WO2015079918A1 - Aqueous dispersion composition containing modified polyolefin - Google Patents
Aqueous dispersion composition containing modified polyolefin Download PDFInfo
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- WO2015079918A1 WO2015079918A1 PCT/JP2014/080012 JP2014080012W WO2015079918A1 WO 2015079918 A1 WO2015079918 A1 WO 2015079918A1 JP 2014080012 W JP2014080012 W JP 2014080012W WO 2015079918 A1 WO2015079918 A1 WO 2015079918A1
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- 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
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- 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
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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 ethene-propene copolymers
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- 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
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- 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
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- 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
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- 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
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- 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
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/027—Dispersing agents
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
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- 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
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- 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
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- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
Definitions
- the present invention relates to an aqueous dispersion composition containing a modified polyolefin. More specifically, an aqueous dispersion containing a modified polyolefin and a basic substance suitable for use in paints, inks, sealants, primers or adhesives, and further containing at least one of an anionic group-containing water-soluble polymer and an electrolyte Relates to the composition.
- Polyolefin resins such as polypropylene are excellent in properties and inexpensive, and are therefore used in large quantities in automobile parts, various films, various molded products, and the like.
- the polyolefin-based resin has a problem that it is difficult to paint and adhere because it is crystalline and the surface is nonpolar.
- modified polyolefins such as acid-modified polyolefins and acid-modified chlorinated polyolefins have been developed for painting, printing, and laminating and adhering polyolefin resins.
- Dispersion compositions have been proposed (for example, Patent Documents 1 and 2).
- This aqueous dispersion composition of modified polyolefin does not substantially use an emulsifier, so there is no occurrence of unevenness of the coating film, and the coating film has physical properties such as gasohol resistance, water resistance, and blocking resistance. It is an excellent method because it is good.
- the viscosity of the aqueous dispersion composition may not be stable.
- the viscosity is unstable, there is a problem that handling during production becomes poor and production efficiency is lowered.
- additives such as various viscosity modifiers are blended in addition to the modified polyolefin-containing aqueous dispersion composition.
- the present invention has been made in view of the above problems, and as a result of intensive studies, the present inventors have found that an aqueous dispersion composition containing a modified polyolefin has an anionic group-containing water-soluble polymer and / or electrolyte. It has been found that the aqueous dispersion composition can be stabilized at a low viscosity by containing the water, and the present invention has been completed.
- An aqueous dispersion composition containing at least one of an anionic group-containing water-soluble polymer (C) having an acid value of 150 to 500 mgKOH / g-resin and an electrolyte (D)
- An aqueous dispersion composition An aqueous dispersion composition.
- the modified polyolefin (A) is preferably acid-modified polyolefin (A1) and / or acid-modified chlorinated polyolefin (A2).
- the aqueous dispersion composition contains 0.5 to 10 parts by mass of the basic substance (B) with respect to 100 parts by mass of the modified polyolefin (A), and contains an anionic group-containing water-soluble polymer (C) and an electrolyte. It is preferable to contain 0.1 to 20 parts by mass of the total amount of (D).
- a paint, ink, sealant, primer or adhesive containing the aqueous dispersion composition A paint, ink, sealant, primer or adhesive containing the aqueous dispersion composition.
- the aqueous dispersion composition according to the present invention contains an anionic group-containing water-soluble polymer and / or electrolyte, the viscosity when the modified polyolefin solid content in the aqueous dispersion composition is 30% by mass is 500 mPa ⁇ s. It can be made constant in the following range. Furthermore, since an emulsifier is not substantially used, the coating film produced using the aqueous dispersion composition has no unevenness and has good adhesion and water resistance.
- the modified polyolefin (A) used in the present invention is not particularly limited, but is preferably acid-modified polyolefin (A1) and / or acid-modified chlorinated polyolefin (A2).
- the acid-modified polyolefin (A1) used in the present invention is not limited, but at least one of polyethylene, polypropylene and propylene- ⁇ -olefin copolymer includes at least ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride. What is obtained by grafting 1 type is preferable.
- the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
- ⁇ -olefin for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate or the like can be used. Of these ⁇ -olefins, ethylene and 1-butene are preferred.
- the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
- Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
- acid anhydrides are preferable, and maleic anhydride is more preferable.
- Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like.
- These acid-modified polyolefins can be used alone or in combination of two or more.
- the method for producing the acid-modified polyolefin (A1) is not particularly limited, and for example, radical graft reaction (that is, a radical species is generated for a polymer to be a main chain, and the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride).
- radical graft reaction that is, a radical species is generated for a polymer to be a main chain, and the unsaturated carboxylic acid and Reaction for graft polymerization of an acid anhydride).
- organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.
- the acid-modified chlorinated polyolefin (A2) used in the present invention is not limited, but is preferably obtained by chlorinating the acid-modified polyolefin (A1).
- the production method of the acid-modified chlorinated polyolefin (A2) is not particularly limited, and can be obtained, for example, by dissolving the acid-modified polyolefin (A1) in a halogenated hydrocarbon such as chloroform and introducing chlorine.
- the acid-modified amount of the modified polyolefin (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more. 1% by mass or more is most preferable. Moreover, 10 mass% or less is preferable, 8 mass% or less is more preferable, 7 mass% or less is more preferable, 6 mass% or less is especially preferable, and 5 mass% or less is the most preferable. If the amount is too small, it may be difficult to disperse sufficiently. If the amount is too large, the water resistance of the coating film may be adversely affected.
