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
  • 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
  • C08F255/04—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 on to ethylene-propylene copolymers
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/002—Priming paints
• • 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
  • 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
  • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
  • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene 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
  • 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
  • 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
  • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface

Definitions

• the present invention relates to a modified polyolefin resin and a dispersion composition. More specifically, the present invention relates to a modified polyolefin resin and a dispersion composition having excellent water adhesion resistance under high temperature conditions.
• Polyolefins such as polypropylene and polyethylene are generally inexpensive and have many excellent properties such as moldability, chemical resistance, water resistance, and electrical properties. Therefore, polyolefins have been widely adopted in recent years as materials for sheets, films, molded articles and the like.
• the polyolefin base material is a non-polar and crystalline base material, unlike polar base materials such as polyurethane resin, polyamide resin, acrylic resin, and polyester resin. Therefore, it is difficult to paint or adhere to the polyolefin substrate.
• a method for improving the above-mentioned problems related to adhesiveness a method has been proposed in which a primer capable of adhering to a polyolefin resin is undercoated on the surface of the base material, and a urethane resin paint or the like is applied on the undercoat layer.
• a primer a modified polyolefin resin to which a polar group (carboxy group, acid anhydride group, etc.) is added is used, and by adding a polar group, not only a polyolefin resin base material but also a urethane resin paint or the like can be used.
• a polar group carboxy group, acid anhydride group, etc.
• Modified polyolefin resins are widely used as primers for resin substrates such as automobile bumpers.
• automobile manufacturers have a policy of replacing the steel plate base material of the body with a resin base material for the purpose of reducing the weight of the vehicle body.
• a primer for a resin base material for a body having a coating film performance equivalent to that of a steel plate coating has become required.
• Adhesives for body coatings especially those for the direct glazing method that directly bond wind glass and body, and adhesives for side window glass and window frames in vehicles require long-term adhesive strength and high temperatures. It is required that the deterioration is small even when exposed to. Therefore, the test is performed under high temperature conditions as compared with the water adhesion resistance of the primer for bumpers. More specifically, in terms of water resistance under high temperature conditions for adhesives such as those for the direct glazing method, first, a urethane-based adhesive is applied on the coating film coated on the resin base material to prepare a test plate. To do. Subsequently, the prepared test plate is immersed in a constant temperature water bath set at 60 ° C.
• the test piece obtained by coating the resin base material is immersed in a constant temperature water tank at 40 ° C. for 10 days, and then the coating film is peeled off and evaluated. Therefore, the modified polyolefin resin used for the conventional primer for bumpers cannot impart sufficient strength and adhesive force to the coating film in the adhesive for the direct glazing method, which has a high test temperature, and the coating film becomes difficult. It may cause coagulation failure. Therefore, it is difficult for a primer using a conventional polyolefin resin to exhibit sufficient physical characteristics of a coating film in terms of water adhesion resistance.
• An object of the present invention is to provide a modified polyolefin resin capable of producing a coating film having excellent water adhesion resistance under high temperature conditions.
• the present inventors have graft-modified a polyolefin resin with ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof so that the tensile elastic modulus and the weight average molecular weight are within a predetermined range.
• a dispersion composition containing the same have found that the above-mentioned problems can be solved, and have completed the present invention. That is, the present inventors provide the following [1] to [10].
• the component (A) contains at least one selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer.
• [4] The modified polyolefin resin according to any one of [1] to [3] above, wherein the graft weight of the component (B) in the modified graft is 0.1 to 10% by weight.
• a coating film having excellent water adhesion resistance under high temperature conditions can be produced.
• AA to BB means AA or more and BB or less.
• the modified polyolefin resin of the present invention contains a component (A): a polyolefin resin (hereinafter, also referred to as “component (A)”) and a component (B): ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof (hereinafter, “” It also contains a graft-modified product graft-modified with (also referred to as “component (B)”).
