Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
  • C08J2323/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention relates to an aqueous dispersion composition having good dispersibility, a method for producing the aqueous dispersion composition, and an ethylene / ⁇ -olefin copolymer acid-modified product.
• base materials such as plastic films, vapor-deposited films, metal foils, papers, and non-woven fabrics, or base materials and other adherends are bonded (that is, heat-sealed) by heat and pressure. It is known.
• heat sealing a method of directly bonding the base materials to each other or the base material and the adherend is usually used, but in order to improve the heat sealability between the base material and the adherend.
• a method is also used in which a heat sealant (adhesive) layer is formed on the base material in advance, and the base materials or the base material and other adherends are bonded to each other via the adhesive layer. ..
• Adhesives used in such heat sealants include, for example, at least one highly crystallinity polyolefin having a crystallinity greater than 50%, at least one dispersant, and an aqueous dispersion containing water. Proposed. (See, for example, Patent Document 1).
• the applicant contains at least one selected from the specific ethylene / ⁇ -olefin copolymer (A) and the acid-modified product (B) of the above (A) in the range of 0.01 to 50% by mass.
• the aqueous dispersion composition to be used has been found to improve the dispersibility of the acid-modified product (B) and the like, and has been proposed as Japanese Patent Application Laid-Open No. 2016-102157 (Patent Document 2). There is a demand for an aqueous dispersion having a good coating property on a base material or the like.
• An object of the present invention is to obtain an aqueous dispersion having excellent coatability on a substrate or the like having improved dispersibility of an ethylene / ⁇ -olefin copolymer acid-modified product.
• the present inventors modified the ethylene / ⁇ -olefin copolymer forming the aqueous dispersion with an unsaturated carboxylic acid and a derivative thereof. It has been found that the above object can be achieved by using an acid-modified product having a high modification rate, in other words, an acid-modified product having a low content of unreacted molecules.
• the present invention is an acid-modified product of the ethylene / ⁇ -olefin copolymer (A) satisfying the following (A1) to (A6), and the ethylene / ⁇ - satisfying the following (B1) to (B5).
• the present invention relates to an aqueous dispersion composition comprising an olefin copolymer acid-modified product (B) in the range of 0.01 to 50% by mass.
• A1 The content of ethylene units is in the range of 30 to 85 mol%.
• the kinematic viscosity at 100 ° C. is in the range of 10 to 5,000 mm 2 / s.
• the weight average molecular weight measured by gel permeation chromatography (GPC) and obtained by polystyrene conversion is in the range of 1,000 to 50,000.
• the molecular weight distribution (Mw / Mn) is 2.5 or less in the molecular weight obtained by polystyrene conversion as measured by gel permeation chromatography (GPC).
• the B value represented by the following formula [1] is 1.1 or more.
• PE indicates the mole fraction of ethylene units
• PO indicates the mole fraction of ⁇ -olefin units
• PO E indicates the mole fraction of the ethylene / ⁇ -olefin chain of the entire dyad chain. Indicates the fraction.
• A6 The amount of unsaturated bonds measured by 1 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.
• the weight average molecular weight measured by gel permeation chromatography (GPC) and obtained by polystyrene conversion is in the range of 1,000 to 50,000.
• the molecular weight distribution (Mw / Mn) is 2.5 or less in the molecular weight obtained by polystyrene conversion as measured by gel permeation chromatography (GPC).
• the weight fraction of unreacted molecules measured by high performance liquid chromatography (HPLC) is 59% or less.
• the particle size of the ethylene / ⁇ -olefin copolymer acid-modified product (B) forming the aqueous dispersion becomes smaller and the dispersibility is further improved, so that the emulsion becomes difficult to separate.
• the long-term stability is improved, the interaction between particles is increased and the viscosity is increased, so that the adhesion to the substrate is improved, and the liquid dripping is suppressed, so that the coating property to the substrate etc. is improved. Also improves.
• the aqueous dispersion composition of the present invention contains an acid-modified product (B) of the ethylene / ⁇ -olefin copolymer (A) described below.
• component (A) and “component (B)"
• a structural unit derived from a monomer is also referred to as a “monomer unit”.
• the ethylene / ⁇ -olefin copolymer (A) which is the source of the acid-modified product (B) of the ethylene / ⁇ -olefin copolymer forming the aqueous dispersion of the present invention, satisfies the following (A1) to (A6). ..
• the content of ethylene units is in the range of 30 to 85 mol%.
• the content of ethylene units in the component (A) is in the range of 30 to 85 mol%, preferably in the range of 40 to 70 mol%, and particularly preferably in the range of 45 to 65 mol%. If the content is excessively out of the above range, the copolymer becomes crystalline, and as a result, the viscosity of the copolymer increases or becomes solid, and the dispersibility of the copolymer in water becomes high. Getting worse.
• the aqueous dispersion composition of the present invention when used as, for example, a die-casting mold release agent, it is heated by heat. It is not preferable because the generated oxidative deterioration product is likely to be deposited on the mold surface.
• the content of ethylene units in the component (A) is measured by 13 C-NMR according to the method described in the "Polymer Analysis Handbook" (Asakura Shoten, First Edition, P184-211). It is also possible to measure the sample obtained by this method as a known sample by using Fourier transform infrared spectroscopy (FT-IR). The total content of all monomer units is 100 mol%.
• FT-IR Fourier transform infrared spectroscopy
• the kinematic viscosity at 100 ° C. is in the range of 10 to 5,000 mm 2 / s.
• the kinematic viscosity of the component (A) is a value measured by the method described in JIS K2283.
• the kinematic viscosity of component (A) at 100 ° C. is in the range of 10 to 5,000 mm 2 / s, preferably 10 to 2,500 mm 2 / s, more preferably 15 to 2,500 mm 2 / s, and particularly preferably. It is in the range of 15 to 500 mm 2 / s.
• the kinematic viscosity is excessively lower than the above range, it is easily ignited due to a large amount of easily volatile components and the storage stability is deteriorated, the evaporation weight loss is increased in the aqueous dispersion, and for example, it is used as a mold release agent for die casting. It is not preferable that the high molecular weight component that easily adheres to the mold is reduced. If the kinematic viscosity exceeds the above range excessively, the viscosity of the copolymer increases and it becomes difficult to uniformly disperse it in water.
• the weight average molecular weight is in the range of 1,000 to 50,000.
• the weight average molecular weight (Mw) of the component (A) is a value obtained by gel permeation chromatography (GPC) according to a method described later and converted to standard polystyrene.
• the weight average molecular weight (Mw) of the component (A) is in the range of 1,000 to 50,000, preferably 1,500 to 30,000, more preferably 1,500 to 20,000, and particularly preferably 1,. It is in the range of 500 to 7,000.
• Mw is excessively lower than the above range, it is easily ignited due to a large amount of volatile components and the storage stability is deteriorated, the evaporation weight loss is increased in the aqueous dispersion, and for example, when it is used as a mold release agent for die casting. It is not preferable because the high molecular weight component that easily adheres to the mold is reduced. If Mw exceeds the above range excessively, the viscosity of the copolymer increases and it becomes difficult to uniformly disperse it in water.
• the molecular weight distribution is 2.5 or less.
• the molecular weight distribution of the component (A) was measured by gel permeation chromatography (GPC) according to the method described later, and the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by standard polystyrene conversion was obtained. / Mn) is calculated.
• the Mw / Mn of the component (A) is 2.5 or less, preferably 2.3 or less, and more preferably 2.0 or less. If the molecular weight distribution exceeds the above range excessively, it means that the copolymer contains a large amount of low molecular weight components and high molecular weight components.
• the copolymer contains a large amount of low molecular weight components, it is easily ignited due to a large amount of easily volatile components, which deteriorates the storage stability and increases the evaporation loss in the aqueous dispersion.
