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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
• • 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
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/108—Hydrocarbon resins
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention relates to polyether-modified polyolefin resins.
• Polyolefin-based substrates have excellent performance and are inexpensive, so they are widely used in plastic molded components and various films for food packaging.
• polyolefin-based substrates are non-polar substrates, have low surface free energy, and are crystalline, so they generally have the disadvantage that inks and paints do not adhere easily to them.
• Patent Document 1 it is known that the adhesion can be improved by acid-modifying polyolefin resins.
• the objective of the present invention is to provide a polyolefin resin that exhibits good antistatic properties and adhesive properties.
• the present invention provides the following: [1] (A) a polyolefin resin graft-modified with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, (B) a polyetheramine, A polyether-modified polyolefin resin obtained by grafting, A polyether-modified polyolefin resin, in which the weight ratio of a structure derived from component (A) to a structure derived from component (B) contained therein (structure derived from component (A):structure derived from component (B)) is 70:30 to 30:70.
• the present invention provides a polyolefin resin that exhibits good antistatic properties and adhesion.
• AA-BB means "greater than or equal to AA and less than or equal to BB.”
• AA and BB each represent a numerical value, with AA ⁇ BB.
• the units of “AA” are the same as those of “BB” unless otherwise specified.
• (meth)acrylic acid ((meth)acrylate) includes “acrylic acid” (acrylate), “methacrylic acid” (methacrylate), and combinations thereof.
• the present invention provides a polyether-modified polyolefin resin obtained by grafting (B) a polyetheramine onto (A) a polyolefin resin graft-modified with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, in which the weight ratio of the structure derived from component (A) to the structure derived from component (B) contained in the polyether-modified polyolefin resin (structure derived from component (A):structure derived from component (B)) is 70:30 to 30:70.
• Such a polyether-modified polyolefin resin can exhibit good antistatic properties and adhesive properties.
• the polyether-modified polyolefin resin of the present invention can be obtained by using a component (A) obtained by graft-modifying a polyolefin resin with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof.
• Polyolefin resins are polymers of olefins (usually ⁇ -olefins). Examples of ⁇ -olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.
• the polyolefin resin may be a polymer of one type of olefin (usually an ⁇ -olefin) or a copolymer of two or more types of olefins (usually an ⁇ -olefin).
• the polyolefin resin is a copolymer, it may be a random copolymer or a block copolymer.
• preferred polyolefin resins are polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-butene copolymer, and ethylene-propylene-1-butene copolymer.
• polypropylene refers to a polymer whose constituent units are propylene-derived constituent units.
• Ethylene-propylene copolymer refers to a copolymer containing ethylene-derived constituent units and propylene-derived constituent units as constituent units.
• Propylene-1-butene copolymer refers to a copolymer containing propylene-derived constituent units and 1-butene-derived constituent units as constituent units.
• “Ethylene-propylene-1-butene copolymer” refers to a copolymer containing ethylene-derived constituent units, propylene-derived constituent units, and 1-butene-derived constituent units as constituent units.
• these (co)polymers may contain small amounts of other olefin-derived constituent units as constituent units.
• the polyolefin resin preferably contains 15 mol% or more of propylene-derived structural units out of 100 mol% of all structural units, more preferably 30 mol% or more, and even more preferably 50 mol% or more. If the propylene-derived structural units are contained in the above range, adhesion to non-polar resin substrates such as propylene resins can be maintained.
• the polyolefin resin is an ethylene-propylene copolymer, a propylene-1-butene copolymer, or an ethylene-propylene-1-butene copolymer, out of 100 mol% of all constituent units, the ethylene-derived constituent units and/or the butene-derived constituent units are preferably 3 to 85 mol%, more preferably 10 to 70 mol%, and the propylene-derived constituent units are preferably 15 to 97 mol%, more preferably 30 to 90 mol%.
• the polyolefin resin is preferably one obtained using a metallocene catalyst as a polymerization catalyst. Any known metallocene catalyst can be used. When a metallocene catalyst is used, the molecular weight distribution of the polyolefin resin becomes narrow. Furthermore, when the polyolefin resin is a copolymer, it has excellent random copolymerization properties, a narrow composition distribution, and can broaden the range of comonomers that can be copolymerized.
• the structure of the polyolefin resin may be any of an isotactic structure, an atactic structure, a syndiotactic structure, etc.
• a polyolefin resin with an isotactic structure which can be obtained when a metallocene catalyst is used, is preferred.