• component (A) a polyolefin resin
• component (B) ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof
• the modified polyolefin resin has a tensile elastic modulus of 250 MPa or more and a weight average molecular weight (hereinafter, also referred to as “Mw”) of 70,000 or more and less than 200,000.
• the melting point (hereinafter, also referred to as “Tm”) of the modified polyolefin resin by the differential scanning calorimeter (hereinafter, also referred to as “DSC”) is preferably 85 ° C. or higher and lower than 110 ° C.
• the modified polyolefin resin of the present invention can produce a coating film having excellent water adhesion resistance under high temperature conditions.
• the modified polyolefin resin of the present invention has Mw within a predetermined range and a tensile elastic modulus of a predetermined value or more.
• Mw is within a predetermined range
• cohesive force and adhesiveness can be imparted to the coating film, and solvent solubility can be ensured. Therefore, the adhesiveness with the base material can be ensured.
• the tensile elastic modulus is equal to or higher than a predetermined value, sufficient strength can be imparted to the coating film. Therefore, the strength of the coating film can be maintained even under high temperature conditions, and the adhesion to the substrate can be ensured.
• the Mw of the modified polyolefin resin of the present invention is 70,000 or more and less than 200,000, preferably 80,000 or more and less than 150,000.
• Mw is 70,000 or more, the coating film after drying exerts a cohesive force, and can impart coating film strength and adhesiveness.
• it is less than 200,000 sufficient solvent solubility can be ensured.
• good stability can be ensured when the aqueous dispersion is prepared.
• Mw is a value measured and calculated by gel permeation chromatography (standard substance: polystyrene).
• the Tm of the modified polyolefin resin of the present invention is preferably 85 ° C. or higher and lower than 110 ° C., more preferably 90 ° C. or higher and lower than 105 ° C.
• Tm is 85 ° C. or higher, sufficient water resistance under high temperature conditions can be further improved.
• the melting point is less than 110 ° C., good film forming property at the time of baking the coating film can be ensured.
• Tm by DSC is a value measured under the following conditions. According to JIS K7121-1987, a DSC measuring device (manufactured by TA Instruments) is used to heat and melt a sample of about 5 mg at 150 ° C. for 10 minutes.
• the temperature is lowered at a rate of 10 ° C./min and stably maintained at ⁇ 50 ° C. Then, the temperature is raised to 150 ° C. at 10 ° C./min, and the melting peak temperature at the time of melting is evaluated as Tm.
• the tensile elastic modulus of the modified polyolefin resin of the present invention is 250 MPa or more, preferably 300 MPa or more. When the tensile elastic modulus is 250 MPa or more, sufficient strength can be imparted to the coating film.
• the upper limit thereof is not particularly limited, but is usually 8000 MPa or less, preferably 5000 MPa or less, 3000 MPa or less, 1000 MPa or less, more preferably 800 MPa or less, further preferably 600 MPa or less, still more preferably 500 MPa or less.
• the tensile elastic modulus of the modified polyolefin resin is a value measured under the following conditions.
• the aqueous dispersion composition of the modified polyolefin resin is dried to obtain a dried product.
• the obtained dried product is dissolved by heating in an organic solvent, and the obtained solution is applied to a release paper so as to have a film thickness of about 20 ⁇ m. Dry for 5 minutes in a blower dryer set at 100 ° C., and store for 24 hours under constant temperature and humidity conditions of 23 ° C. and 50% relative humidity. Then, the film is cut into a width of 15 mm and a length of 150 mm, and the release paper is peeled off to obtain a test film.
• the tensile elastic modulus of the obtained test film is measured using a tensile tester under the conditions of a tensile speed of 10 mm / min and a distance between chucks of 100 mm.
• the tensile elastic modulus of the modified polyolefin resin is measured under the conditions of a tensile speed of 10 mm / min and a chuck distance of 100 mm using a test film made of the modified polyolefin resin and having a width of 15 mm and a length of 150 mm. It is the value that was set.
• the component (A) is not particularly limited, and may be a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins. Further, when it is a copolymer, it may be a random copolymer or a block copolymer.