• the copolymer contains a large amount of high molecular weight components, the viscosity of the copolymer increases and it becomes difficult to uniformly disperse in water.
• the B value is 1.1 or more.
• the B value of the 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.
• PE indicates the mole fraction of ethylene units
• PO indicates the mole fraction of ⁇ -olefin units
• PO E indicates the mole fraction of the ethylene / ⁇ -olefin chain of the entire dyad chain. Shows the rate.
• the B value is an index showing the randomness of the copolymer chain distribution in the copolymer, and PE, PO and POE in the above formula [1] are measured in 13 C-NMR spectra and J. .. C. Randall [Macropolymers, 15,353 (1982)], J. Mol. It can be obtained based on the reports of Ray [Macromolecules, 10, 773 (1977)] and other publicly known documents such as "Polymer Analysis Handbook" (Asakura Shoten, first edition, pp. 184 to 211).
• the B value is larger, the crystallinity of the component (A) is less likely to occur, the viscosity of the component (A) does not increase or the component (A) does not become solid, and the dispersibility in water is less likely to deteriorate. ..
• the specific measurement conditions for the B value are as described in the examples.
• (A6) 1 The amount of unsaturated bonds measured by 1 H-NMR is less than 0.5 per 1000 carbon atoms.
• the total number of double bonds derived from vinyl, vinylidene, disubstituted olefins, trisubstituted olefins, etc. measured by 1 H-NMR in the molecule of component (A) (hereinafter also referred to as "unsaturated bond amount"). However, for every 1000 carbon atoms, the number is less than 0.5, preferably less than 0.3, more preferably less than 0.2, and particularly preferably less than 0.1. When the unsaturated bond amount is within the range, the heat resistance of the component (A) becomes good.
• the specific measurement conditions for the unsaturated bond amount are as described in the examples.
• the component (A) further satisfies the following (A7).
• A7 No melting point is observed. It is preferable that the melting point of the component (A) is not observed in the differential scanning calorimetry (DSC).
• the fact that the melting point (Tm) is not observed means that the heat of fusion ( ⁇ H) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured.
• the fact that the heat of fusion ( ⁇ H) is not substantially measured means that no peak is observed in the differential scanning calorimetry (DSC), or the amount of heat of fusion observed is 1 J / g or less.
• the melting point (Tm) and heat of fusion ( ⁇ H) of the component (A) were measured by differential scanning calorimetry (DSC), cooled to -100 ° C, and then raised to 150 ° C at a heating rate of 10 ° C / min. Sometimes the DSC curve is analyzed and obtained with reference to JIS K7121. If the melting point is not observed, it means that the crystallinity of the component (A) is low as a result, the viscosity of the component (A) does not increase or the component (A) does not become solid, and the dispersibility in water is excellent.
• Examples of the ⁇ -olefin forming the component (A) include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eikosen and the like, exemplifying linear or branched ⁇ -olefins having 3 to 20 carbon atoms. Can be done.
• ⁇ -olefin a linear or branched ⁇ -olefin having 3 to 10 carbon atoms is preferable, and at least one selected from propylene, 1-butene, 1-hexene and 1-octene is more preferable.
• Propylene is most preferable from the viewpoint of the fluidity of the aqueous dispersion composition using the copolymer.
• the ⁇ -olefin can be used alone or in combination of two or more. Further, the polymerization is promoted by allowing at least one other monomer selected from the polar group-containing monomer, the aromatic vinyl compound, the alicyclic vinyl compound and the cyclic olefin to coexist in the reaction system together with the ⁇ -olefin, and the component (A). ) Can also be obtained.
• the other monomer can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the total of ethylene and ⁇ -olefin.
• Examples of the polar group-containing monomer include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid.
• ⁇ , ⁇ -unsaturated carboxylic acid esters such as n-propyl, methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate, etc. Can be exemplified.
• aromatic vinyl compounds examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, and hydroxystyrene.
• examples thereof include p-chlorostyrene, divinylbenzene, ⁇ -methylstyrene, and allylbenzene.
• Examples of the alicyclic vinyl compound include vinylcyclohexane.
• 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.
• the component (A) may be used alone or in combination of two or more.
• two or more kinds of components (A) having different molecular weights and / or different monomer compositions may be used in combination.
• the method for producing the component (A) is not particularly limited, but a method using a vanadium-based catalyst containing a vanadium compound and an organoaluminum compound as described in Japanese Patent Publication No. 2-1163 and Japanese Patent Publication No. 2-7998. Can be mentioned. Further, as a method for producing a copolymer with high polymerization activity, a metallocene compound as described in JP-A-61-221207, JP-A-7-121969, Patent No. 2796376, and Patent No. 4367687.
• a method using a metallocene-based catalyst containing (eg, zirconosen) and an organic aluminum oxy compound (eg, aluminoxane) may be used, and the chlorine content of the obtained copolymer and the amount of 2,1-insertion of propylene are inserted.
• the method using a metallocene-based catalyst is more preferable.
• the vanadium-based catalyst uses more chlorine compounds as the co-catalyst than the metallocene-based catalyst, so there is a possibility that a small amount of chlorine may remain in the obtained component (A).
• the chlorine content in the copolymer is preferably 100 wtppm or less, more preferably 50 wtppm or less, further preferably 20 wtppm or less, and particularly preferably 5 wtppm or less.
• the chlorine content can be quantified by various known methods. The specific measurement method in the present invention is as described in the examples.
• the reduction of the 2,1-insertion amount of propylene in the component (A) makes it possible to further reduce the ethylene chain in the copolymer molecule and suppress the intramolecular crystallinity of ethylene.
• Copolymer has excellent dispersibility in water.
• the amount of 2,1-insertion of propylene is determined by analysis of 13 C-NMR measurement according to the method described in JP-A-7-145212, and is preferably less than 1%, more preferably 0 to 0.5%, and further. It is preferably 0 to 0.1%. It is particularly preferable that no peak is observed in the range of 15.0 to 17.5 ppm.
• the component (A) having a good performance balance in terms of molecular weight control, molecular weight distribution, amorphousness, and B value can be obtained.
• the component (A) is a crosslinked metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and the crosslinked metallocene compound (a). It is produced by copolymerizing ethylene and ⁇ -olefin in the presence of an olefin polymerization catalyst containing at least one compound (b) selected from the compound (b-3) that reacts with and forms an ion pair. be able to.
• Y, M, R 1 to R 14 , Q, n and j in the formula [I] will be described below.
• Y, M, R 1 to R 14 , Q, n and j Y is a Group 14 atom, and examples thereof include a carbon atom, a silicon atom, a germanium atom, and a tin atom, preferably a carbon atom or a silicon atom, and more preferably a carbon atom.
• M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.
• R 1 to R 12 are atoms or substituents 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 are the same. But it can be different. Further, the adjacent substituents R 1 to R 12 may or may not be bonded to each other to form a ring.
• Hydrocarbon groups 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 3 carbon atoms. 20 to 20 cyclic unsaturated hydrocarbon groups and the like are exemplified.
• the alkyl group having 1 to 20 carbon atoms includes a linear saturated hydrocarbon group such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group.
• N-octyl group, n-nonyl group, n-decanyl group and other branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3 -Methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group , 1-Methyl-1-isopropyl-2-methylpropyl group, cyclopropylmethyl group and the like are exemplified.
• the alkyl group preferably has 1 to 6 carbon atoms.
• Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornenyl group, which are unsubstituted cyclic saturated hydrocarbon groups.
• a 3-methylcyclopentyl group which is a group in which one or more hydrogen atoms contained in an unsubstituted cyclic saturated hydrocarbon group, such as an adamantyl group and a 2-adamantyl group, are replaced with a hydrocarbon group having 1 to 17 carbon atoms.
• Examples thereof include a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 4-cyclohexylcyclohexyl group, and a 4-phenylcyclohexyl group.
• the cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.