- the amount of acid modification when acid-modified with maleic anhydride can be determined by FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC).
- FT-IR manufactured by Shimadzu Corporation, FT-IR8200PC.
- a calibration curve solution is prepared by dissolving maleic anhydride at an arbitrary concentration.
- the calibration curve solution is subjected to FT-IR measurement, and a calibration curve is prepared from the absorbance of the stretching peak (1780 cm ⁇ 1 ) of the carbonyl (C ⁇ O) bond of maleic anhydride.
- the modified polyolefin (A) was dissolved in chloroform and subjected to FT-IR measurement. Based on the calibration curve, the acid-modified amount of maleic anhydride was determined from the absorbance of the stretching peak (1780 cm ⁇ 1 ) of the carbonyl bond of maleic anhydride.
- the weight average molecular weight (Mw) of the modified polyolefin (A) is preferably in the range of 40,000 to 170,000. More preferably, it is in the range of 50,000 to 160,000, more preferably in the range of 60,000 to 150,000, particularly preferably in the range of 70,000 to 140,000, and most preferably 80. , 13,000 to 130,000. If it is too small, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when too large, solubility may fall and a problem may arise in preparation of an aqueous dispersion composition.
- the weight average molecular weight in the present invention is a value measured under an atmosphere of 40 ° C. by gel permeation chromatography (hereinafter also referred to as GPC. Standard substance: polystyrene resin, mobile phase: tetrahydrofuran).
- the modified polyolefin (A) is preferably crystalline.
- the crystallinity is advantageous because it has higher cohesion than amorphous and has excellent adhesion, water resistance, heat resistance, and chemical resistance.
- the crystallinity referred to in the present invention means a differential scanning calorimeter (hereinafter also referred to as DSC, manufactured by TA Instruments Japan, Q-2000) at a temperature of 10 ° C./100° C. to 250 ° C. min.
- the temperature is raised at a temperature of 1 and a clear melting peak is indicated in the temperature raising process.
- the melting point and the heat of fusion were measured at 10 ° C./min.
- DSC It is a value measured from the top temperature and the area of the melting peak when the temperature is melted at a rate of temperature, the resin is cooled, and the temperature is melted again.
- the melting point (Tm) of the modified polyolefin (A) is preferably in the range of 50 ° C to 120 ° C. More preferably, it is in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If it is less than the above value, the cohesive force derived from the crystal becomes weak, and the adhesiveness, water resistance, heat resistance, and chemical resistance may be inferior. On the other hand, when the above value is exceeded, the solubility may be lowered and a problem may occur in the production of the aqueous dispersion composition.
- the chlorine content of the acid-modified chlorinated polyolefin (A2) depends on the solution stability and the polyolefin substrate and the resin substrate or metal substrate.
- the lower limit is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, particularly preferably 12% by mass or more, and most preferably. Is 14% by mass or more. If it is less than the above value, the solution stability may be lowered and emulsification may not be possible.
- the upper limit is preferably 40% by mass or less, more preferably 38% by mass or less, still more preferably 35% by mass or less, particularly preferably 32% by mass or less, and most preferably 30% by mass or less. is there.
- the crystallinity of the acid-modified chlorinated polyolefin may decrease, and the adhesive strength may decrease.
- the chlorine content of the acid-modified chlorinated polyolefin (A2) can be measured by titration according to JIS K-7229-1995.
- the basic substance (B) used in the present invention can neutralize the acidic group (carboxyl group) of the modified polyolefin (A) and improve the dispersibility of the modified polyolefin (A).
- the basic substance (B) is not particularly limited, but a volatile basic substance is preferable, and among them, ammonia and amines are preferable.
- the amines are not particularly limited, but monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine , N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, and the like are particularly preferable. Triethylamine, N, N-dimethylethanolamine. These volatile amines can be used alone or in combination of two or more.
- the basic substance (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 2 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). Is more preferable, and 3 parts by mass or more is particularly preferable. Further, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, still more preferably 8 parts by mass or less, and particularly preferably 7 parts by mass or less. If the amount is too small, the particle size of the dispersed particles of the resulting aqueous dispersion composition is large, and the storage stability may be lowered. If the amount is too large, the water resistance of the coating film may be lowered.
- the anionic group-containing water-soluble polymer (C) used in the present invention can reduce the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition. Thereby, the viscosity when the modified polyolefin solid content in the aqueous dispersion composition is 30% by mass can be made constant within a range of 500 mPa ⁇ s or less.
- Viscosity modifiers exhibit the desired viscosity by hydration and association between polar groups in the paint, but when low-molecular compounds such as electrolytes are used as charge reducing agents, these hydration and association between polar groups In order to inhibit this, the viscosity modifier may not function.
- the anionic group-containing water-soluble polymer (C) is a polymer compound, the flow in the paint is suppressed, the interaction with the viscosity modifier is small, and the effect of the viscosity modifier is not affected. Conceivable. That is, when preparing paints, inks, sealants, primers, adhesives, etc., it is necessary to mix various additives such as viscosity modifiers in addition to the aqueous dispersion composition to prevent dripping during coating. There is.
- the anionic group-containing water-soluble polymer (C) does not hinder the effects of viscosity modifiers, so there is no dripping during coating, and good paints, inks, sealants, primers and adhesion An agent or the like can be obtained.
- the anionic group-containing water-soluble polymer (C) refers to a polymer compound that dissolves in water and reduces the charge on the particle surface of the modified polyolefin (A).