• ⁇ -olefin is preferably used as the olefin. Examples of ⁇ -olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
• polypropylene (propylene homopolymer), ethylene-propylene copolymer, propylene-1-, from the viewpoint of exhibiting sufficient adhesion to a non-polar resin base material such as a polypropylene base material.
• Butene copolymers and ethylene-propylene-1-butene copolymers are more preferably used.
• polypropylene represents a polymer whose basic unit is a constituent unit derived from propylene.
• the ethylene-propylene copolymer represents a copolymer whose basic unit is an ethylene-derived structural unit and a propylene-derived structural unit.
• the propylene-1-butene copolymer represents a copolymer whose basic unit is a structural unit derived from propylene and a structural unit derived from 1-butene.
• These polymers may contain a small amount of structural units derived from olefins other than the above basic units. This content may be an amount that does not significantly impair the original performance of the resin.
• Such other olefin-derived structural units may be mixed, for example, in the process up to the production of the modified polyolefin resin.
• the component (A) preferably contains 60 mol% or more of the propylene-derived constituent unit in 100 mol% of the constituent unit.
• the propylene-derived structural unit is included in the above range, the adhesiveness to a base material such as a non-polar resin (for example, propylene resin) or a molded product can be ensured.
• the component (A) is preferable because the polyolefin resin obtained by using a metallocene catalyst as a polymerization catalyst has the following characteristics.
• the component (A) obtained by using a metallocene catalyst has a narrow molecular weight distribution. Further, when the component (A) is a copolymer, it is excellent in random copolymerizability, has a narrow composition distribution, and has a wide range of copolymerizable comonomer.
• the metallocene catalyst a known one can be used.
• the metallocene catalyst is preferably obtained by combining the components (1) and (2) described below with, if necessary, (3).
• -Component (1) a metallocene complex which is a transition metal compound of Groups 4 to 6 of the Periodic Table having at least one conjugated five-membered ring ligand; -Component (2); Ion-exchangeable layered silicate; -Component (3); organoaluminum compound.
• the ethylene-derived constituent unit or the butene-derived constituent unit is contained in a proportion of 5 to 50 mol% in 100 mol% of the constituent units.
• Propylene-derived constituent units are preferably contained in a proportion of 50 to 95 mol%.
• the tensile elastic modulus of the component (A) is preferably 150 MPa or more, more preferably 250 MPa or more.
• the upper limit is usually 8000 MPa or less, preferably 5000 MPa or less, 3000 MPa or less, 1000 MPa or less, more preferably 800 MPa or less, still more preferably 600 MPa or less.
• the tensile elastic modulus of the component (A) can be measured in the same manner as the tensile elastic modulus of the modified polyolefin resin.
• the melting point of the component (A) is preferably 80 ° C. or higher and lower than 110 ° C., more preferably 85 ° C. or higher and 105 ° C. Thereby, a modified polyolefin resin having a melting point in the above range can be easily obtained.
• the weight average molecular weight of the component (A) is 70,000 or more and less than 500,000, preferably 80,000 or more and less than 400,000.
• the component (A) may be used alone or in combination of two or more. When two or more types are used in combination, the ratio is not particularly limited.
• Component (B): ⁇ , ⁇ -unsaturated carboxylic acid or its derivative The component (B) is an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof.
• ⁇ , ⁇ -unsaturated carboxylic acid and its derivatives include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, and aconitic anhydride.
• Examples include maleic anhydride, (meth) acrylic acid, and (meth) acrylic acid ester. Of these, maleic anhydride is preferred.
• the component (B) may be at least one compound selected from the group consisting of ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof, and may be one or more ⁇ , ⁇ -unsaturated carboxylic acids and one or more kinds. It may be a combination of derivatives of ⁇ , ⁇ -unsaturated carboxylic acid, a combination of two or more kinds of ⁇ , ⁇ -unsaturated carboxylic acid, and a combination of two or more kinds of derivatives of ⁇ , ⁇ -unsaturated carboxylic acid.