• the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms includes an alkenyl group, an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), and a 1-methylethenyl group (isopropenyl group). Examples thereof include an ethynyl group, a 1-propynyl group, and a 2-propynyl group (propargyl group), which are alkynyl groups.
• the chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
• Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopentadienyl group, a norbornyl group, a phenyl group, a naphthyl group, an indenyl group, an azulenyl group, and a phenanthryl group, which are unsubstituted cyclic unsaturated hydrocarbon groups.
• One or more hydrogen atoms contained in a linear saturated hydrocarbon group or a branched saturated hydrocarbon group such as a phenyl group and a 2,4,6-trimethylphenyl group (mesityl group) have 3 to 19 carbon atoms. Examples thereof include a benzyl group, a cumyl group, etc., which are groups substituted with a substituted or substituted cyclic unsaturated hydrocarbon group.
• the cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.
• Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group, which are groups in which at least one carbon atom is replaced with a silicon atom in a hydrocarbon group having 1 to 20 carbon atoms.
• Alkylsilyl group such as, dimethylphenylsilyl group, methyldiphenylsilyl group, arylsilyl group such as t-butyldiphenylsilyl group, pentamethyldisilanyl group, trimethylsilylmethyl group and the like are exemplified.
• the alkylsilyl group preferably has 1 to 10 carbon atoms
• the arylsilyl group preferably has 6 to 18 carbon atoms.
• At least one CH-structural unit is replaced with a nitrogen atom in the amino group, the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or the silicon-containing group, and at least one -CH 2 -Structural unit is replaced with a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, and at least one-CH 3 structural unit is replaced with a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms.
• N-morpholinyl group and nitro group are exemplified.
• the nitrogen-containing group a dimethylamino group and an N-morpholinyl group are preferable.
• the oxygen-containing group is a hydroxyl group, a above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group in which at least one -CH 2 -structural unit is replaced with an oxygen atom or a carbonyl group.
• a methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group in which at least one -CH 3 structural unit is replaced with an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded.
• Methoxyethoxy group hydroxymethyl group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group Group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, Examples thereof include a carbamoyl group, a methylaminocarbonyl group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an etocarboxymethyl group, a carbamoylmethyl group, a furanyl group and a pyranyl group.
• oxygen-containing group As the
• halogen atom examples include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.
• the halogen-containing group is a trifluoromethyl group in which at least one hydrogen atom is substituted with a halogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group.
• Tribromomethyl group, pentafluoroethyl group, pentafluorophenyl group and the like are exemplified.
• Adjacent substituents R 1 to R 12 are bonded to each other to form an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like, and R 1 to R 12 are bonded to each other.
• a ring may be formed together with the ring carbon.
• alkylene group having 1 to 20 carbon atoms examples include a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), an ethylmethylene group, a methylethylene group, and an n-propylene group.
• the alkylene group preferably has 1 to 6 carbon atoms.
• Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 4,4'-biphenylene group.
• the allyrene group preferably has 6 to 12 carbon atoms.
• Q is selected from halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, anionic ligands and neutral ligands that can be coordinated with lone electron pairs in the same or different combinations. 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, a chlorine atom is preferable. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.
• anion ligand examples include an alkoxy group such as a methoxy group, a t-butoxy group and a phenoxy group, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.
• Examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane.
• organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane.
• An ether compound and the like can be exemplified.
• R 13 and R 14 are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms (excluding the following aryl groups and substituted aryl groups), aryl groups, substituted aryl groups, silicon-containing groups, nitrogen-containing groups, and oxygen-containing groups. It is an atom or a substituent selected from a group, a halogen atom and a halogen-containing group, and may be the same or different from each other. Further, R 13 and R 14 may or may not be bonded to each other to form a ring.
• 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.
• the aryl group although it partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, it is a substituent derived from an aromatic compound, such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group.
• Examples thereof include a group, anthrasenyl group, phenanthrenyl group, tetrasenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like.
• a phenyl group or a 2-naphthyl group is preferable.
• aromatic compound examples include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, inden, azulene, pyrrole, pyridine, furan, and thiophene. ..
• the substituted aryl group partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but one or more hydrogen atoms of the aryl group are hydrocarbons having 1 to 20 carbon atoms.
• Examples thereof include a group substituted with at least one substituent selected from a group (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.
• R 13 and R 14 are bonded to each other to form an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like to form a ring together with Y to which R 13 and R 14 are bonded. May be.
• Specific examples of the alkylene group and the arylene group are as described above.
• n is preferably 1.
• crosslinked metallocene compound (a-1) Such a crosslinked metallocene compound is also hereinafter referred to as “crosslinked metallocene compound (a-1)”.
• the crosslinked metallocene compound (a-1) simplifies the manufacturing process, reduces the manufacturing cost, and thus the crosslinked metallocene compound (a-).
• 1) there is an advantage that the production cost of the ethylene / ⁇ -olefin copolymer (A) is reduced.
• crosslinked metallocene compound (a-2) it is preferable that R 1 , R 2 , R 3 and R 4 are all hydrogen atoms.
• Such a crosslinked metallocene compound is also hereinafter referred to as “crosslinked metallocene compound (a-2)”.
• the crosslinked metallocene compound (a-2) has a manufacturing step as compared with a compound in which any one or more of R 1 , R 2 , R 3 and R 4 in the above formula [I] is substituted with a substituent other than a hydrogen atom.
• the production cost is reduced, and by using this crosslinked metallocene compound (a-2), the production cost of the ethylene / ⁇ -olefin copolymer (A) can be reduced.
• the randomness of the ethylene / ⁇ -olefin copolymer (A) is lowered by performing high temperature polymerization, but the olefin polymerization catalyst containing the crosslinked metallocene compound (a-2) is used.
• ethylene and ⁇ -olefin are copolymerized in the presence of the polymer, there is an advantage that the obtained ethylene / ⁇ -olefin copolymer (A) has high randomness even in high temperature polymerization.
• crosslinked metallocene compound (a-2) it is preferable that either R 13 or R 14 is an aryl group or a substituted aryl group.
• Such a crosslinked metallocene compound is also hereinafter referred to as “crosslinked metallocene compound (a-3)”.
• the crosslinked metallocene compound (a-3) has two of (A) in the produced ethylene / ⁇ -olefin copolymer, as compared with the case where R 13 and R 14 are both substituents other than the aryl group and the substituted aryl group. The advantage of a small amount of double bonds can be obtained.
• crosslinked metallocene compound (a-3) it is more preferable that one of R 13 and R 14 is an aryl group or a substituted aryl group, and the other is an alkyl group having 1 to 20 carbon atoms, and R 13 and R are more preferable. It is particularly preferred that any one of 14 is an aryl group or a substituted aryl group and the other is a methyl group.
• Such a crosslinked metallocene compound is also hereinafter referred to as “crosslinked metallocene compound (a-4)”.
• the crosslinked metallocene compound (a-4) has a double bond amount in the produced ethylene / ⁇ -olefin copolymer (A) as compared with the case where R 13 and R 14 are both aryl groups or substituted aryl groups. It has an excellent balance with the polymerization activity, and by using this crosslinked metallocene compound, it is possible to obtain an advantage that the production cost of the ethylene / ⁇ -olefin copolymer (A) is reduced.
• the ethylene / ⁇ -olefin copolymer (A) is produced using the crosslinked metallocene compound (a-4), it is introduced into the polymerization reactor as compared with the case where the crosslinked metallocene compound (a-3) is used.
• the advantages are that the amount of hydrogen is reduced, the polymerization activity is improved, and the production cost of the ethylene / ⁇ -olefin copolymer (A) is reduced.
• R 6 and R 11 are alkyl groups having 1 to 20 carbon atoms, or alkylene groups having 1 to 20 carbon atoms formed by bonding with adjacent substituents. Is preferable.
