was synthesized by the method described in Japanese Patent No. 4367687.

[0311] <Polymerization Example 1>

[0312] A 2 L stainless steel autoclave fully purged with nitrogen was charged with 760 ml of heptane and 120 g of propylene. After the temperature in the system was raised to 150° C., 0.85 MPa of hydrogen and 0.19 MPa of ethylene were supplied to adjust the total pressure to 3 MPaG. Subsequently, 0.4 mmol of triisobutylaluminum, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)] zirconium dichloride 0.0002mmol and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate 0.002mmol, the stirring speed was set to 400rpm, thereby starting polymerization. Then, only ethylene was continuously supplied, thereby maintaining the total pressure at 3MPaG, and polymerization was carried out at 150°C for 5 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, the unreacted ethylene, propylene and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000ml of 0.2mol / L hydrochloric acid, then washed 3 times with 1000ml of distilled water, dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain 60.9g of ethylene·propylene copolymer. The ethylene·propylene copolymer was further subjected to hydrogenation operation.

[0313] The above-described operation yielded the ethylene-propylene copolymer (A-1) shown in Table 1. Table 1 shows the analysis results of the obtained ethylene-propylene copolymer (A-1).

[0314] <Polymerization Example 2>

[0315] A 2 L stainless steel autoclave fully purged with nitrogen was charged with 710 mL of heptane and 145 g of propylene. After the temperature in the system was raised to 150° C., 0.40 MPa of hydrogen and 0.27 MPa of ethylene were supplied to adjust the total pressure to 3 MPaG. Subsequently, 0.4 mmol of triisobutylaluminum, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5-2,7-di-tert-butylfluorenyl)] zirconium dichloride 0.0001mmol and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate 0.001mmol, the stirring speed was set to 400rpm, thereby starting polymerization. Then, only ethylene was continuously supplied, thereby maintaining the total pressure at 3MPaG, and polymerization was carried out at 150°C for 5 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, the unreacted ethylene, propylene and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000ml of 0.2mol / L hydrochloric acid, then washed 3 times with 1000ml of distilled water, dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried under reduced pressure at 80°C overnight to obtain 52.2g of ethylene·propylene copolymer. The ethylene·propylene copolymer was further subjected to hydrogenation operation.

[0316] The above-described operation yielded the ethylene-propylene copolymer (A-3) shown in Table 1. Table 1 shows the analysis results of the obtained ethylene-propylene copolymer (A-3).

[0317] In addition, ethylene-propylene copolymers (A-2), (A-4), and (A-5) obtained by a method similar to that described in Japanese Patent Publication No. 2-1163 and Japanese Patent Publication No. 2-7998 using a vanadium-based catalyst containing a vanadium compound and an organoaluminum compound were used in the examples. The analysis results of the ethylene-propylene copolymers (A-2), (A-4), and (A-5) used are shown in Table 1.

[0318] <Production Example 1>

[0319] 95.5 wt% of the ethylene-propylene copolymer (A-1) and 4.5 wt% of the ethylene-propylene copolymer (A-3) were mixed to obtain an ethylene-propylene copolymer (A-6). The analysis results of the obtained ethylene-propylene copolymer (A-6) are shown in Table 1.

[0320] <Production Example 2>

[0321] 94.3 wt% of the ethylene-propylene copolymer (A-2) and 5.7 wt% of the ethylene-propylene copolymer (A-4) were mixed to obtain an ethylene-propylene copolymer (A-7). The analysis results of the obtained ethylene-propylene copolymer (A-7) are shown in Table 1.

[0322] <Production Example 3>

[0323] An ethylene-propylene copolymer (A-8) was obtained by mixing 91.4% by weight of an ethylene-propylene copolymer (A-2), 4.3% by weight of an ethylene-propylene copolymer (A-4), and 4.3% by weight of an ethylene-propylene copolymer (A-5). The analysis results of the obtained ethylene-propylene copolymer (A-8) are shown in Table 1.