• the graft weight of the component (B) in the modified graft is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on 100% by weight of the modified graft.
• the graft weight of the component (B) is a value determined by an alkaline titration method.
• the graft-modified product can be prepared by graft-modifying (graft polymerization) the component (B) with the component (A).
• the graft modification can be carried out by a known method, and a component (C): radical generator (hereinafter, also referred to as “component (C)”) may be used.
• component (C): radical generator hereinafter, also referred to as “component (C)”
• graft modification for example, a solution method in which a mixture of the component (A) and the component (B) is heated and dissolved in an organic solvent such as toluene and the component (C) is added, or a Banbury mixer, kneader, extruder, etc.
• a method of adding the component (A), the component (B) and the component (C) using a kneader and obtaining a graft modified product by a melt-kneading reaction under heating can be mentioned.
• the component (A), the component (B) and the component (C) may be added all at once or sequentially.
• the component (C) can be appropriately selected from known radical generators, and an organic peroxide compound is preferable.
• organic peroxide compound examples include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroper.
• the component (C) may be a single radical generator or a combination of a plurality of types of radical generators.
• the amount of the component (C) added in the graft polymerization reaction is preferably 1 to 100% by weight, more preferably 10 to 50% by weight, based on the amount (weight) of the component (B) added. When it is 1% by weight or more, sufficient graft efficiency can be ensured. When it is 100% by weight or less, a decrease in the weight average molecular weight of the graft modified product can be prevented.
• the modified polyolefin resin may contain at least one graft-modified product (for example, two or more graft-modified products having different types and compositions of the components (A) and / or (B)). May include a combination of.
• the graft-modified product is a component other than the graft-modified product, for example, a component other than the graft-modified product generated during graft modification (for example, a polymer of unreacted components (A), (B), and components (B)). Further may be included.
• the modified polyolefin resin of the present invention may be used as it is (for example, in a solid state such as pellets), but it is preferably added to a dispersion medium (solvent) and used as a dispersion.
• a dispersion medium solvent
• the dispersion composition of the present invention contains a modified polyolefin resin.
• the dispersion composition of the present invention may contain other components, if necessary.
• the dispersion composition is preferably used as a film-forming composition for primers, paints, inks, adhesives and the like.
• the dispersion composition usually contains a modified polyolefin resin and a dispersion medium, and may further contain other resin components.
• resin components include urethane resins, epoxy resins, acrylic resins, phenol resins, alkyd resins, polyamide resins, polyimide resins, silicone resins, resins such as vitrified cotton, and combinations of two or more of these. These resins may be blended with the modified polyolefin or a dispersion thereof as an aqueous product (for example, an aqueous acrylic resin or an aqueous polyurethane resin).
• the dispersion composition may contain, for example, an aqueous acrylic resin, an aqueous urethane resin, lower alcohols, lower ketones, lower esters, preservatives, leveling agents, antioxidants, and photostabilizing agents.
• Additive components such as agents, ultraviolet absorbers, dyes, pigments, metal salts, and acids may be blended.
• the dispersion medium may be non-aqueous or aqueous (hereinafter, the dispersion composition containing the aqueous dispersion medium is also referred to as “aqueous dispersion composition”).
• the non-aqueous dispersion medium include organic solvents such as xylene, toluene, and benzene.
• the aqueous dispersion medium is usually water, but an alcohol solvent, a glycol solvent, a ketone solvent, and an ester solvent may be used in combination.
• a cross-linking agent may be contained as another component.
• crosslinking agent refers to a compound that reacts with a group such as a hydroxyl group, a carboxy group, or an amino group present in a component such as a modified polyolefin resin, a surfactant, or a neutralizing agent to form a crosslinked structure.
• examples of the cross-linking agent include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins.
• the method of adding the cross-linking agent is not particularly limited. For example, it may be added during the waterification step or after the waterification.
• Nonionic surfactants are preferably used because the resulting aqueous dispersion composition has better water resistance.
• Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, and polyoxyethylene sorbitan.
• examples thereof include fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth) acrylates.
• polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable.
• alkyl sulfate ester salts polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, ⁇ -olefin sulfonates, methyl taurylate salts, sulfosuccinates, ether sulfonates, ether carboxylate salts, etc.
• examples thereof include fatty acid salts, naphthalene sulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines and alkylamine oxides.
• polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.
• the surfactant When a surfactant is used in preparing the aqueous dispersion composition, it is preferable that the surfactant is added in as little amount as possible or not added. The reason for this is that the addition of a surfactant may reduce the film performance when forming a film, or may cause a plasticizing effect or bleeding phenomenon when a dry film is formed, resulting in blocking. Because.
• the aqueous dispersion composition may further contain a neutralizing agent.
• a neutralizing agent examples include ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, isobutylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, and N.
• the boiling point of the neutralizer at normal pressure is preferably 200 ° C or lower. If the boiling point is more than 200 ° C., for example, when the aqueous dispersion composition is used as a coating film, it may be difficult to remove the neutralizing agent by the drying treatment in the water removing step. Therefore, the water resistance and moisture resistance of the coating film, especially during low-temperature drying, may deteriorate, or the adhesiveness to a base material such as a non-polar resin molded product may deteriorate.
• the neutralizing agent may be used alone or in combination of two or more.
• the compounding ratio of each compound is not particularly limited.
• the content of the neutralizing agent in the aqueous dispersion composition is not particularly specified, but it is preferably 3.0 times or less the amount of the carboxyl group in the graft modified product. Thereby, an excessive increase in pH of the aqueous dispersion composition can be suppressed.
• the lower limit is preferably 0.5 times or more. Thereby, an excessive decrease in pH of the aqueous dispersion composition can be suppressed.
• the pH of the aqueous dispersion composition is preferably 5 or more, more preferably pH 6 to 11. If the pH is less than 5, neutralization may be insufficient and the modified polyolefin resin may not be dispersed in water. Further, even when dispersed, precipitation and separation are likely to occur over time, and storage stability may be inferior. On the other hand, if the pH exceeds 11, problems may occur in compatibility with other components and work safety.
• the pH can be adjusted by the amount of neutralizing agent added when preparing the aqueous dispersion composition.
• the average particle size of the resin emulsified and dispersed in water is preferably 300 nm or less, more preferably 200 nm or less. If it exceeds 300 nm, the storage stability of the aqueous dispersion composition and the compatibility with other resins may deteriorate. In addition, the physical characteristics of the film such as adhesion to the substrate, solvent resistance, water resistance, and blocking resistance when the film is formed may be deteriorated.
• the average particle size can be adjusted according to conditions such as the composition of the modified polyolefin resin, the amount of the dispersion medium, the amount of the emulsifier added, the type, and the stirring power at the time of dispersion. In the present specification, the average particle size is a value obtained by measuring the particle size distribution using the light diffusion method.
• the particle size can be made as small as possible.
• the physical characteristics of the film such as adhesion to the substrate, water resistance, and gas hole resistance tend to decrease.
• the Tm of the dispersion composition is preferably 85 ° C. or higher and lower than 110 ° C., or 90 ° C. or higher and lower than 110 ° C., and more preferably 90 ° C. or higher and lower than 105 ° C.
• Tm 85 ° C. or higher
• the melting point is less than 110 ° C.
• good film forming property at the time of baking the coating film can be ensured.
• the Tm of the dispersion composition is a dried product obtained by drying the dispersion composition at 40 ° C. for 24 hours, and using DSC (manufactured by TA Instruments) in the same manner as the Tm of the modified polyolefin resin described above. Can be measured using.
• the dispersion composition of the present invention can function as an intermediate medium for a base material having low adhesiveness and difficult to apply such as a paint, for example, a non-polar resin molded product.
• a paint for example, a non-polar resin molded product.