- Specific examples include, but are not limited to, an acrylic resin, a urethane resin, an epoxy resin, and the like containing a carboxyl group, a sulfonic acid group, a sulfate ester group, and a phosphate ester group, and more specifically, polystyrene sulfonic acid.
- anionic group-containing water-soluble polymer mainly composed of polyacrylic acid, styrene-maleic anhydride copolymer, styrene-acrylic monomer copolymer, styrene-methacrylic monomer copolymer, and the like.
- anionic group-containing water-soluble polymers (C) can be used alone or in combination of two or more.
- the acid value of the anionic group-containing water-soluble polymer (C) needs to be 150 mgKOH / g-resin or more, preferably 160 mgKOH / g-resin or more, more preferably 170 mgKOH / g-resin or more. More preferably, it is 180 mgKOH / g-resin or more, particularly preferably 190 mgKOH / g-resin or more, and most preferably 200 mgKOH / g-resin or more. If it is too low, the effect of lowering the viscosity of the aqueous dispersion composition may be reduced.
- 500 mgKOH / g-resin or less preferably 490 mgKOH / g-resin or less, more preferably 480 mgKOH / g-resin or less, further preferably 470 mgKOH / g-resin or less, particularly Preferably it is 460 mgKOH / g-resin or less, most preferably 450 mgKOH / g-resin or less. If it is too high, the water resistance of the coating film may be lowered, and the effect of the viscosity modifier during coating may be impaired.
- the acid value of the anionic group-containing water-soluble polymer (C) can be measured according to JIS K-0070-1992.
- the weight average molecular weight (Mw) of the anionic group-containing water-soluble polymer (C) is preferably 1,500 or more, more preferably 2,000 or more, more preferably 3,000 or more, More preferably, it is 5,000 or more, Especially preferably, it is 7,000 or more, Most preferably, it is 9,000 or more.
- Mw weight average molecular weight
- it is preferably 30,000 or less, more preferably 29,000 or less, more preferably 28,000 or less, further preferably 27,000 or less, and particularly preferably 26,000 or less. Yes, most preferably 25,000 or less.
- the solubility to water may fall and the effect of a viscosity fall may become small.
- the weight average molecular weight of the anionic group-containing water-soluble polymer (C) is a value measured by GPC under an atmosphere of 40 ° C.
- the solubility of the anionic group-containing water-soluble polymer (C) in water (20 ° C.) is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. Is more preferable, and more preferably 30% by mass or more. Although an upper limit is not specifically limited, Practically, it is 50 mass% or less.
- the anionic group-containing water-soluble polymer (C) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the modified polyolefin (A).
- the amount is more preferably 5 parts by mass or more, and particularly preferably 2 parts by mass or more. Further, it is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 17 parts by mass or less. If the amount is too small, the effect of decreasing the viscosity may be reduced. If the amount is too large, the water resistance of the coating film may be decreased, and the effect of the viscosity modifier at the time of coating may be impaired.
- the electrolyte (D) used in the present invention is one that dissolves in water and ionizes cations and anions to show conductivity.
- the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition can be reduced, whereby the solid content of the modified polyolefin in the aqueous dispersion composition is 30% by mass.
- the viscosity can be made constant in the range of 500 mPa ⁇ s or less.
- the electrolyte (D) is not particularly limited.
- citric acid isocitric acid, malic acid, leucine acid, mevalonic acid, pytoic acid, ricinoleic acid, ricineramic acid, cerebric acid, quinic acid, shikimic acid, lactic acid, tartaric acid, Aliphatic hydroxy acids such as citramalic acid, hydroxybutyric acid, glycolic acid, tartronic acid, glyceric acid; salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orthoric acid, gallic acid , Aromatic acids such as mandelic acid, benzic acid, atrolactic acid, mellilotic acid, furoletic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, sinapinic acid; lithium chloride, sodium chloride, potassium chloride, magnesium chloride, Calcium chloride, sodium bromide,
- the electrolyte (D) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 1.5 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A). Is more preferable and 2 parts by mass or more is particularly preferable. Further, it is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 17 parts by mass or less. If the amount is too small, the effect of decreasing the viscosity may be small, and if it is too large, the water resistance of the coating film may be decreased.
- the total amount of the anionic group-containing water-soluble polymer (C) and the electrolyte (D) is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the modified polyolefin (A), and is 1 part by mass or more. More preferably, it is more preferably 1.5 parts by mass or more, and particularly preferably 2 parts by mass or more. Further, it is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 17 parts by mass or less. If the amount is too small, the effect of decreasing the viscosity may be reduced. If the amount is too large, the water resistance of the coating film may be decreased, and the effect of the viscosity modifier at the time of coating may be impaired.
- the aqueous dispersion composition of the present invention contains the modified polyolefin (A) and the basic substance (B), and further contains at least one of an anionic group-containing water-soluble polymer (C) and an electrolyte (D). It is a mixture.
- the aqueous dispersion composition has a viscosity at 25 ° C. of 500 mPa ⁇ s or less measured using a Brookfield viscometer (rotor rotation speed: 60 rpm) when the solid content of the modified polyolefin (A) is 30% by mass.