• Such a crosslinked metallocene compound is also hereinafter also referred to as a “crosslinked metallocene compound (a-5)”.
• the crosslinked metallocene compound (a-5) simplifies the manufacturing process as compared with a compound in which R 6 and R 11 are substituted with a substituent other than an alkyl group having 1 to 20 carbon atoms and an alkylene group having 1 to 20 carbon atoms. Therefore, the production cost is reduced, and by using this crosslinked metallocene compound (a-5), there is an advantage that the production cost of the ethylene / ⁇ -olefin copolymer (A) is reduced.
• M is a zirconium atom.
• the polymerization activity is higher than in the case where M is a titanium atom or a hafnium atom, and ethylene.
• Examples of these compounds include a compound in which the zirconium atom is replaced with a hafnium atom or a compound in which the chloro ligand is replaced with a methyl group, but the crosslinked metallocene compound (a) is not limited to these examples.
• the ⁇ 5-tetramethyloctahydrodibenzofluorenyl, which is a constituent part of the exemplified crosslinked metallocene compound (a), is 4,4,7,7-tetramethyl- (5a, 5b, 11a, 12, 12a- ⁇ 5).
• ⁇ 5-octamethyloctahydrodibenzofluorenyl is 1,1,4,4,7,7 , 10,10-Octamethyl- (5a, 5b, 11a, 12, 12a- ⁇ 5) -1,2,3,4,7,8,9,10-octahydrodibenzo [b, H] fluorenyl groups, respectively. ..
• the polymerization catalyst preferably used in the present invention reacts with the crosslinked metallocene compound (a), the organometallic compound (b-1), the organoaluminum oxy compound (b-2), and the crosslinked metallocene compound (a) to form ions. It contains at least one compound (b) selected from the pairing compound (b-3).
• organometallic compound (b-1) specifically, the following organometallic compounds of Groups 1, 2 and 12 and 13 of the Periodic Table are used.
• B-1a General formula RamAl (OR b ) nHpXq
• Examples of such compounds include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, triisopropylaluminum, triisobutylaluminum, and tri.
• tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum, triisopropylaluminum, triisobutylaluminum, and tri.
• Tri-branched alkylaluminum such as sec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum, tricyclohexylaluminum, tricyclooctylaluminum
• Tricycloalkylaluminum such as, triphenylaluminum, triarylaluminum such as tri (4-methylphenyl) aluminum, diisopropylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, general formula (i-C 4H 9 ) xAly ( C 5 H 10 ) Alkenyl aluminum such as isoprenyl aluminum represented by z (where x, y, z are positive numbers and z ⁇ 2x in the formula), isobutylaluminum methoxydo, and isobutylalum
• Alkylaluminum alkoxides such as, dimethylaluminum methoxydo, diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutylaluminum butoxide, alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo, butylaluminum sesquibutoxide , general formula Ra 2.5 Al (OR).
• Alkylaluminum aryloxy such as partially alkoxylated alkylaluminum, diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide) having an average composition represented by 0.5 etc.
• Dialkylaluminum halides such as do, dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromid, ethylaluminum Partial such as alkylaluminum dihalide such as dichloride Dialkylaluminum hydrides such as alkylaluminum, diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydrides, alkylaluminum dihydrides such as propylaluminum dihydrides, and other partially hydrogenated alkylaluminum, ethyl. Examples thereof include partially alkoxylated and hydrogenated alkylaluminum such
• a compound similar to the compound represented by the above general formula RamAl (OR b ) nHpXq can also be used.
• an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom can be mentioned.
• Specific examples of such a compound include (C 2 H 5 ) 2 AlN (C 2 H 5 ) Al (C 2 H 5 ) 2 .
• R a R b M 3 (In the formula, R a and R b may be the same or different from each other, and show hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. , M 3 is Mg, Zn or Cd), a dialkyl compound of a Group 2 or Group 12 metal of the periodic table.
• organoaluminum oxy compound (b-2) conventionally known aluminoxane can be used as it is. Specifically, a compound represented by the following general formula [II] and a compound represented by the following general formula [III] can be mentioned.
• R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.
• methylaluminoxane in which R is a methyl group and n of 3 or more, preferably 10 or more is used. It does not matter if some organoaluminum compounds are mixed in these aluminoxanes.
• a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied.
• organoaluminum oxy compounds described in JP-A-2-167305, and aluminoxane having two or more types of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 are also available. It can be preferably used.
• the "benzene-insoluble organic aluminum oxy compound” that may be used in the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less in terms of Al atom. It is a compound having 2% or less and being insoluble or sparingly soluble in benzene.
• organoaluminum oxy compound (b-2) modified methylaluminoxane as represented by the following general formula [IV] can also be mentioned.
• Me represents a methyl group
• R represents a hydrocarbon group having 2 to 10 carbon atoms
• m and n each independently represent an integer of 2 or more.
• This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584. Further, from Tosoh Finechem Co., Ltd. and the like, those prepared by using trimethylaluminum and triisobutylaluminum and having R as an isobutyl group are commercially available under the names of MMAO and TMAO.
• Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability, and specifically, among the compounds represented by the above formula [II] and the compounds represented by the above formula [III]. Unlike compounds that are insoluble or sparingly soluble in benzene, they are soluble in aliphatic or alicyclic hydrocarbons.
• organoaluminum oxy compound (b-2) an organoaluminum oxy compound containing boron represented by the following general formula [V] can also be mentioned.
• R c represents a hydrocarbon group having 1 to 10 carbon atoms.
• R d may be the same or different from each other and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
• ionic ionic compound As the compound (b-3) that reacts with the crosslinked metallocene compound (a) to form an ion pair (hereinafter, may be abbreviated as "ionic ionic compound” or simply “ionic compound"), JP. 1-501950, 1-502306, 3-179005, 3-179006, 3-207703, 3-207703, 3-207704, US Pat. No. 5,321,106. Examples thereof include Lewis acid, an ionic compound, a borane compound and a carborane compound described in Japanese publications. Further, heteropoly compounds and isopoly compounds can also be mentioned.
• the ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VI].
• Re + examples include H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptiltyrienyl cation, ferrosenium cation having a transition metal, and the like.
• R f to R i may be the same 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. Yes, preferably a substituted aryl group.
• carbocation cation examples include trisubstituted carbocation cations such as triphenylcarbenium cation, tris (4-methylphenyl) carbocation cation, and tris (3,5-dimethylphenyl) carbenium cation. ..
• the ammonium cation is a trialkyl-substituted ammonium such as a trimethylammonium cation, a triethylammonary cation, a tri (n-propyl) ammonium cation, a triisopropylammonium cation, a tri (n-butyl) ammonium cation, or a triisobutylammonium cation.
• a trialkyl-substituted ammonium such as a trimethylammonium cation, a triethylammonary cation, a tri (n-propyl) ammonium cation, a triisopropylammonium cation, a tri (n-butyl) ammonium cation, or a triisobutylammonium cation.
• N, N-dialkylanilinium cations such as cations, N, N-dimethylanilinium cations, N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, Examples thereof include dialkylammonium cations such as dicyclohexylammonium cations.
• phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tris (4-methylphenyl) phosphonium cation, and tris (3,5-dimethylphenyl) phosphonium cation.
• Re + is preferably a carbonium cation, an ammonium cation, or the like, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.
• ionized ionic compounds as compounds containing a carbenium cation, triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis ⁇ 3, 5-Di- (trifluoromethyl) phenyl ⁇ borate, tris (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate, etc. It can be exemplified.
• ionized ionic compounds as compounds containing a trialkyl-substituted ammonium cation, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium Tetrax (4-methylphenyl) borate, trimethylammonium tetrakis (2-methylphenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (tripropylammonium tetrakis) Pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-di
• N, N-dialkylanilinium cations N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) Borate, N, N-dimethylanilinium tetrakis ⁇ 3,5-di (trifluoromethyl) phenyl ⁇ borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) Borate, N, N-diethylanilinium tetrakis ⁇ 3,5-di (trifluoromethyl) phenyl ⁇ borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4 , 6-Penta
• examples of the compound containing a dialkylammonium cation include di-n-propylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
• ionic compounds exemplified by JP-A-2004-51676 can be used without limitation.