• the lower limit of the melting point of the polyolefin resin is preferably 30°C or higher, more preferably 60°C or higher, and the upper limit is preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 165°C or lower.
• the melting point of the polyolefin resin is 30°C or higher, the polyether-modified polyolefin resin can exhibit sufficient coating strength when used for applications such as inks and paints. Therefore, adhesion to the substrate can be sufficiently exhibited. In addition, when used as an ink, blocking during printing can be suppressed.
• the melting point of the polyolefin resin is 180°C or lower, the polyether-modified polyolefin resin can be suppressed from becoming too hard when used for applications such as inks and paints. Therefore, the coating film can exhibit moderate flexibility.
• the lower limit of the weight average molecular weight (Mw) of the polyolefin resin is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 40,000 or more, and particularly preferably 50,000 or more, and the upper limit is preferably 500,000 or less, more preferably 400,000 or less, even more preferably 200,000 or less, even more preferably 170,000 or less, and particularly preferably 150,000 or less.
• the weight average molecular weight (Mw) of the polyolefin resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
• the component (A) used in the present invention is a polyolefin resin modified with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof.
• Examples of the derivative of an ⁇ , ⁇ -unsaturated carboxylic acid include an ⁇ , ⁇ -unsaturated carboxylic anhydride and an ⁇ , ⁇ -unsaturated carboxylic ester.
• Modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative can be performed, for example, by graft copolymerization of ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative into the polyolefin chain of the raw material polyolefin resin.
• the graft copolymerization is not particularly limited, and can be performed using known methods such as the melt method and solution method. When the melt method is used, the operation is simple and the reaction can be performed in a shorter time. When the solution method is used, there are fewer side reactions and a more uniform graft polymer is obtained.
• the heating and melting temperature is usually equal to or higher than the melting point of the raw polyolefin resin, preferably equal to or higher than the melting point of the raw polyolefin resin and lower than 300°C, more preferably equal to or higher than the melting point of the raw polyolefin resin and lower than 250°C, and particularly preferably equal to or higher than the melting point of the raw polyolefin resin and lower than 200°C.
• modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is carried out by the melting method, it can be carried out using equipment such as a Banbury mixer, kneader, extruder, etc., and it is preferable to use an extruder (extrusion modification).
• the extrusion modification method includes a method in which raw materials are fed to the feed section of an extruder (e.g., a co-rotating multi-screw extruder, a twin-screw extruder), and the steps of raw material mixing, melt kneading, reaction, and devolatilization cooling are carried out in sequence in the extruder, and the resin emerging from the tip die is cooled (e.g., immersed in a water tank) to obtain a modified solid resin composition.
• the progress of the reaction can be adjusted by adjusting the temperature of each part of the barrel and the screw rotation speed.
• modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is carried out by a solution method, it is preferable to carry out, for example, by dissolving the raw material polyolefin resin in a hydrophobic solvent and then heating it to react with the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative.
• the temperature during the reaction is preferably 100 to 180°C.
• the hydrophobic solvent in the system may be distilled off under reduced pressure, or the hydrophobic solvent may be removed using an extruder.
• an aromatic hydrocarbon solvent such as toluene, o-xylene, m-xylene, p-xylene, or ethylbenzene
• an aliphatic hydrocarbon solvent such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, ethylcyclohexane, n-nonane, or n-decane
• an aromatic hydrocarbon solvent such as toluene, o-xylene, m-xylene, p-xylene, or ethylbenzene
• an aliphatic hydrocarbon solvent such as n-pentane, cyclopentane, n-hexane, isohexane, cyclohexane, n-heptane, methylcyclohe
• Examples of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, himic anhydride, (meth)acrylic acid, (meth)acrylic acid esters, etc. It is preferable that the ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof include one or more selected from maleic anhydride and (meth)acrylic acid esters.
• the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative contains a (meth)acrylic acid ester.
• (meth)acrylic acid ester alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, 2,4,6-trimethylheptyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetrade
• the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1 to 30, more preferably 4 to 20, even more preferably 8 to 16, and particularly preferably 10 to 14.
• the alkyl (meth)acrylate may be one type or a combination of two or more types, and in one embodiment, it is more preferable that it contains lauryl (meth)acrylate and/or tridecyl (meth)acrylate.
• the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative more preferably contains maleic anhydride.
• the cyclic structure derived from the maleic anhydride contained in the modified polyolefin resin may be partially hydrolyzed and ring-opened.