- a Brookfield viscometer rotor rotation speed: 60 rpm
- it is 400 mPa ⁇ s or less, further preferably 300 mPa ⁇ sPa ⁇ s or less, and particularly preferably 200 mPa ⁇ s or less. If it is too large, the operability and the like during production of the aqueous dispersion composition and preparation of the paint may be poor. Further, the lower the viscosity is, the better the handling property is, so there is no particular lower limit, but practically it is 5 mPa ⁇ s or more.
- the solid content concentration of the modified polyolefin (A) in the aqueous dispersion composition according to the present invention is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, still more preferably 15 to 40% by mass, Most preferably, it is in the range of 20 to 35% by mass. If the solid content concentration of the modified polyolefin (A) is too high, the viscosity becomes high and aggregation between the modified polyolefin particles tends to occur, so that the dispersion stability may be significantly lowered. On the other hand, if it is too low, it is difficult to say that it is practical in terms of both production and application.
- the particle size of the modified polyolefin (A) contained in the aqueous dispersion composition is preferably 5 to 500 nm, more preferably 10 to 400 nm, and even more preferably 15 to 300 nm. If the particle size is too small, the film formability tends to be improved. For this reason, fusion and aggregation between the dispersed particles are likely to occur, and as a result, the dispersion stability is lowered, which is not preferable. On the other hand, if it is too large, not only the dispersion stability is greatly lowered but also the film formability is lowered, so that the appearance and performance of the resulting film may be deteriorated.
- the particle size of the modified polyolefin (A) contained in the aqueous dispersion composition can be measured using a laser diffraction / scattering particle size distribution analyzer (Zetasizer Nano manufactured by Malvern).
- the coating film produced using the aqueous dispersion composition has no unevenness and has good adhesion and water resistance. is there.
- the fact that it does not substantially contain an emulsifier is preferably 0.5 parts by mass or less, and 0.2 parts by mass or less with respect to 100 parts by mass of the modified polyolefin (A). Is more preferable, 0.1 part by mass or less is further preferable, and 0 part by mass is particularly preferable.
- the total amount of the modified polyolefin (A), basic substance (B), anionic group-containing water-soluble polymer (C), electrolyte (D) and water in the aqueous dispersion composition is 99.85% by mass or more. It is preferable that it is 99.94 mass% or more, it is more preferable that it is 99.97 mass% or more, and it is especially preferable that it is 100 mass%.
- the emulsifier examples include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier.
- surfactants are also included.
- anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates.
- Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide.
- Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters
- amphoteric emulsifiers lauryl betaine, lauryl dimethyl amine oxide, and the like.
- the modified polyolefin (A) is heated and dissolved in one or more solvents selected from the group consisting of ether solvents, alcohol solvents and aromatic solvents, and water, after adding a basic substance and cooling. It can be obtained by removing these solvents.
- the formulation of the anionic group-containing water-soluble polymer (C) and / or the electrolyte (D) is not particularly limited, but can be arbitrarily selected during emulsification, before solvent concentration, after solvent concentration, and the like.
- Tetrahydrofuran (henceforth THF), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc. are mentioned, These are single 1 type or 2 types. A combination of the above can be used. Of these, tetrahydrofuran is preferred.
- the alcohol solvent is not particularly limited, and examples thereof include aliphatic alcohols having 1 to 7 carbon atoms, aromatic alcohols, and alicyclic alcohols. These may be used alone or in combination of two or more. it can. Among these, aliphatic alcohols having 3 to 5 carbon atoms are preferable, and isopropyl alcohol (hereinafter also referred to as IPA) is more preferable.
- aromatic solvent examples include benzene, toluene, xylene, ethylbenzene, isopropylbenzene, solvent naphtha and the like, and these can be used alone or in combination of two or more. Of these, toluene is preferable.
- A modified polyolefin
- solvent 100: 50 to 800: 11 to 900 (mass ratio)
- the modified polyolefin is more easily dispersed in water.
- the amount of the solvent is small, the viscosity is remarkably increased at the time of dissolution by heating, so that uniform dissolution cannot be achieved and eventually uniform dispersion may not be possible.
- the temperature at the time of melting by heating is not particularly limited, but is preferably 50 ° C. or higher. Moreover, if it is 75 degrees C or less, it is below the boiling point of the organic solvent to be used, and a pressure vessel is unnecessary for melt
- the dissolution time is not particularly limited, but can be completely dissolved usually in 1 to 2 hours.
- the aqueous dispersion composition according to the present invention includes the modified polyolefin (A), the basic substance (B), and the anionic group-containing water-soluble polymer (C) as long as the performance of the present invention is not impaired as necessary.
- various additives can be blended and used. Although it does not specifically limit as an additive, It is preferable to use a viscosity modifier, a film-forming auxiliary
- Aqueous dispersion compositions containing these various additives can be used for paints, inks, sealants, primers or adhesives.
- the viscosity modifier is not particularly limited, and examples thereof include alkali swelling viscosity modifiers, alkali swelling association viscosity modifiers, urethane association viscosity modifiers, and the like.
- Specific examples of the alkali swelling type viscosity modifier are not particularly limited, but specific examples of the Primal (registered trademark) ASE 60 and the alkali swelling association type viscosity modifier are not particularly limited, but include Primal DR-72, urethane association type.
- Specific examples of the viscosity modifier are not particularly limited, and examples include Adecanol (registered trademark) UH-752.
- the laminate of the present invention refers to a laminate of a polyolefin substrate bonded with the adhesive of the present invention and a resin substrate, metal substrate or wood substrate.
- resin base material Resin sheets or resin films, such as polyvinyl chloride, polyester, polyolefin, polyamide, a poval, or a polyurethane, are mentioned.