• the above-mentioned ionic compound (b-3) may be used alone or in combination of two or more.
• organometallic compound (b-1) trimethylaluminum, triethylaluminum and triisobutylaluminum, which are easily available because they are commercially available products, are preferable. Of these, triisobutylaluminum, which is easy to handle, is particularly preferable.
• organoaluminum oxy compound (b-2) methylaluminoxane, which is easily available because it is a commercially available product, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferable. Of these, MMAO having improved solubility in various solvents and storage stability is particularly preferable.
• triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilyi are easily available as commercial products and contribute greatly to the improvement of polymerization activity. Ionic tetrakis (pentafluorophenyl) borate is preferred.
• the carrier (c) may be used as a constituent component of the olefin polymerization catalyst, if necessary.
• the carrier (c) that may be used in the present invention is an inorganic or organic compound and is a solid in the form of granules or fine particles.
• an inorganic compound a porous oxide, an inorganic chloride, clay, a clay mineral or an ion-exchange layered compound is preferable.
• porous oxide examples include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , etc., or a composite or mixture containing these, for example.
• Uses natural or synthetic zeolite, SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , SiO 2 -TiO 2 -MgO, etc. can do. Of these, those containing SiO 2 and / or Al 2 O 3 as main components are preferable.
• the carrier preferably used in the present invention has a particle size of 0.5 to 300 ⁇ m, preferably 1.0 to 200 ⁇ m, and has a specific surface area. Is in the range of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and the pore volume is in the range of 0.3 to 3.0 cm 3 / g.
• Such a carrier is used after firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
• the inorganic chloride MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 and the like are used.
• the inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it may be used that the inorganic chloride is dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitant.
• Clay is usually composed mainly of clay minerals.
• the ion-exchangeable layered compound is a compound having a crystal structure in which the constituent planes are stacked in parallel with each other by an ionic bond or the like with a weak bonding force, and the contained ions can be exchanged.
• Most clay minerals are ion-exchange layered compounds.
• these clays, clay minerals, and ion-exchange layered compounds not only naturally produced ones but also artificial synthetic compounds can be used.
• clay mineral or ion-exchangeable layered compound clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl 2 type and CdI 2 type can be used.
• Such clays and clay minerals include kaolin, bentonite, knot clay, gailome clay, alophen, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dicite.
• ion-exchangeable layered compound examples include ⁇ -Zr (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Zr (KPO 4 ) 2.3 H 2 O, ⁇ -Ti (HPO 4 ) 2 , ⁇ -Ti (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Sn (HPO 4 ) 2 ⁇ H 2 O, ⁇ -Zr (HPO 4 ) 2 , ⁇ -Ti (HPO 4 ) ) 2 , ⁇ -Ti (NH 4 PO 4 ) 2 ⁇ H 2 O and other crystalline acidic salts of polyvalent metals.
• any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used.
• Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment.
• the ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with another large bulky ion.
• Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars.
• guest compound introducing another substance (guest compound) between the layers of the layered compound in this way is called intercalation.
• Guest compounds include cationic inorganic compounds such as TiCl 4 , ZrCl 4 , and metal alkoxides such as Ti (OR) 4 , Zr (OR) 4 , PO (OR) 3 , and B (OR) 3 (R is a hydrocarbon.
• clays or clay minerals preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
• organic compound as the carrier (c) include granular or fine particle solids having a particle size in the range of 0.5 to 300 ⁇ m.
• a (co) polymer or vinylcyclohexane or styrene produced mainly of an ⁇ -olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene.
• (co) polymers produced with the above as a main component and variants thereof are examples of (co) polymers produced with the above as a main component and variants thereof.
• High-temperature polymerization is possible by a polymerization method using an olefin polymerization catalyst capable of producing an ethylene / ⁇ -olefin copolymer (A) having high randomness. That is, by using the olefin polymerization catalyst, it is possible to suppress a decrease in the randomness of the ethylene / ⁇ -olefin copolymer (A) produced during high-temperature polymerization.
• the viscosity of the polymerization solution containing the produced ethylene / ⁇ -olefin copolymer (A) decreases at high temperatures, so the ethylene / ⁇ -olefin copolymer (A) in the polymer is compared to that at low temperature polymerization. ) Can be increased, and as a result, the productivity per polymerizer is improved.
• the copolymerization of ethylene and ⁇ -olefin in the present invention can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization (slurry polymerization) or a gas phase polymerization method. Solution polymerization is particularly preferable from the viewpoint that the above can be enjoyed to the maximum extent.
• each component of the olefin polymerization catalyst are arbitrarily selected. Further, at least two or more of each component in the catalyst may be contacted in advance.
• the amount of the crosslinked metallocene compound (a) (hereinafter, also referred to as “component (a)”) is usually 10 -9 to 10 -1 mol, preferably 10 -8 to 10-2 mol, per liter of the reaction volume. Used in.
• the organometallic compound (b-1) (hereinafter, also referred to as “component (b-1)”) is a molar ratio of the component (b-1) to the transition metal atom (M) in the component (a) [(b). -1) / M] is usually used in an amount of 0.01 to 50,000, preferably 0.05 to 10,000.
• the organic aluminum oxy compound (b-2) (hereinafter, also referred to as “component (b-2)”) is composed of an aluminum atom in the component (b-2) and a transition metal atom (M) in the component (a). It is used in an amount such that the molar ratio [(b-2) / M] is usually 10 to 5,000, preferably 20 to 2,000.
• the ionic compound (b-3) (hereinafter, also referred to as “component (b-3)”) is a molar ratio of the component (b-3) to the transition metal atom (M) in the component (a) [(b). -3) / M] is usually used in an amount of 1 to 10,000, preferably 1 to 5,000.
• the polymerization temperature is usually ⁇ 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. In the polymerization temperature range in the above range, as the temperature increases, the viscosity of the solution during polymerization decreases, and the heat of polymerization becomes easier to remove.
• the polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.
• the polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization continuously in two or more polymerizers having different reaction conditions.
• the molecular weight of the obtained copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can be adjusted according to the amount of compound (b) used. When hydrogen is added, the amount of hydrogen is appropriately about 0.001 to 5,000 NL per 1 kg of the copolymer to be produced.
• 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.
• Specific examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Hexane, heptane, octane, decane, and cyclohexane are particularly preferred.
• the ⁇ -olefin itself to be polymerized can also be used as the polymerization solvent.
• 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 viewpoint of reducing the burden on the environment and for human health. From the perspective of minimizing the effects of these, their use is undesirable.
• the kinematic viscosity of the ethylene / ⁇ -olefin copolymer (A) at 100 ° C. depends on the molecular weight of the copolymer. That is, if the molecular weight is high, the viscosity is high, and if the molecular weight is low, the viscosity is low. Therefore, the kinematic viscosity at 100 ° C. is adjusted by the above-mentioned molecular weight adjustment. Further, the molecular weight distribution (Mw / Mn) of the obtained copolymer can be adjusted by removing the low molecular weight component of the copolymer obtained by a conventionally known method such as vacuum distillation.
• the obtained copolymer may be hydrogenated (hereinafter, also referred to as “hydrogenation”) by a conventionally known method. If the amount of unsaturated bonds of the obtained copolymer is reduced by hydrogenation, oxidative stability and heat resistance are improved.
• the ethylene / ⁇ -olefin copolymer acid-modified product (B) forming the aqueous dispersion of the present invention is an acid-modified product of the ethylene / ⁇ -olefin copolymer (A).