• it is also useful as an adhesive between polyolefin-based substrates such as polypropylene and polyethylene, which have poor adhesiveness, regardless of whether or not there is a surface treatment such as plasma treatment or corona treatment on the surface of the substrate such as a non-polar resin molded product. Can be used without.
• the adhesion stability of the paint and the like can be obtained. Can be improved. Further, it is also suitable for polar substrates such as polyester such as polyethylene terephthalate, polyurethane and polyamide.
• the dispersion composition of the present invention can be suitably used as a primer, a paint, an ink, an adhesive and the like.
• the method for producing the dispersion composition is not particularly limited.
• a method including at least a dispersion step of adding a modified polyolefin resin to a dispersion medium and dispersing the modified polyolefin resin can be mentioned.
• the dispersion composition is an aqueous dispersion composition, even if the modified polyolefin resin is added to the organic solvent and dissolved (preferably under heating conditions) before the dispersion step, the organic solvent is distilled off. Good.
• a neutralizing agent it is preferable to add the neutralizing agent when it is dissolved in an organic solvent.
• the dispersion composition contains other resin components, it is preferable that the resin components are blended after the above dispersion step.
• a resin component blending step may be performed in which the resin component is blended and the solid content is adjusted as necessary (for example, a dispersion medium is added and diluted).
• the present invention will be described in detail by way of examples.
• the following examples are for the purpose of preferably explaining the present invention, and do not limit the present invention.
• the measurement method for the physical property value or the like is the measurement method described above.
• the "part" is a weight part unless otherwise specified.
• Tm melting point, ° C.
• [Tensile modulus] The aqueous dispersion composition was dried at 40 ° C. for 24 hours, and the obtained dried product was dissolved in an organic solvent to obtain a solution. The obtained solution was applied to a release paper so as to have a film thickness of about 20 ⁇ m, dried in a blower dryer set at 100 ° C. for 5 minutes, and under constant temperature and humidity conditions of 23 ° C. and 50% relative humidity 24. The coating film was prepared by storing for a long time. A test film was obtained by cutting the coating film into a width of 15 mm and a length of 150 mm and peeling off the release paper.
• the tensile elastic modulus of the obtained test film was measured using a tensile tester (Tensilon universal material tester: manufactured by A & D Co., Ltd.) under the conditions of a tensile speed of 10 mm / min and a distance between chucks of 100 mm.
• Average particle size (nm) It was measured with a particle size distribution measuring device (manufactured by Malvern Instruments).
• Example 1 In a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel, propylene-1-butene copolymer (I) (propylene component 80 mol%, 1-butene component 20 mol%, Mw 100, 000, Tm is 85 ° C., tensile elasticity is 160 MPa) and propylene-1-butene copolymer (II) (propylene component is 90 mol%, 1-butene component is 10 mol%, Mw is 100,000, Tm is (100 ° C., tensile elasticity of 360 MPa) was heated and dissolved in 400 g of toluene so as to have a total of 100 parts at a weight ratio of 50:50.
• propylene-1-butene copolymer (I) propylene component 80 mol%, 1-butene component 20 mol%, Mw 100, 000, Tm is 85 ° C., tensile elasticity is 160 MPa
• aqueous dispersion composition (1) containing the modified polyolefin resin (1) was obtained.
• the Tm of the dried product of the aqueous dispersion composition (1) was 91 ° C.
• Example 2 100 parts of propylene-1-butene copolymer (III) (90 mol% propylene component, 10 mol% 1-butene component, 400,000 Mw, 100 ° C. Tm, 360 MPa tensile modulus), maleic anhydride 3.0 parts of acid and 2.0 parts of dilauryl peroxide were kneaded and reacted using a twin-screw extruder set at 200 ° C. Deaeration under reduced pressure was performed in the extruder to remove residual unreactant, and a modified polyolefin resin (2) having a Mw of 80,000, a Tm of 100 ° C., and a maleic anhydride graft weight of 3.0% by weight was used.