- metal base material Various metals, such as aluminum, SUS, copper, iron, zinc, metal plates, such as each alloy and a plating product, and metal foil are mentioned.
- ⁇ Viscosity of aqueous dispersion composition The viscosity when the solid content of the modified polyolefin in the aqueous dispersion composition of the present invention is 30% by mass is evaluated by measuring the viscosity of the solution at 25 ° C. at a rotor rotational speed of 60 rpm using a Brookfield viscometer.
- a viscosity modifier is added to the aqueous dispersion composition before and after the addition of the anionic group-containing water-soluble polymer and / or electrolyte (charge reducing agent), the viscosity is measured, and evaluation is performed according to the following formula.
- a film forming aid and a wetting agent are added to the aqueous dispersion composition to prepare a primer paint simulation liquid (also called a flash primer).
- the flash primer is applied to the substrate 1 (polypropylene plate) so that the film thickness after drying with a bar coater is 10 ⁇ m.
- a two-component urethane paint is applied with a spray gun and dried with a warm air dryer for about 35 minutes in an atmosphere of about 80 ° C for a coating sample Get.
- Evaluation as an adhesive containing the aqueous dispersion composition of the present invention was performed by preparing a laminate sample and evaluating the adhesiveness.
- aqueous dispersion composition is applied to a polyolefin substrate using a bar coater so that the thickness of the dried aqueous dispersion composition layer is adjusted to 3 ⁇ m.
- the coated surface is dried for about 10 minutes in an atmosphere of about 80 ° C. with a warm air dryer.
- a metal substrate is superimposed on the surface of the aqueous dispersion composition layer, and a laminate is obtained by thermocompression bonding at about 120 ° C. and about 0.1 MPa for about 2 minutes.
- Production Example 1 A 1 L autoclave was charged with 100 parts by weight of a propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals), 300 parts by weight of toluene and 25 parts by weight of maleic anhydride, and the temperature was raised to 120 ° C. 8 parts by mass of di-tert-butyl peroxide was added and stirred for 1 hour. Then, after cooling the obtained reaction liquid, it poured into the container containing a lot of methyl ethyl ketone, and resin was deposited.
- a propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals)
- the resin-containing liquid was centrifuged to separate and purify the acid-modified propylene-butene copolymer grafted with maleic anhydride and the ungrafted maleic anhydride and low molecular weight substances. Thereafter, it is dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-butene copolymer (PO-1, modified amount of maleic anhydride is 2.0 mass%, weight average molecular weight is 50,000). It was.
- PO-1 maleic anhydride-modified propylene-butene copolymer
- Production Example 2 A maleic anhydride modified propylene-butene copolymer (PO-2, modified amount of maleic anhydride 1.0 mass), except that the amount of maleic anhydride charged was changed to 15 parts by mass. %, Weight average molecular weight 80,000).
- Production Example 3 A maleic anhydride-modified propylene-butene copolymer (PO-3, modified amount of maleic anhydride: 1.5 mass), except that the amount of maleic anhydride charged was changed to 21 parts by mass. %, Weight average molecular weight 70,000).
- the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-ethylene copolymer grafted with maleic anhydride, (poly) maleic anhydride and low molecular weight substances. Thereafter, it was dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-ethylene copolymer.
- 100 parts by mass of maleic anhydride-modified propylene-ethylene copolymer and 1700 parts by mass of chloroform were sealed in a 2 L glass-lined reaction can and sealed. The solution in the reaction can was heated while being stirred and dispersed, and dissolved in the can at a temperature of 120 ° C. for 1 hour.
- Example 1 After 210 parts by weight of ion-exchanged water, 100 parts by weight of PO-1, 110 parts by weight of tetrahydrofuran, 45 parts by weight of isopropyl alcohol, and 55 parts by weight of toluene were placed in a flask equipped with a stirrer and heated to 70 ° C. And dissolved at the same temperature for 1 hour. Next, 3.6 parts by mass (2 chemical equivalents) of N, N-dimethylethanolamine was added, and after gradually cooling to 40 ° C. over 1 hour, the organic solvent was removed at a reduced pressure of about 10 kPa (absolute pressure). The aqueous dispersion composition (a1-1) which was distilled off and became cloudy was obtained.
- aqueous dispersion composition (a2-1) 5 parts by mass (solid content) of Jonkrill (registered trademark) PDX-6137A was added to obtain an aqueous dispersion composition (a2-1).
- the aqueous dispersion composition (a2-1) had a solid content concentration of 30% by mass, a viscosity at 25 ° C. of 64 mPa ⁇ s, a pH of 9.0, and an average particle size of 92 nm.
- aqueous dispersion composition 100 parts by weight of aqueous dispersion composition (a2-1), 10 parts by weight of film-forming aid (butyl cellosolve) and wetting agent (Enviromem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.)
- a flash primer was prepared by adding 1 part by weight.
- the flash primer was applied to a polypropylene plate (manufactured by Yajima Seisakusho Co., Ltd.) using a bar coater.
- the coated surface was pre-dried for 10 minutes in an 80 ° C. atmosphere with a warm air dryer, and then a two-component urethane coating was applied with a spray gun, and dried for 35 minutes in an 80 ° C. atmosphere with a warm air dryer to form a coating sample 1 Obtained.
- Coating film samples 2 to 28 were prepared using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the coating film sample 1.