• the acid-modified product (B) is also referred to as "component (B)” or "acid-modified ethylene / ⁇ -olefin copolymer (B)".
• the acid-modified product (B) according to the present invention is a modified product obtained by modifying the ethylene / ⁇ -olefin copolymer (A) with a compound selected from an unsaturated carboxylic acid and a derivative thereof, and is preferably the compound. It is an ethylene / ⁇ -olefin copolymer modified with.
• Examples of the unsaturated carboxylic acid and its derivative include an unsaturated carboxylic acid having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, and a derivative of the unsaturated carboxylic acid.
• Derivatives of unsaturated carboxylic acids include, for example, acid anhydrides, esters, amides and imides of unsaturated carboxylic acids.
• the component (A) which is the starting material of the component (B), has a small amount of unsaturated bonds as described above, the component (B) has a structure in which the graft component is randomly grafted to the main clavicle of the component (A). It is presumed to be.
• 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-norbornen-2,3-dicarboxylic acid. Be done.
• Examples of the acid anhydride of the unsaturated carboxylic acid include acid anhydrides of dibasic acids such as maleic acid, itaconic acid, citraconic acid and 5-norbornene-2,3-dicarboxylic acid.
• ester of the unsaturated carboxylic acid examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleic acid ester, diethyl maleic acid ester, monomethyl fumarate ester, and fumaric acid.
• esters and half esters such as dimethyl ester, monomethyl ester of itaconic acid and diethyl ester of itaconic acid.
• Examples of the unsaturated carboxylic acid amide include acrylamide, methacrylic acid, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, and maleic acid-N-monobutyl.
• Examples thereof include amides, maleic acid-N, N-dibutylamides, fumaric acid monoamides, fumaric acid diamides, fumaric acid-N-monobutylamides and fumaric acid-N, N-dibutylamides.
• the unsaturated carboxylic acid imide examples include maleimide, N-butylmaleimide, and N-phenylmaleimide.
• at least one selected from maleic acid and maleic anhydride is characterized by having high polarity as one monomer and being difficult to form by-products such as homopolymers in the modification reaction using peroxide. Seeds are preferred.
• the graft component may be used alone or in combination of two or more.
• the grafting reaction is carried out, for example, by the method described in JP-A-61-126120, usually in the presence of a radical initiator such as dit-butyl peroxide, etc., in the presence of an ethylene / ⁇ -olefin copolymer (A).
• the graft component is added to the mixture.
• the reaction temperature is usually 150 to 200 ° C., preferably 160 to 180 ° C.
• the reaction time is usually 1 to 50 hours, preferably 1 to 10 hours.
• the graft component is preferably used in an amount such that the acid value of the obtained component (B) falls within the following range.
• the ethylene / ⁇ -olefin copolymer acid-modified product (B) is an acid-modified product of the ethylene / ⁇ -olefin copolymer (A) satisfying the above (A1) to (A6), and is as follows. Satisfy (B1) to (B5).
• the acid value is in the range of 1 to 300 mgKOH / g.
• the acid value is used as an index of the graft amount of the graft component.
• the acid value of component (B) is preferably in the range of 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and even more preferably 10 to 150 mgKOH / g. If the acid value is lower than the above range, the polarity of the copolymer may be lowered and the stability of the aqueous dispersion may be lowered. 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.
• the acid value of the component (B) can be adjusted by the amount of graft of the graft component with respect to the component (A). For example, in order to increase the acid value of the component (B), it is preferable to increase the amount of graft.
• the acid value of the component (B) indicates 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 conforming to JIS K0070. Specifically, it is as described in the examples.
• the apparent viscosity at 150 ° C. is in the range of 1 to 1,000 cPs.
• the apparent viscosity (Brookfield viscosity) of the 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.
• the apparent viscosity is in the above range, it is excellent in terms of balance between low volatility, handleability, and dispersibility in water.
• the weight average molecular weight measured by gel permeation chromatography (GPC) and obtained by polystyrene conversion is in the range of 1,000 to 50,000.
• the weight average molecular weight (Mw) of the component (B) is a value obtained by gel permeation chromatography (GPC) according to a method described later and converted to standard polystyrene.
• the weight average molecular weight (Mw) of the component (B) is preferably in the range of 1,000 to 50,000, more preferably 1,000 to 30,000, still more preferably 1,500 to 30,000, and particularly preferably. It is in the range of 2,000 to 7,000, most preferably 5,000 to 6,000.
• Mw is excessively lower than the above range, it may be easily ignited due to a large amount of volatile components, resulting in deterioration of storage stability or an increase in evaporation loss in the aqueous dispersion. If Mw exceeds the above range excessively, the viscosity of the copolymer increases, and it may be difficult to disperse the copolymer uniformly in water.
• the molecular weight distribution (Mw / Mn) is 2.5 or less in the molecular weight obtained by polystyrene conversion as measured by gel permeation chromatography (GPC).
• the molecular weight distribution of the component (B) was measured by gel permeation chromatography (GPC) according to the method described later, and the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by standard polystyrene conversion was obtained. / Mn) is calculated.
• the Mw / Mn of the component (B) is preferably 2.5 or less, more preferably 2.3 or less, still more preferably 2.0 or less. If the molecular weight distribution exceeds the above range excessively, it means that the copolymer contains a large amount of low molecular weight components and high molecular weight components.
• the copolymer When the copolymer contains a large amount of low molecular weight components, it may easily ignite due to a large amount of easily volatile components, resulting in deterioration of storage stability or an increase in evaporation loss in the aqueous dispersion. When the copolymer contains a large amount of high molecular weight components, the viscosity of the copolymer increases, and it may be difficult to disperse the copolymer uniformly in water.
• the weight fraction of unreacted molecules measured by high performance liquid chromatography (HPLC) is 59% or less.
• HPLC high performance liquid chromatography
• the component (B) according to the present invention preferably further satisfies the following (B6).
• B6 Among the unreacted molecules contained in the acid-modified product (B), the molecular weight is larger than the weight average molecular weight of the acid-modified product (B) obtained by gel permeation chromatography (GPC) and obtained by polystyrene conversion. The weight fraction of unreacted molecules with high molecular weight is 20% or less.
• the unreacted molecule When the weight fraction of the unreacted molecule having a molecular weight higher than the weight average molecular weight of the acid-modified product (B) is less than the above range, the unreacted molecule has a high molecular weight, which is inferior in dispersibility in water. This is preferable because the proportion of molecules is small and the component (B) is easily uniformly dispersed in water.
• the component (B) according to the present invention preferably further satisfies the following (B7).
• B7) No melting point is observed. It is preferable that the melting point of the component (B) is not observed in the differential scanning calorimetry (DSC).
• the fact that the melting point (Tm) is not observed means that the heat of fusion ( ⁇ H) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured.
• the fact that the heat of fusion ( ⁇ H) is not substantially measured means that no peak is observed in the differential scanning calorimetry (DSC), or the amount of heat of fusion observed is 1 J / g or less.
• the melting point (Tm) and heat of fusion ( ⁇ H) of the component (B) were measured by differential scanning calorimetry (DSC), cooled to -100 ° C, and then raised to 150 ° C at a heating rate of 10 ° C / min. Sometimes the DSC curve is analyzed and obtained with reference to JIS K7121. If the melting point is not observed, it means that the crystallinity of the component (B) is low as a result, the viscosity of the component (B) does not increase or the component (B) does not become solid, and the dispersibility in water is excellent.
• the component (B) may be used alone or in combination of two or more.
• ⁇ Aqueous dispersion composition> The aqueous dispersion composition of the present invention contains the above ethylene / ⁇ -olefin copolymer acid-modified product (B) in the range of 0.01 to 50% by mass, preferably 0.05 to 30% by mass.