• a modified polyolefin resin (2) having a Mw of 80,000, a Tm of 100 ° C., and a maleic anhydride graft weight of 3.0% by weight was used.
• the obtained modified polyolefin resin (2) was used to prepare an aqueous dispersion composition (2) in the same manner as in Example 1 except that the amount of DMEA added in Example 1 was 7 g.
• the Tm of the dried product of the aqueous dispersion composition (2) was 94 ° C.
• Example 3 A modified polyolefin resin (3) was obtained by modification in the same manner as in Example 2 except that the reaction temperature by the twin-screw extruder of Example 2 was set to 180 ° C.
• the obtained modified polyolefin resin (3) had a Mw of 100,000, a Tm of 100 ° C., and a graft weight of maleic anhydride of 3.0% by weight.
• the aqueous dispersion composition was also prepared in the same manner as in Example 2. The Tm of the dried product of the aqueous dispersion composition (3) was 95 ° C.
• the obtained modified polyolefin resin (5) had an Mw of 60,000, a Tm of 90 ° C., and a graft weight of maleic anhydride of 3.0% by weight.
• the aqueous dispersion composition was prepared in the same manner as in Example 1 except that the amount of DMEA added in Example 1 was 7 g.
• the Tm of the dried product of the aqueous dispersion composition (5) was 89 ° C.
• the resin base material for the body was coated with an aqueous primer paint adjusted to have a dry film thickness of about 25 ⁇ m by an air spray gun, allowed to stand for 5 minutes, and then preheated at 60 ° C. for 3 minutes.
• the aqueous metallic color base coat paint was applied so that the dry film thickness was about 20 ⁇ m, allowed to stand for 5 minutes, and then preheated at 80 ° C. for 3 minutes.
• an acrylic urethane solvent type clear paint was applied so that the dry film thickness was about 35 ⁇ m, allowed to stand for 7 minutes, and then baked at 120 ° C. for 20 minutes to prepare an object to be coated.
• a urethane adhesive (trade name "3740", manufactured by Sunstar Co., Ltd., a windshield agent for automobiles) is applied to the produced object to be coated so that the coating shape is 20 mm in width, 3 mm in thickness, and 100 mm or more in length.
• a release paper After covering with a release paper, it was pressed evenly with a flat plate. After removing the flat plate, it was allowed to stand for 72 hours under a constant temperature and humidity condition of 23 ° C. and a relative humidity of 50% to cure. Then, the release paper was peeled off to prepare a test plate.
• Diameter (Large) 1-10 (Small) Frequency: None, (low) F, M, MD, D (high) The diameter is the size of the blister, and the numerical value that can be visually confirmed is up to 8. Further, the frequency is the number of blisters, and is an abbreviation for F (Few), M (Medium), MD (Medium Dense), and D (Dense).
• the aqueous dispersion composition of Comparative Example 2 has a blister of 2 M (diameter evaluation is 2 and frequency evaluation is M), and the number of remaining cells is 0, so that the water dispersion resistance under high temperature conditions is high. I know there isn't. Further, from the results of the water resistance test under high temperature conditions, the aqueous dispersion compositions of Examples 1 to 3 are all evaluated as "A" or "B" and can be used for direct glazing method applications and the like. It is a thing.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=74684215

Family Applications (1)

Country Status (6)

Cited By (3)

Citations (4)

Family Cites Families (7)

• 2020
  • 2020-08-24 WO PCT/JP2020/031862 patent/WO2021039729A1/ja not_active Ceased
  • 2020-08-24 US US17/638,050 patent/US12071499B2/en active Active
  • 2020-08-24 JP JP2021542897A patent/JP7536021B2/ja active Active
  • 2020-08-24 CA CA3152676A patent/CA3152676A1/en active Pending
  • 2020-08-24 EP EP20857697.5A patent/EP4023683A4/en active Pending
  • 2020-08-24 CN CN202080060844.9A patent/CN114269801B/zh active Active

Patent Citations (4)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events