- Coating film samples 2 to 28 were also measured in the same manner as coating film sample 1. The results are shown in Tables 1 to 4.
- Coating film samples 2 to 28 were also measured in the same manner as coating film sample 1. The results are shown in Tables 1 to 4.
- Laminate Sample Aqueous dispersion composition 100 parts by weight 10 parts by weight of a film-forming aid (butyl cellosolve) and a wetting agent (Envirogem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.) 1 part by weight was added to produce an adhesive 1.
- Adhesive 1 was applied to an unstretched polypropylene film (Toyobo Pyrene (registered trademark) film CT, thickness 40 ⁇ m) using a bar coater so that the thickness of the adhesive layer after drying was adjusted to 3 ⁇ m. .
- Laminate sample 1 was obtained by thermocompression bonding at 1 MPa for 2 minutes.
- Laminate samples 2 to 28 were prepared using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the laminate sample 1.
- the anionic group-containing water-soluble polymer (C) used in Tables 1 to 4 is as follows.
- Anionic group-containing water-soluble polymer (c-1) Joncryl (registered trademark) PDX-6137A (styrene-acrylic monomer copolymer), nonvolatile content 28.0 wt%, solid content acid value 240 mgKOH / g-resin , Weight average molecular weight 16,500, manufactured by BASF.
- Anionic group-containing water-soluble polymer (c-4): Joncryl (registered trademark) 52J (styrene-acrylic monomer copolymer), non-volatile content 60.0% by weight, solid content acid value 238 mgKOH / g-resin, weight Average molecular weight 1,700, manufactured by BASF.
- the aqueous dispersion composition according to the present invention contains a modified polyolefin, a basic substance, and an anionic group-containing water-soluble polymer and / or an electrolyte
- the modified polyolefin solid content in the aqueous dispersion composition is 30% by mass.
- the viscosity at the time is constant in the range of 500 mPa ⁇ s or less.
- an anionic group-containing water-soluble polymer is used, the effects of additives used at the time of coating, particularly the viscosity modifier, are not hindered. Therefore, it is suitable for fields such as automotive exterior paint applications, automotive interior paint applications, and home appliance adhesive applications.
Abstract
Description
本発明で用いる変性ポリオレフィン(A)は、特に限定されないが、酸変性ポリオレフィン(A1)および/または酸変性塩素化ポリオレフィン(A2)であることが好ましい。 <Modified polyolefin (A)>
The modified polyolefin (A) used in the present invention is not particularly limited, but is preferably acid-modified polyolefin (A1) and / or acid-modified chlorinated polyolefin (A2).
本発明で用いる塩基性物質(B)は、変性ポリオレフィン(A)の酸性基(カルボキシル基)を中和させ、変性ポリオレフィン(A)の分散性を向上させることができる。 <Basic substance (B)>
The basic substance (B) used in the present invention can neutralize the acidic group (carboxyl group) of the modified polyolefin (A) and improve the dispersibility of the modified polyolefin (A).
本発明に用いるアニオン性基含有水溶性高分子(C)は、水性分散体組成物中の変性ポリオレフィン(A)の粒子表面の電荷を低減することができる。これにより、水性分散体組成物中の変性ポリオレフィン固形分30質量%のときの粘度を500mPa・s以下の範囲で一定にすることができる。 <Anionic group-containing water-soluble polymer (C)>
The anionic group-containing water-soluble polymer (C) used in the present invention can reduce the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition. Thereby, the viscosity when the modified polyolefin solid content in the aqueous dispersion composition is 30% by mass can be made constant within a range of 500 mPa · s or less.
本発明に用いる電解質(D)は、水に溶解して、陽イオンと陰イオンに電離し導電性を示すものをいう。電解質を用いることにより、水性分散体組成物中の変性ポリオレフィン(A)の粒子表面の電荷を低減することができ、これにより、水性分散体組成物中の変性ポリオレフィン固形分30質量%のときの粘度を500mPa・s以下の範囲で一定にすることができる。電解質(D)は、特に限定されないが、例えば、クエン酸、イソクエン酸、リンゴ酸、ロイシン酸、メバロン酸、パイトイン酸、リシノール酸、リシネライジン酸、セレブロン酸、キナ酸、シキミ酸、乳酸、酒石酸、シトラマル酸、ヒドロキシ酪酸、グリコール酸、タルトロン酸、グリセリン酸等の脂肪族ヒドロキシ酸;サリチル酸、クレオソート酸、バニリン酸、シリング酸、ピロカテク酸、レソルシル酸、プロトカテク酸、ゲンチジン酸、オルセリン酸、没食子酸、マンデル酸、ベンジン酸、アトロラクチン酸、メリロト酸、フロレト酸、クマル酸、ウンベル酸、コーヒー酸、フェルラ酸、シナピン酸等の芳香族ヒドロキシ酸;塩化リチウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、臭化ナトリウム、臭化カリウム、臭化マグネシウム、臭化カルシウム、ヨウ化ナトリウム、ヨウ化カルシウム等のハロゲン化アルカリ(土類)金属塩;が挙げられる。この中でも、クエン酸、イソクエン酸、塩化ナトリウムが好ましい。これら、電解質(D)を単独でまたは2種以上を併用して使用することができる。 <Electrolyte (D)>
The electrolyte (D) used in the present invention is one that dissolves in water and ionizes cations and anions to show conductivity. By using the electrolyte, the charge on the particle surface of the modified polyolefin (A) in the aqueous dispersion composition can be reduced, whereby the solid content of the modified polyolefin in the aqueous dispersion composition is 30% by mass. The viscosity can be made constant in the range of 500 mPa · s or less. The electrolyte (D) is not particularly limited. For example, citric acid, isocitric acid, malic acid, leucine acid, mevalonic acid, pytoic acid, ricinoleic acid, ricineramic acid, cerebric acid, quinic acid, shikimic acid, lactic acid, tartaric acid, Aliphatic hydroxy acids such as citramalic acid, hydroxybutyric acid, glycolic acid, tartronic acid, glyceric acid; salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orthoric acid, gallic acid , Aromatic acids such as mandelic acid, benzic acid, atrolactic acid, mellilotic acid, furoletic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, sinapinic acid; lithium chloride, sodium chloride, potassium chloride, magnesium chloride, Calcium chloride, sodium bromide, bromide Potassium, magnesium bromide, calcium bromide, sodium iodide, alkali halides (earth) or calcium metal iodide salt; and the like. Among these, citric acid, isocitric acid, and sodium chloride are preferable. These electrolytes (D) can be used alone or in combination of two or more.