• the content of maleic anhydride in the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 10% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, and particularly preferably 50% by weight or more, assuming the total amount of the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative to be 100% by weight.
• the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative contains both a (meth)acrylic acid ester and maleic anhydride.
• the weight ratio of the (meth)acrylic acid ester and maleic anhydride contained in the ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative ((meth)acrylic acid ester:maleic anhydride) is preferably 10:90 to 90:10, more preferably 30:70 to 70:30, and particularly preferably 40:60 to 60:40.
• the amount of (meth)acrylic acid ester used for modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 30% or less, more preferably 20% or less, even more preferably 10% or less, and particularly preferably 5% or less, based on 100% by weight of the raw material polyolefin resin.
• the amount of maleic anhydride used for modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 30% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, and particularly preferably 5% by weight or less, relative to 100% by weight of the raw material mixed polyolefin resin.
• the total amount of ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative used for modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, relative to 100% by weight of the raw material mixed polyolefin resin.
• the lower limit is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, even more preferably 1% by weight or more, and particularly preferably 3% by weight or more.
• the modification with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative is preferably carried out in the presence of a radical reaction initiator.
• the radical reaction initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated, such as organic peroxides and azonitriles.
• organic peroxides examples include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, dibenzoyl peroxide, benzoyl m-tolyl peroxide, di(m-tolyl)benzoyl, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-
• the azonitriles include 3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate,
• azonitriles examples include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile).
• the polyether-modified polyolefin resin of the present invention is obtained by grafting a polyetheramine, which is a component (B), onto a component (A).
• the polyetheramine of component (B) used in the present invention is usually a compound having a polyether skeleton and at least one amino group (e.g., a primary amino group).
• the amino group (e.g., a primary amino group) of the polyetheramine can be bonded to a structure (e.g., an acid anhydride group, a carboxyl group) derived from an ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative in component (A).
• a linear or branched polyetheramine having a polyether skeleton formed by addition polymerization of an alkylene oxide such as ethylene oxide (EO) or propylene oxide (PO) and having one or more primary amino groups at the terminal can be mentioned.
• an alkylene oxide such as ethylene oxide (EO) or propylene oxide (PO)
• the polyether skeleton may be random or block-shaped.
• the average molar ratio (EO:PO) of ethylene oxide (EO) and propylene oxide (PO) forming the polyether skeleton contained in the polyetheramine of component (B) is preferably 5:95 to 100:0, 10:90 to 100:0, or 15:85 to 100:0, more preferably 20:80 to 100:0, even more preferably 35:65 to 100:0, even more preferably 50:50 to 99:1, even more preferably 60:50 to 95:5, and particularly preferably 70:50 to 93:7.
• the polyetheramine of component (B) preferably has a polyoxyalkylene structure selected from a polyoxyethylene structure, a polyoxypropylene structure, and a poly(oxyethylene/oxypropylene) structure, and more preferably has a poly(oxyethylene/oxypropylene) structure and is a linear or branched polyetheramine having one or more primary amino groups at the terminal.
• polyetheramine of component (B) include: The following formula (1):
• R 1 is a hydrocarbon group.
• x and y are each independently 0 or an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 60), and the sum of x and y is an integer of 2 or more (preferably an integer of 5 to 200, more preferably an integer of 10 to 100).
• the positions of the x unit and the y unit are not fixed to the positions shown in the formula, and the copolymer may be any block copolymer of ethylene oxide and propylene oxide, or may be a random copolymer.
• the y unit may have an isotactic structure or a syndiotactic structure, or may have an atactic structure.
• Polyetheramine having a structure represented by the formula: The following formula (2):
• R2 is a hydrogen atom or a methyl group.
• x and y are each independently 0 or an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 60), and the sum of x and y is an integer of 2 or more (preferably an integer of 5 to 200, more preferably an integer of 10 to 100).
• the positions of the x unit and the y unit are not fixed to the positions shown in the formula, and the copolymer may be any block copolymer of ethylene oxide and propylene oxide, or may be a random copolymer.
• the y unit may have an isotactic structure or a syndiotactic structure, but may also have an atactic structure.