[0324] [Table 1]

[0325]

[0326] [Production of Acid-Modified Ethylene-α-Olefin Copolymer (B)]

[0327] Using the ethylene-propylene copolymers (A-6) to (A-8) shown in Table 1 above, graft modification was performed using a graft component.

[0328] <Basic Operations for Olefin Polymer Composition Production>

[0329] Any of the above-mentioned ethylene-propylene copolymers (A-6) to (A-8) is placed in a stirrer-equipped reactor equipped with a nitrogen inlet pipe, a water-cooled condenser, a thermometer, a maleic anhydride supply device, and a free radical generator supply device. The temperature is then raised, and nitrogen is then introduced into the reactor at 120°C to purge the system of oxygen. The system is then maintained at 160°C. Maleic anhydride Wako Teku (manufactured by FUJIFILM Wako Pure Chemical Corporation, approximately 70°C: liquid) and di-tert-butyl peroxide Perbutyl D (manufactured by NOF Corporation) are then supplied to the reactor for a predetermined time, at a predetermined rate, and at a predetermined stirring rate. After the supply is completed, the reactor is maintained at 160°C for 1 hour while stirring is continued. The reactor is then heated to 175°C, the system is depressurized, and unnecessary components (such as unreacted maleic anhydride and decomposition products of di-tert-butyl peroxide) are removed under reduced pressure and nitrogen flow.

[0330] <Modification Examples 1 to 10>

[0331] According to the basic operation for producing the olefin polymer composition described above, acid-modified ethylene / propylene copolymers (B-1) to (B-10) were produced under the various production conditions shown in Table 2. The results are shown in Table 2.

[0332] <Production Example 4>

[0333] 95% by mass of the acid-modified ethylene-propylene copolymer (B-7) and 5% by mass of the acid-modified ethylene-propylene copolymer (A-6) were uniformly mixed to obtain an acid-modified ethylene-propylene copolymer (B-11). The analysis results of the obtained acid-modified ethylene-propylene copolymer (B-11) are shown in Table 3.

[0334] <Production Example 5>

[0335] 95% by mass of the acid-modified ethylene-propylene copolymer (B-7) and 5% by mass of the acid-modified ethylene-propylene copolymer (A-3) were uniformly mixed to obtain an acid-modified ethylene-propylene copolymer (B-12). The analysis results of the obtained acid-modified ethylene-propylene copolymer (B-12) are shown in Table 3.

[0336] <Production Example 6>

[0337] 80% by mass of the acid-modified ethylene-propylene copolymer (B-10) and 20% by mass of the acid-modified ethylene-propylene copolymer (A-6) were uniformly mixed to obtain an acid-modified ethylene-propylene copolymer (B-13). The analysis results of the obtained acid-modified ethylene-propylene copolymer (B-13) are shown in Table 3.

[0338] [Table 2]

[0339]

[0340] [Table 3]

[0341]

[0342] <Aqueous Dispersion Composition>

[0343] [Example 1]

[0344] Take 41.6g of ethylene-propylene copolymer acid-modified product (B-1) and 10.4g of polyoxyethylene alkyl ether EMULGEN 1108 (made by Kao Corporation) to a 500mL round-bottom flask with a stirrer, stir at a stirring speed of 50rpm while heating to 96°C. Next, add a solution of 7.5g of morpholine deer grade 1 (made by Kanto Chemical Co., Ltd.) and 10.0g of pure water, make the stirring speed 250rpm, and react for 30 minutes. Then, put into 134g of hot water at 97°C, make the stirring speed 500rpm, stir for 60 minutes, and then place it under a stirring speed of 250rpm to cool for 30 minutes to obtain an aqueous dispersion composition. For the obtained aqueous dispersion composition, stability, viscosity and average particle size are evaluated according to the following method. The analysis results of the obtained aqueous dispersion composition are shown in Table 4.

[0345] [Examples 2 to 10]

[0346] A water dispersion composition was obtained by the same method as in Example 1, except that the acid-modified ethylene-propylene copolymer used was changed to that shown in Table 4. Table 4 shows the analysis results of the obtained water dispersion composition.