• the aqueous dispersion composition of the present invention preferably has a viscosity of 15 mPa ⁇ s or more, more preferably 20 to 200 mPa ⁇ s, still more preferably 30 to 200 mPa ⁇ s, and particularly preferably. It is in the range of 60 to 200 mPa ⁇ s, most preferably in the range of 100 to 200 mPa ⁇ s.
• the viscosity of the aqueous dispersion composition is within such a range, it is excellent in spreading on the surface of the base material when the aqueous dispersion composition is applied / coated on the base material, and dripping is less likely to occur, so that the base material is coated. It is preferable because it has excellent properties.
• the average particle size of the dispersed particles of the ethylene / ⁇ -olefin copolymer acid-modified product (B) forming the dispersion composition is preferably 100 nm or less, more preferably 10 to 10 to It is in the range of 95 nm, more preferably in the range of 10-60 nm, particularly preferably in the range of 20-40 nm, and most preferably in the range of 20-30 nm. If the average particle size of the dispersed particles is larger than the above range, the particles are easily separated, which is not preferable from the viewpoint of stability.
• the average particle size of the dispersed particles is smaller than the above range, the interaction between the particles becomes strong and the viscosity of the aqueous dispersion composition tends to increase, which is not preferable because it is difficult to spread on the surface of the base material.
• the average particle size of the dispersed particles is in the above range, the stability of the aqueous dispersion composition is excellent and the coating property on the substrate is also excellent, which is preferable.
• the average particle size in the present invention means the diameter of particles when the cumulative volume is 50% when the total volume is 100%, and a dynamic light scattering type particle size distribution measuring device or a nanotrack particle size distribution measuring device is used. Can be measured.
• the average particle size of the particles in the dispersion was measured using Nanotrack WAVE2-EX150 (manufactured by MicrotracBEL).
• the excellent stability of the aqueous dispersion composition in the present invention means that the dispersed state of the aqueous dispersion composition when stored in a room temperature environment is good.
• the stability of the aqueous dispersion composition is as follows: The aqueous dispersion composition is placed in a transparent cylindrical glass container having a length of 120 mm and a diameter of 40 mm, and allowed to stand at 23 ° C. for 15 hours, and then visually checked for separation. Evaluated.
• the aqueous dispersion composition of the present invention preferably has a water content of 50 to 99.99% by mass, preferably 60 to 99.95% by mass.
• the aqueous dispersion composition of the present invention contains a surfactant, a corrosion inhibitor, an antioxidant, an animal or vegetable oil or a fatty acid ester thereof, and a synthetic lubricating oil.
• Wax, inorganic powder, and various other additives may be contained. The additive may be used alone or in combination of two or more.
• alkylene oxide adduct of nonylphenol alkylene oxide adduct of linear higher alcohol having 12 to 18 carbon atoms
• alkylene oxide adduct of higher amine polyoxyethylene adduct of fatty acid such as castor oil, alkylene oxide of fatty acid amide.
• examples include adducts, alkyl sulfates, tamol types, tetraalkylammonium salts, alkylbetaines and the like.
• the amount added thereof is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass in the aqueous dispersion composition.
• the corrosion inhibitor examples include sodium nitrite, sodium benzoate, triethanolamine salt and the like.
• the amount added is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass in the aqueous dispersion composition.
• antioxidants examples include phenolic and amine compounds such as 2,6-di-t-butyl-4-methylphenol.
• the amount of the antioxidant added is preferably 0 to 3% by mass in the aqueous dispersion composition.
• animal and vegetable oils include mineral oil, rapeseed oil, soybean oil, palm oil, palm oil, beef tallow, and lard.
• synthetic lubricating oil include polyalphaolefin, polybutadiene, polyisobutylene, and various ester oils.
• waxes synthetic waxes such as polyethylene wax and polypropylene wax, oxides and acid-modified products of these synthetic waxes, carnauba, montan, beeswax, etc., as long as the dispersibility in water and adhesion to the mold are not deteriorated.
• Natural wax and the like can be exemplified.
• Inorganic powders include talc, mica, mica, viscosity, organic clay, boronite, mortar, sericite, calcium carbonate, borate, alumina, titanium oxide, baking soda, zirconium oxide, graphite, carbon black, diamond powder, etc. Can be exemplified.
• silicone compounds such as silicone, dimethyl silicone, alkyl-modified silicone, and alkylaralkyl-modified silicone, zinc dialkyldithiophosphate (ZnDTP) for reducing friction, molybdenum dialkyldithiophosphate (MoDTP), and zinc dithiocarbamate (ZnDTC).
• ZnDTP zinc dialkyldithiophosphate
• MoDTC zinc dithiocarbamate
• Molybdenum dithiocarbamate Molybdenum dithiocarbamate
• phosphorus-based sulfur-based extreme pressure agents
• antifoaming agents preservatives, and the like
• aqueous dispersion composition of the present invention for example, water, the ethylene / ⁇ -olefin copolymer acid-modified product (B), and the additive as appropriate are homogenized manually or by using a stirrer.
• a method of emulsifying by a usual method such as using an emulsifying machine such as a mixer, a colloid mill, a line mixer, or a homogenizer.
• the water temperature at the time of emulsification is preferably 40 to 99 ° C, more preferably 50 to 99 ° C.
• Morpholine may be added when preparing the aqueous dispersion composition, or may be mixed in advance with the acid-modified product (B) and reacted. Morpholine is preferably added in an amount of 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 20 parts by mass with respect to 100 parts by mass of the acid-modified product (B).
• the ethylene / ⁇ -olefin copolymer acid-modified product (B) has an arbitrary acid value, apparent viscosity at 150 ° C., weight average molecular weight, molecular weight distribution, weight fraction of unreacted molecules, and unreacted.
• an ethylene / ⁇ -olefin copolymer acid-modified product having a weight fraction of unreacted molecules having a molecular weight higher than the weight average molecular weight of the ethylene / ⁇ -olefin copolymer acid-modified product (B) (by using B), the stability, viscosity, and average molecular weight of the aqueous dispersion composition can be adjusted without changing the equipment and conditions at the time of emulsification.
• the adjusted weight fraction of the unreacted molecules and the weight of the unreacted molecules having a higher molecular weight than the weight average molecular weight of the ethylene / ⁇ -olefin copolymer acid-modified product (B) among the unreacted molecules The method using the ethylene / ⁇ -olefin copolymer acid-modified product (B) having a ratio determines the total amount of polar groups, the molecular weight and the molecular weight distribution in the ethylene / ⁇ -olefin copolymer acid-modified product (B).
• the stability, viscosity, and average molecular weight of the aqueous dispersion composition can be adjusted without changing the composition, for example, changes in properties when the aqueous dispersion composition is applied or coated and dried are likely to be small, and various types are available. It is preferable as a method for producing an aqueous dispersion composition having stability, viscosity and average molecular weight suitable for the application.
• the aqueous dispersion composition of the present invention is not particularly limited in use, and is a modifier, a modifier, a softener, a gel modifier, a latex modifier, and other water-soluble agents for various resins or rubber-like polymers.
• Emulsifying aids such as sex resin modifiers and emulsion polymerization aids, lubricating oil additives, adhesives, dispersants, dispersion aids, printing inks, printing pastes, lacquers, inks, coating agents for food packaging materials , Flooring materials, shoes coatings, automobile coatings, other water-based paints, papermaking / spinning / textile finishing agents, cutting oils, drawing oils and other metal processing oils, die-casting mold release agents, etc.
• the aqueous dispersion composition of the present invention can ensure good adhesion to a substrate when used as a heat sealant and is excellent in dispersibility in water. It can be preferably used.
• ⁇ Viscosity characteristics (A2)> 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.
• PE indicates the mole fraction of ethylene units
• PO indicates the mole fraction of ⁇ -olefin units
• PO E indicates the mole fraction of the ethylene / ⁇ -olefin chain of the entire dyad chain. Shows the rate.