• Polyetheramine having a structure represented by the formula: The following formula (3):
• R3 is a hydrogen atom, a methyl group, an ethyl group, or a propyl group; n is 0 or 1; x, y, and z are each independently 0 or an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 60), and the sum of x, y, and z is an integer of 3 or more (preferably an integer of 5 to 200, more preferably an integer of 10 to 100).) Polyetheramine having a structure represented by the formula: The following formula (4):
• R3 is a hydrogen atom, a methyl group, an ethyl group, or a propyl group.
• n is 0 or 1.
• x, y, and z are each independently an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 60), and the sum of x, y, and z is an integer of 3 or more (preferably an integer of 5 to 200, more preferably an integer of 10 to 100).
• the x unit, y unit, and z unit may each have an isotactic structure or a syndiotactic structure, or may have an atactic structure.
• the hydrocarbon group for R 1 in formula (1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a hydrocarbon group having 1 to 5 carbon atoms.
• the hydrocarbon group include alkyl groups (e.g., methyl, ethyl, and propyl groups), aryl groups (e.g., phenyl groups), aralkyl groups (e.g., benzyl groups), and alkyl-substituted aryl groups (e.g., methylphenyl groups).
• the weight average molecular weight (Mw) of the polyetheramine of component (B) is preferably 200 to 20,000, more preferably 300 to 10,000, even more preferably 400 to 6,000, even more preferably 450 to 4,000, and particularly preferably 500 to 2,500.
• the weight average molecular weight of component (B) can be calculated from the average number of moles added of ethylene oxide or propylene oxide and the molecular weight of the terminal structure.
• component (B) examples include "JEFFAMINE (registered trademark, the same applies below) M-600", “JEFFAMINE M-1000", “JEFFAMINE M-2005”, “JEFFAMINE M-2070", “JEFFAMINE M-3085", “JEFFAMINE D-230", “JEFFAMINE D-430", “JEFFAMINE D-2000”, “JEFFAMINE D-4000”, “JEFFAMINE ED-600”, “JEFFAMINE ED-900”, “JEFFAMINE ED-2003”, “JEFFAMINE EDR-148", “JEFFAMINE T-403", “JEFFAMINE T-3000”, and “JEFFAMINE T-5000", manufactured by Huntsman.
• Component (B) may be one polyetheramine or a combination of two or more polyetheramines.
• the polyether-modified polyolefin resin of the present invention can be obtained, for example, by graft-modifying a polyolefin resin graft-modified with an ⁇ , ⁇ -unsaturated carboxylic acid and/or a derivative thereof, component (A), with a polyether amine, component (B).
• the grafting reaction of component (B) onto component (A) is preferably carried out, for example, by reacting component (A) with component (B) in a hydrophobic solvent under heating conditions.
• the weight ratio of component (A) to component (B) (component (A): component (B)) added to the reaction system is 70:30 to 30:70, preferably 65:35 to 35:65, more preferably 65:35 to 40:60, and particularly preferably 65:35 to 45:55.
• the reaction temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and particularly preferably 90 to 160°C.
• the reaction time is preferably 30 minutes or longer.
• the weight ratio of the structure derived from component (A) to the structure derived from component (B) contained in the polyether-modified polyolefin resin of the present invention is 70:30 to 30:70, preferably 65:35 to 35:65, more preferably 65:35 to 40:60, and particularly preferably 65:35 to 45:55.
• the weight ratio can be confirmed from the ratio of components (A) and (B) added to the reaction system.
• the polyether-modified polyolefin resin of the present invention may be used to form a resin composition together with other components as necessary, such as hydrophobic solvents, hydrophilic solvents, curing agents, adhesive components, stabilizers, basic substances, emulsifiers, crosslinking agents, diluents, light stabilizers, UV absorbers, pigments, dyes, and inorganic fillers.
• other components such as hydrophobic solvents, hydrophilic solvents, curing agents, adhesive components, stabilizers, basic substances, emulsifiers, crosslinking agents, diluents, light stabilizers, UV absorbers, pigments, dyes, and inorganic fillers.
• hydrophobic solvents examples include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aliphatic hydrocarbon solvents such as nonane and decane.
• aromatic hydrocarbon solvents such as toluene and xylene
• ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate
• ketone solvents such as acetone, methyl ethyl ket
• hydrophilic solvents include water; glycol solvents such as ethylene glycol; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-ethyl-hexanol; and glycol monoether solvents such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether.
• glycol solvents such as ethylene glycol
• alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-e
• Solvents may be used alone or in combination of two or more.
• the resin composition may take the form of either a dispersion or a solution depending on the solubility in the solvent.