本発明の水性分散体組成物は、前記変性ポリオレフィン(A)および塩基性物質(B)を含有し、さらにアニオン性基含有水溶性高分子(C)および電解質(D)の少なくとも一方を含有する混合物である。 <Aqueous dispersion composition>
The aqueous dispersion composition of the present invention contains the modified polyolefin (A) and the basic substance (B), and further contains at least one of an anionic group-containing water-soluble polymer (C) and an electrolyte (D). It is a mixture.
本発明の積層体は、本発明の接着剤で接着されたポリオレフィン基材と、樹脂基材、金属基材または木基材との積層体をいう。樹脂基材としては、特に限定されないが、ポリ塩化ビニル、ポリエステル、ポリオレフィン、ポリアミド、ポバールまたはポリウレタン等の樹脂シートまたは樹脂フィルムが挙げられる。また、金属基材としては、特に限定されないが、アルミニウム、SUS、銅、鉄、亜鉛等の各種金属、及びそれぞれの合金、めっき品等の金属板、金属箔が挙げられる。 <Laminate>
The laminate of the present invention refers to a laminate of a polyolefin substrate bonded with the adhesive of the present invention and a resin substrate, metal substrate or wood substrate. Although it does not specifically limit as a resin base material, Resin sheets or resin films, such as polyvinyl chloride, polyester, polyolefin, polyamide, a poval, or a polyurethane, are mentioned. Moreover, it does not specifically limit as a metal base material, Various metals, such as aluminum, SUS, copper, iron, zinc, metal plates, such as each alloy and a plating product, and metal foil are mentioned.
本発明の水性分散体組成物中の変性ポリオレフィン固形分30質量%のときの粘度は、ブルックフィールド型粘度計を用いて25℃の溶液の粘度をローター回転数60rpmで測定して評価する。
(評価基準)
◎(実用上特に優れる):200mPa・s以下
○(実用上優れる):200mPa・sを超えて300mPa・s以下
△(実用可能):300mPa・sを超えて500mPa・s以下
×(実用不可能):500mPa・sを超えるか、ゲル化により粘度測定不可 <Viscosity of aqueous dispersion composition>
The viscosity when the solid content of the modified polyolefin in the aqueous dispersion composition of the present invention is 30% by mass is evaluated by measuring the viscosity of the solution at 25 ° C. at a rotor rotational speed of 60 rpm using a Brookfield viscometer.
(Evaluation criteria)
◎ (particularly excellent in practical use): 200 mPa · s or less ○ (excellent in practical use): over 200 mPa · s to 300 mPa · s or less Δ (practical use): over 300 mPa · s to 500 mPa · s × (impractical) ): Over 500 mPa · s, or viscosity cannot be measured due to gelation
水性分散体組成物を含有する塗料、インキ、シール剤、プライマーまたは接着剤は、基材等に塗布するために、粘性調整剤を配合して一定の粘性を発現させる必要がある。このとき、電解質等の電荷低減剤が粘性調整剤の効果を阻害することがある。そのため、電荷低減剤による粘性調整剤への影響を評価した。具体的には、アニオン性基含有水溶性高分子および/または電解質(電荷低減剤)添加前後の水性分散体組成物に粘性調整剤を添加して粘度を測定し、下記式により評価する。
(評価基準)
ηd=電荷低減剤添加後の粘度/電荷低減剤添加前の粘度
◎(実用上特に優れる):ηd=0.9以上
○(実用上優れる):ηd=0.7以上、0.9未満
△(実用可能):ηd=0.5以上、0.7未満
×(実用不可能):ηd=0.5未満 <Evaluation of effects on viscosity modifier>
In order to apply the coating material, ink, sealant, primer or adhesive containing the aqueous dispersion composition to a substrate or the like, it is necessary to add a viscosity modifier to develop a certain viscosity. At this time, a charge reducing agent such as an electrolyte may inhibit the effect of the viscosity adjusting agent. Therefore, the influence of the charge reducing agent on the viscosity modifier was evaluated. Specifically, a viscosity modifier is added to the aqueous dispersion composition before and after the addition of the anionic group-containing water-soluble polymer and / or electrolyte (charge reducing agent), the viscosity is measured, and evaluation is performed according to the following formula.