[0347] [Comparative Examples 1 and 2]

[0348] A water dispersion composition was obtained in the same manner as in Example 1, except that the acid-modified ethylene-propylene copolymer used was changed to that shown in Table 4. The stability of the obtained water dispersion composition was evaluated, but separation occurred, and therefore the viscosity and average particle size could not be measured.

[0349] [Stability of aqueous dispersion composition]

[0350] The stability of the aqueous dispersion composition was evaluated by placing the aqueous dispersion composition in a transparent cylindrical glass container 120 mm long and 40 mm in diameter and visually observing the presence of separation after standing at 23°C for 15 hours. A uniform turbidity of the aqueous dispersion composition in the glass container was considered to indicate no separation, while a difference in turbidity along the height direction was considered to indicate separation.

[0351] [Viscosity of aqueous dispersion composition]

[0352] The viscosity of the aqueous dispersion composition was measured using a Brookfield viscometer TVB-10M (manufactured by Toki Sangyo Co., Ltd.) at 23° C. The sample whose stability was evaluated for the aqueous dispersion composition was used directly for the measurement.

[0353] [Average particle size of aqueous dispersion composition]

[0354] The average particle size of the aqueous dispersion composition was measured using a Nanotrac WAVE2-EX150 (manufactured by Microtrac BEL). For the measurement, 1 g of a sample (evaluated for stability) was placed in a polypropylene cup, diluted with 10 g of pure water, and measured. Based on the measurement results, the average particle size was determined as the particle diameter at which the cumulative volume reached 50%, with the total volume set to 100%.

[0355] [Table 4]

[0356]

[0357] Comparison of Examples 1 to 10 of the aqueous dispersion compositions with Comparative Examples 1 and 2 reveals that aqueous dispersion compositions using acid-modified ethylene-propylene copolymers with a low weight fraction of unreacted molecules exhibit superior stability. Furthermore, aqueous dispersion compositions using acid-modified ethylene-propylene copolymers with a low proportion of high molecular weight components among the unreacted molecules exhibit superior stability. Furthermore, among Examples 1 to 10, aqueous dispersion compositions using acid-modified ethylene-propylene copolymers with a low weight fraction of unreacted molecules and a low proportion of high molecular weight components among the unreacted molecules exhibit smaller average particle sizes and higher viscosities, resulting in superior aqueous dispersion composition stability. Furthermore, when applied to a substrate, these compositions exhibit excellent adhesion and are less prone to liquid dripping, leading to the expectation of good substrate coating properties, making them more desirable.

[0358] Industrial applicability

[0359] The aqueous dispersion composition, the method for producing the aqueous dispersion composition, and the acid-modified ethylene-α-olefin copolymer of the present invention provide an aqueous dispersion having excellent stability and excellent coating properties on substrates. Therefore, the aqueous dispersion can be used as a modifier for various resins or rubbery polymers, a modifying aid, a softener, a gel modifier, a latex modifier, other water-soluble resin modifiers, emulsifying aids such as emulsion polymerization aids, lubricant additives, adhesives, dispersants, dispersing aids, printing inks, printing pastes, spray paints, inks, coatings for food packaging materials, coatings for flooring materials, coatings for shoes, coatings for automobiles, other water-based coatings, finishing agents for papermaking, spinning, and textiles, metalworking oils such as cutting oils and drawing oils, various release agents such as mold release agents for die casting, various modifiers such as heat sealants and cosmetics, modifying aids, inks, coatings, coating materials, adhesives, and the like. Among them, it can be particularly suitably used as a heat sealant because of its excellent stability and coating properties on a substrate.