• the solid content is usually 5% by weight or more, preferably 7% by weight or more, and more preferably 10% by weight or more (in the case of a hydrophilic solvent, even more preferably 20% by weight or more) relative to 100% by weight of the composition.
• the resin composition may be solvent-free (solid).
• the curing agent may be, for example, a polyisocyanate compound, an epoxy compound, a polyamine compound, a polyol compound, a crosslinking agent in which the functional groups of these are blocked with a protecting group, or a combination of two or more of these.
• the content of the curing agent may be appropriately selected depending on the content of the modified polyolefin resin.
• a catalyst such as an organotin compound or a tertiary amine compound may be used in combination depending on the purpose.
• the curing agent may be used alone or in combination of two or more.
• the adhesive component may be, for example, a known adhesive component such as a polyester adhesive, a polyurethane adhesive, or an acrylic adhesive.
• the adhesive component may be used alone or in combination of two or more types.
• Stabilizers include, for example, compounds containing an epoxy ring, such as epoxy stabilizers (epoxy stabilizers).
• Epoxy stabilizers include, for example, epoxy compounds with an epoxy equivalent of about 100 to 500 and containing one or more epoxy groups in one molecule.
• epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid
• epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid
• epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate
• monoepoxy compounds typified by condensation of bisphenol A or polyhydric alcohol with epichlorohydrin, such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether
• butyl glycidyl ether 2-ethylhexyl glycid
• the stabilizer may be a compound that does not contain an epoxy ring, and examples of the stabilizer include metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; and hydrotalcite compounds.
• the stabilizer may be used alone or in combination of two or more types.
• the resin composition contains a basic substance. This allows the pH to be appropriately adjusted, and the dispersibility and storage stability of the resin in the solvent to be further improved.
• Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol, and preferably include ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol.
• the basic substance may be used alone or in combination of two or more.
• the resin composition contains a diluent.
• diluents include alcohol and propylene-based glycol ethers.
• alcohol include methanol, ethanol, propanol, isopropanol, and butanol.
• propylene-based glycol ethers include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol tert-butyl ether.
• the diluent may be used alone or in combination of two or more types.
• the resin composition contains a crosslinking agent.
• the crosslinking agent may be any compound that can react with groups present in the resin composition, such as hydroxyl groups, carboxyl groups, and amino groups, to form a crosslinked structure, and may be either a water-soluble crosslinking agent or an aqueous dispersion of a crosslinking agent (a crosslinking agent that is dispersed in water by some method).
• crosslinking agents include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins.
• the crosslinking agents may be used alone or in combination of two or more types.
• the resin composition contains an emulsifier.
• emulsifiers include surfactants such as nonionic surfactants and anionic surfactants, with nonionic surfactants being preferred.
• nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth)acrylates.
• Polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines are preferred.
• anionic surfactants include alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, ⁇ -olefin sulfonates, methyl tauryl salts, sulfosuccinate salts, ether sulfonates, ether carboxylate salts, fatty acid salts, naphthalenesulfonic acid-formaldehyde condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, and alkylamine oxides. Polyoxyethylene alkyl ether sulfate salts and sulfosuccinate salts are preferred.
• the emulsifiers may be used alone or in combination of two or more.
• the resin composition may be produced according to a conventional method, and is not particularly limited.
• the resin composition may be produced in the form of a solution dissolved in the solvent used in the production of the polyether-modified polyolefin resin, the solvent used in the production may be removed, or the solvent used in the production may be replaced with another solvent and dissolved or dispersed.
• Other examples include a method in which the resin composition is produced without a solvent and the resin composition is produced as is, or a method in which the resin composition is dissolved or dispersed in another solvent.
• the resin composition is an aqueous dispersion
• a solvent e.g., an amphipathic solvent, a hydrophilic solvent
• a dispersion medium preferably water
• a neutralizing agent as necessary, and at least a part of the solvent is removed by a vacuum method, an azeotropic method, or the like to obtain an aqueous dispersion
• the other components that can be added as necessary as described above can be added appropriately at any stage of the production of the resin composition.
• the polyether-modified polyolefin resin of the present invention or a resin composition containing the same can exhibit good antistatic properties and adhesion.
• the coating film of the polyether-modified polyolefin resin of the present invention can have a surface resistivity measured in accordance with JIS K 6911 of preferably 1.0 ⁇ 10 13 ⁇ /sq. or less, more preferably 5.0 ⁇ 10 11 ⁇ /sq. or less, even more preferably 5.0 ⁇ 10 10 ⁇ /sq. or less, and particularly preferably 5.0 ⁇ 10 9 ⁇ /sq. or less.