• the temperature is raised at 10 ° C./min, and the temperature at which the enthalpy curve obtained in the temperature raising process shows the maximum value is set as the melting point (Tm), and the total amount of heat absorbed due to melting is taken.
• the amount of heat of fusion ( ⁇ H) was used. If no peak was observed or the value of heat of fusion ( ⁇ H) was 1 J / g or less, the melting point (Tm) was considered not to be observed.
• the melting point (Tm) and the amount of heat of fusion ( ⁇ H) were determined based on JIS K7121.
• Acid value (mgKOH / g) (N / 10 KOH titration (ml) x F x 5.61) / (sample (g) x 0.01) ⁇ Apparent viscosity (B2)>
• the apparent viscosity (Brookfield viscosity) at 150 ° C. was measured and calculated by the method described in JIS K7117-1.
• Weight fraction of unreacted molecule 100 ⁇ S MD / S 0 ⁇ Unreacted molecules having a higher molecular weight than the weight average molecular weight of the ethylene / ⁇ -olefin copolymer acid-modified product (B) among the unreacted molecules contained in the ethylene / ⁇ -olefin copolymer acid-modified product (B).
• a chromatographic tube having a diameter of 50 mm is filled with crushed silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) to a height of 5 cm, impregnated with hexane, and then ethylene / ⁇ .
• -A solution prepared by dissolving 1 g of an olefin copolymer acid-modified product (B) in 5 mL of hexane and 20 mL of hexane were added in order from the upper part, and about 10 mL of the solution eluted from the lower part of the chromatograph tube was collected and dried.
• the molecular weight of the separated unreacted molecules was measured using HLC-8320GPC of Toso Co., Ltd. as follows, and the molecular weight was higher than the weight average molecular weight of the ethylene / ⁇ -olefin copolymer acid-modified product (B).
• the weight fraction of unreacted molecules was calculated.
• TSKgel SuperMultipore HZ-M 4 pieces was used, the column temperature was 40 ° C., tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the developing speed was 0.35 ml / min, and the sample concentration was set to 0.35 ml / min.
• the sample injection volume was 5.5 g / L, the sample injection volume was 20 microliters, and a differential refractometer was used as a detector.
• PStQuick MP-M manufactured by Tosoh Corporation was used.
• the solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After distilling off the solvent under reduced pressure and concentrating, a small amount of hexane was added and left at ⁇ 20 ° C. to precipitate a red-orange solid. After washing this solid with a small amount of hexane, it is dried under reduced pressure to obtain a red-orange solid [methylphenylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5-2,7 -di-t-butylfur). Olenyl)] 1.20 g of zirconium dichloride was obtained.
• ⁇ Polymerization example 1> By charging 760 ml of heptane and 120 g of propylene into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, the temperature in the system is raised to 150 ° C., and then 0.85 MPa of hydrogen and 0.19 MPa of ethylene are supplied. The total pressure was 3 MPaG.
• the ethylene / propylene copolymer (A-1) shown in Table 1 was obtained by the above operation.
• the analysis results of the obtained ethylene / propylene copolymer (A-1) are shown in Table 1.
• ⁇ Polymerization example 2> By charging 710 mL of heptane and 145 g of propylene into a fully nitrogen-substituted stainless steel autoclave with an internal volume of 2 L, raising the temperature in the system to 150 ° C., and then supplying 0.40 MPa of hydrogen and 0.27 MPa of ethylene. The total pressure was 3 MPaG.
• the ethylene / propylene copolymer (A-3) shown in Table 1 was obtained by the above operation.
• the analysis results of the obtained ethylene / propylene copolymer (A-3) are shown in Table 1.
• ethylene obtained by a method using a vanadium-based catalyst containing a vanadium compound and an organoaluminum compound in the same manner as described in Japanese Patent Publication No. 2-1163 and Japanese Patent Publication No. 2-7998.
• Propylene copolymers (A-2), (A-4) and (A-5) were used in the examples.
• Table 1 shows the analysis results of the ethylene / propylene copolymers (A-2), (A-4), and (A-5) used.
• Ethylene-propylene copolymer (A-2) is 91.4% by weight
• ethylene-propylene copolymer (A-4) is 4.3% by weight
• ethylene-propylene copolymer (A-5) is 4.
• An ethylene / propylene copolymer (A-8) was obtained.
• the analysis results of the obtained ethylene / propylene copolymer (A-8) are shown in Table 1.
• the temperature inside the reactor was further raised to 175 ° C., and after depressurization in the system, unnecessary components (unreacted maleic anhydride and decomposition products of di-t-butyl peroxide, etc.) were added under reduced pressure and nitrogen airflow conditions. Removed.
• Table 3 shows the analysis results of the obtained ethylene-propylene copolymer acid-modified product (B-1).
• ⁇ Aqueous dispersion composition > [Example 1] 41.6 g of ethylene / propylene copolymer acid-modified product (B-1) and 10.4 g of polyoxyethylene alkyl ether Emulgen 1108 (manufactured by Kao Co., Ltd.) were taken in a 500 mL round bottom flask with a stirrer, and the stirring speed was 50 rpm. The temperature was raised to 96 ° C. while stirring with. Next, a solution prepared by mixing 7.5 g of morpholine deer first grade (manufactured by Kanto Chemical Co., Inc.) and 10.0 g of pure water was added, and the mixture was reacted at a stirring speed of 250 rpm for 30 minutes.
• morpholine deer first grade manufactured by Kanto Chemical Co., Inc.
• aqueous dispersion composition was evaluated for stability, viscosity, and average particle size according to the following method.
• the analysis results of the obtained aqueous dispersion composition are shown in Table 4.
• Example 2 to 10 An aqueous dispersion composition was obtained in the same manner as in Example 1 except that the ethylene / propylene copolymer acid-modified product used was changed to the contents shown in Table 4. The analysis results of the obtained aqueous dispersion composition are shown in Table 4.
• aqueous dispersion composition was obtained in the same manner as in Example 1 except that the ethylene / propylene copolymer acid-modified product used was changed to the contents shown in Table 4.
• the stability of the aqueous dispersion composition is evaluated by visually observing the presence or absence of separation after placing the aqueous dispersion composition in a transparent cylindrical glass container having a length of 120 mm and a diameter of 40 mm and allowing it to stand at 23 ° C. for 15 hours. did. Those having a uniform turbidity of the aqueous dispersion composition in the glass container were evaluated as having no separation, and those having a difference in the turbidity in the height direction were evaluated as having separation.
• Viscosity of aqueous dispersion composition The viscosity of the aqueous dispersion composition was measured at 23 ° C. using a B-type viscometer TVB-10M (manufactured by Toki Sangyo Co., Ltd.). For the measurement, the sample for which the stability of the aqueous dispersion composition was evaluated was used as it was.
• Average particle size of aqueous dispersion composition The average particle size of the aqueous dispersion composition was measured using Nanotrack WAVE2-EX150 (manufactured by MicrotracBEL). For the measurement, the sample whose stability of the aqueous dispersion composition was evaluated was weighed into a cup made of 1 g polypropylene, diluted with pure 10 g, and measured. From the obtained measurement results, the diameter of the particles when the cumulative volume was 50% when the total volume was 100% was defined as the average particle size.
• the aqueous dispersion composition using the ethylene / propylene copolymer acid-modified product having a low weight fraction of the unreacted molecule and a small proportion of the high molecular weight component in the unreacted molecule is available. Since the average particle size is small and the viscosity is high, the stability of the aqueous dispersion composition is more excellent, and when applied to the substrate, the substrate has excellent adhesion and is resistant to dripping. It is more preferable because it can be expected to have a coat property.
• the aqueous dispersion composition of the present invention, the method for producing the aqueous dispersion composition, and the modified ethylene / ⁇ -olefin copolymer acid are an aqueous dispersion having excellent stability and excellent coating property on a substrate.

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