Claims

1. Aqueous dispersion composition, characterized in that The acid-modified ethylene / α-olefin copolymer (B) is contained in an amount of 0.01 to 50% by mass, wherein the acid-modified ethylene / α-olefin copolymer (B) is an acid-modified ethylene / α-olefin copolymer (A) satisfying the following (A1) to (A6) and further satisfying the following (B1) to (B6), (A1) The content of ethylene units is within the range of 30 to 85 mol%, (A2) Kinematic viscosity at 100°C is 10-5,000 mm 2 / s range, (A3) a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) within the range of 1,000 to 50,000, (A4) a molecular weight distribution (Mw / Mn) of 2.5 or less in terms of polystyrene, as measured by gel permeation chromatography (GPC), (A5) The B value represented by the following formula [1] is 1.1 or more, [Mathematical formula 1] In formula [1], P E Indicates the molar fraction of ethylene units, P O represents the molar fraction of α-olefin units, P OE represents the molar fraction of ethylene·α-olefin chains in all binary chains, (A6) Utilization 1 The amount of unsaturated bonds measured by H-NMR is less than 0.5 per 1000 carbon atoms. (B1) Acid value is in the range of 1 to 300 mgKOH / g, (B2) The apparent viscosity at 150°C is in the range of 1 to 1,000 cPs, (B3) a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) within the range of 1,000 to 50,000, (B4) a molecular weight distribution (Mw / Mn) of 2.5 or less in terms of polystyrene, as measured by gel permeation chromatography (GPC), (B5) The weight fraction of unreacted molecules measured by high performance liquid chromatography (HPLC) is 54% or less, (B6) Among the unreacted molecules contained in the acid-modified product (B), the weight fraction of unreacted molecules having a molecular weight higher than the weight average molecular weight of the acid-modified product (B) measured by gel permeation chromatography (GPC) and calculated as polystyrene is 18.5% or less.

2. The aqueous dispersion composition according to claim 1, wherein The acid-modified product (B) is a copolymer obtained by modifying the ethylene / α-olefin copolymer (A) with at least one selected from maleic acid and maleic anhydride.

3. The aqueous dispersion composition according to claim 1 or 2, wherein The viscosity of the aqueous dispersion composition is 15 mPa·s or more.

4. The aqueous dispersion composition according to claim 1 or 2, wherein The average particle size of the dispersed particles in the water dispersion composition is 100 nm or less. 5 . The method for producing the water dispersion composition according to claim 1 , comprising the step of emulsifying water and the acid-modified product (B).

6. Acid-modified ethylene-α-olefin copolymer (B), characterized in that: It is an acid-modified product of an ethylene·α-olefin copolymer (A) satisfying the following (A1) to (A6), and also satisfying the following (B1) to (B6), (A1) The content of ethylene units is within the range of 30 to 85 mol%, (A2) Kinematic viscosity at 100°C is 10-5,000 mm 2 / s range, (A3) a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) within the range of 1,000 to 50,000, (A4) a molecular weight distribution (Mw / Mn) of 2.5 or less in terms of polystyrene, as measured by gel permeation chromatography (GPC), (A5) The B value represented by the following formula [1] is 1.1 or more, [Mathematical formula 1] In formula [1], P E Indicates the molar fraction of ethylene units, P O represents the molar fraction of α-olefin units, P OE represents the molar fraction of ethylene·α-olefin chains in all binary chains, (A6) Utilization 1 The amount of unsaturated bonds measured by H-NMR is less than 0.5 per 1000 carbon atoms. (B1) Acid value is in the range of 1 to 300 mgKOH / g, (B2) The apparent viscosity at 150°C is in the range of 1 to 1,000 cPs, (B3) a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) within the range of 1,000 to 50,000, (B4) a molecular weight distribution (Mw / Mn) of 2.5 or less in terms of polystyrene, as measured by gel permeation chromatography (GPC), (B5) The weight fraction of unreacted molecules measured by high performance liquid chromatography (HPLC) is 54% or less, (B6) Among the unreacted molecules contained in the acid-modified ethylene·α-olefin copolymer (B), the weight fraction of unreacted molecules having a molecular weight higher than the weight average molecular weight of the acid-modified ethylene·α-olefin copolymer (B) measured by gel permeation chromatography (GPC) and converted to polystyrene is 18.5% or less.

7. The acid-modified ethylene / α-olefin copolymer (B) according to claim 6, wherein the ethylene / α-olefin copolymer (A) is modified with at least one selected from maleic acid and maleic anhydride.

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