• the surface resistivity can be measured as in Test Example 1 below.
• the polyether-modified polyolefin resin of the present invention or a resin composition containing the same can be used for paints, inks, binders (e.g., paint binders, ink binders, etc.), adhesives (e.g., metal adhesives, resin adhesives, etc.), and molded articles.
• binders e.g., paint binders, ink binders, etc.
• adhesives e.g., metal adhesives, resin adhesives, etc.
• molded articles e.g., molded articles.
• the polyether-modified polyolefin resin of the present invention or a resin composition containing the same can be used as a molded body or a material thereof.
• molded bodies or materials thereof include plastic containers or packaging for food, beverages, cosmetics, and medicines; plastic molded products such as tableware, furniture, and household goods; and plastic molded parts for automobiles, home appliances, etc.
• the reaction was carried out under conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100°C (1st and 2nd barrels), 200°C (3rd to 8th barrels), 90°C (9th and 10th barrels), and 110°C (11th to 14th barrels).
• a reduced pressure treatment was carried out to remove unreacted maleic anhydride, and a maleic anhydride-modified polyolefin resin was obtained.
• the resulting maleic anhydride-modified polyolefin resin had a weight average molecular weight of 80,000 and a graft amount of maleic anhydride of 3.2% by weight.
• the reaction was carried out under conditions of a residence time of 10 minutes, a rotation speed of 200 rpm, and barrel temperatures of 100°C (1st and 2nd barrels), 200°C (3rd to 8th barrels), 90°C (9th and 10th barrels), and 110°C (11th to 14th barrels).
• a reduced pressure treatment was carried out to remove unreacted maleic anhydride, yielding a maleic anhydride-acrylic acid ester modified polyolefin resin.
• the resulting maleic anhydride-acrylic acid ester modified polyolefin resin had a weight average molecular weight of 80,000, a maleic anhydride graft amount of 3.2% by weight, and an acrylic acid ester graft amount of 2.4% by weight.
• Example 1 Polyether-modified polyolefin resin A-1
• a 10% toluene solution of polyether modified polyolefin resin A-1 was prepared, and the resulting toluene solution was applied to the corona-treated surface of an IPA-wiped OPP film (manufactured by Futamura Chemical, film thickness 60 ⁇ m, dimensions 30 cm x 10 cm) using a Mayer bar to a film thickness of 10 ⁇ m, and then left to cure for 24 hours in an environment with a temperature of 25°C and a humidity of 50%. After curing, a 10 cm section was cut out 5 cm below the starting point of the coating from the coated film, to prepare a 10 cm x 10 cm test piece.
• IPA-wiped OPP film manufactured by Futamura Chemical, film thickness 60 ⁇ m, dimensions 30 cm x 10 cm
• Example 2 Polyether-modified polyolefin resin A-2
• Example 3 Polyether-modified polyolefin resin A-3
• a polyether-modified polyolefin resin A-3 was obtained in the same manner as in Example 1, except that 100 parts of the maleic anhydride-acrylic acid ester-modified polyolefin resin obtained in Production Example 2 was used instead of the maleic anhydride-modified polyolefin resin obtained in Production Example 1, and a test piece was prepared.
• Example 4 Polyether-modified polyolefin resin A-4
• a polyether-modified polyolefin resin A-4 was obtained in the same manner as in Example 1, except that 100 parts of the maleic anhydride-acrylic acid ester-modified polyolefin resin obtained in Production Example 2 was used instead of the maleic anhydride-modified polyolefin resin obtained in Production Example 1, and the amount of Huntsman's "Jeffamine M-1000" used was changed from 67 parts to 100 parts.
• a test piece was prepared from the polyether-modified polyolefin resin A-4.
• Example 5 Polyether-modified polyolefin resin A-5
• Example 6 Polyether-modified polyolefin resin A-6
• Example 7 Polyether-modified polyolefin resin A-7
• Example 8 Polyether-modified polyolefin resin A-8
• a polyether-modified polyolefin resin A-8 was obtained in the same manner as in Example 1, except that 100 parts of the maleic anhydride-acrylic acid ester-modified polyolefin resin obtained in Production Example 2 was used instead of the maleic anhydride-modified polyolefin resin obtained in Production Example 1, and the amount of Huntsman's "Jeffamine M-1000" used was changed from 67 parts to 43 parts.
• a test piece was prepared from the polyether-modified polyolefin resin A-8 in the same manner as in Example 1.
• Test pieces were prepared in the same manner as in Example 1, except that a 10% toluene solution of the maleic anhydride-modified polyolefin resin obtained in Production Example 1 was used in place of the 10% toluene solution of the polyether-modified polyolefin resin A-1.
• Test pieces were prepared in the same manner as in Example 1, except that a 10% toluene solution of the maleic anhydride-acrylic acid ester modified polyolefin resin obtained in Production Example 2 was used in place of the 10% toluene solution of the polyether modified polyolefin resin A-1.
• Example 3 Polyetheramine (raw material comparison)
• the coating liquid did not wet and spread on the substrate, but was repelled, and coating was not possible.
• Example 9 Water Dispersion of Polyether-Modified Polyolefin Resin A-1
• 100 parts of the polyether-modified polyolefin resin (A-1) prepared in Example 1 was dissolved in 17 parts of methylcyclohexane and 17 parts of n-butyl cellosolve, and 6.5 parts of a neutralizer (morpholine) was added under stirring at 100°C, and hot water was added until the solid content reached 24%, and distillation was performed under reduced pressure to obtain an aqueous dispersion with a solid content of 30% by weight.
• a neutralizer morpholine
• the obtained aqueous dispersion was applied to the corona-treated surface of an IPA-wiped PET film (manufactured by Toray, film thickness 100 ⁇ m, dimensions 30 cm x 10 cm) with a Mayer bar to a film thickness of 10 ⁇ m, and the film was left to stand for 24 hours at a temperature of 25°C and a humidity of 50% for aging.
• a 10 cm section 5 cm below the coating start point of the aged coated film was cut out to prepare a 10 cm x 10 cm test piece.
• Example 6 Water Dispersion of Maleic Anhydride-Modified Polyolefin Resin
• a water dispersion operation was carried out in the same manner as in Example 9, except that 100 parts of the polyether-modified polyolefin resin (A-1) prepared in Production Example 1 was used, to obtain an aqueous dispersion having a solid content of 30% by weight. Test pieces were prepared in the same manner as in Example 9 using the obtained aqueous dispersion.
• Example 10 Solid product of polyether modified polyolefin resin A-1
• a 10% toluene solution of polyether-modified polyolefin resin A-10 was prepared, and the resulting toluene solution was applied to the corona-treated surface of an IPA-wiped OPP film (manufactured by Futamura Chemical, film thickness 60 ⁇ m, dimensions 30 cm ⁇ 10 cm) with a Mayer bar to a film thickness of 10 ⁇ m, and then aged for 24 hours in an environment with a temperature of 25° C. and a humidity of 50%. A 10 cm section 5 cm below the coating start point of the aged coated film was cut out to prepare a 10 cm ⁇ 10 cm test piece.
• IPA-wiped OPP film manufactured by Futamura Chemical, film thickness 60 ⁇ m, dimensions 30 cm ⁇ 10 cm
• Test Example 1 Measurement of surface resistivity
• Measurements were performed in accordance with JIS K 6911 using a high resistivity meter "Hi-Resta-UP" (manufactured by Mitsubishi Chemical).
• the 10 cm x 10 cm test pieces prepared in the examples and comparative examples were placed on the Teflon (registered trademark) surface of a register table UFL (manufactured by Mitsubishi Chemical) as a measurement table under conditions of a temperature of 25 ° C. and a humidity of 50%, and a URS probe (manufactured by Mitsubishi Chemical) was used as a probe, and the probe was lightly pressed against the center of the test piece and the measured value after 10 seconds was recorded.
• a register table UFL manufactured by Mitsubishi Chemical
• Table 1 summarizes the components (A) and (B) used in the examples and comparative examples, as well as their weight ratios, and the evaluation and measurement results of the test examples.
• polyether-modified polyolefin resins obtained by grafting (B) polyetheramine onto (A) polyolefin resin graft-modified with ⁇ , ⁇ -unsaturated carboxylic acid and/or its derivative in which the weight ratio of the structure derived from component (A) to the structure derived from component (B) contained in the polyether-modified polyolefin resin (derived from component (A):derived from component (B)) is 70:30 to 30:70, can exhibit good antistatic properties and adhesive properties, regardless of whether they are dissolved or dispersed in a solvent or are solid products.

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