(Evaluation criteria)
η d = viscosity after addition of charge reducing agent / viscosity before addition of charge reducing agent ◎ (particularly excellent in practical use): η d = 0.9 or more ○ (excellent in practical use): η d = 0.7 or more, 0. Less than 9 △ (practical): η d = 0.5 or more, less than 0.7 × (impractical): η d = less than 0.5
本発明の水性分散体組成物を含有する塗料、インキ、シール剤またはプライマーとしての評価は、塗膜サンプルを作製し、その接着性および耐水性によって評価した。 <Evaluation as paint, ink, sealant, primer>
Evaluation as a paint, ink, sealant or primer containing the aqueous dispersion composition of the present invention was performed by preparing a coating film sample and evaluating its adhesion and water resistance.
水性分散体組成物に成膜助剤および濡れ剤を添加してプライマー塗料模擬液(フラッシュプライマーとも言う)を作製する。フラッシュプライマーを基材1(ポリプロピレン板)にバーコーターで乾燥後の膜厚が10μmとなるように塗布する。塗布面を温風乾燥機で80℃雰囲気下10分間予備乾燥させた後、二液ウレタン塗料をスプレーガンで塗布し、温風乾燥機で約80℃雰囲気下約35分間乾燥させて塗膜サンプルを得る。 <Preparation of paint film sample>
A film forming aid and a wetting agent are added to the aqueous dispersion composition to prepare a primer paint simulation liquid (also called a flash primer). The flash primer is applied to the substrate 1 (polypropylene plate) so that the film thickness after drying with a bar coater is 10 μm. After pre-drying the coated surface with a warm air dryer for 10 minutes in an 80 ° C atmosphere, a two-component urethane paint is applied with a spray gun and dried with a warm air dryer for about 35 minutes in an atmosphere of about 80 ° C for a coating sample Get.
前記塗膜サンプルを25℃雰囲気下で36時間静置後、塗装面にカッターナイフにて1mm間隔で100個の碁盤目を作り、その上にセロハン粘着テープを密着させて60°の角度で引き剥がす。新しいセロハン粘着テープを使用して引き剥がしを10回繰り返す。10回繰り返しても塗装面に変化がなかった場合を10点、10回目で剥がれが生じた場合は9点、以下8,7,6点となり1回目で剥がれが生じた場合を0点とした。
(評価基準)
○(実用上優れる):10点
△(実用可能):9点
×(実用不可能):8点以下 <Evaluation of adhesiveness of coating film>
The coating film sample is allowed to stand for 36 hours in an atmosphere of 25 ° C., and 100 grids are made on the painted surface with a cutter knife at intervals of 1 mm, and a cellophane adhesive tape is closely attached on the coated surface and pulled at an angle of 60 °. Remove. Repeat the stripping 10 times using new cellophane adhesive tape. 10 points when the coating surface did not change after 10 repetitions, 9 points when peeling occurred at the 10th time, and 8 points below, 7, 6 points, and 0 points when peeling occurred at the first time .
(Evaluation criteria)
○ (Excellent for practical use): 10 points △ (Practical use): 9 points × (Practical use impossible): 8 points or less
前記塗膜サンプルを25℃雰囲気下で36時間静置後、40℃の温水に10日間浸漬させた。塗膜サンプルの変化を確認した後、接着性の評価を実施した。塗膜サンプルに変化が無く、接着性の評価で10点となった場合を良好で○とした。塗膜サンプルに変化が無く、接着性の評価で9点となった場合を△とした。塗膜サンプルにブリスターが発生したり、接着性の評価で8点以下となった場合を不良で×とした。 <Evaluation of water resistance of coating film>
The coating film sample was allowed to stand for 36 hours in a 25 ° C. atmosphere, and then immersed in warm water of 40 ° C. for 10 days. After confirming the change of the coating film sample, the adhesiveness was evaluated. The case where there was no change in the coating film sample and the adhesive evaluation was 10 points was evaluated as good and good. The case where there was no change in the coating film sample and the adhesion evaluation was 9 points was evaluated as Δ. The case where blister was generated in the coating film sample or the adhesion evaluation was 8 points or less was evaluated as x.
本発明の水性分散体組成物を含有する接着剤としての評価は、積層体サンプルを作製し、その接着性によって評価した。 <Evaluation as an adhesive>
Evaluation as an adhesive containing the aqueous dispersion composition of the present invention was performed by preparing a laminate sample and evaluating the adhesiveness.
水性分散体組成物をポリオレフィン基材にバーコーターを用いて乾燥後の水性分散体組成物層の膜厚が3μmになるように調整して塗布する。塗布面を温風乾燥機で約80℃雰囲気下約10分間乾燥させる。前記水性分散体組成物層表面に金属基材を重ね合わせ、約120℃、約0.1MPaで約2分間熱圧着することで積層体を得る。 <Preparation of laminate sample>
The aqueous dispersion composition is applied to a polyolefin substrate using a bar coater so that the thickness of the dried aqueous dispersion composition layer is adjusted to 3 μm. The coated surface is dried for about 10 minutes in an atmosphere of about 80 ° C. with a warm air dryer. A metal substrate is superimposed on the surface of the aqueous dispersion composition layer, and a laminate is obtained by thermocompression bonding at about 120 ° C. and about 0.1 MPa for about 2 minutes.
ASTM-D1876-61の試験法に準拠し、オリエンテックコーポレーション社製のテンシロンRTM-100を用いて、25℃環境下で、引張速度50mm/分における剥離強度を測定する。金属基材/ポリオレフィン基材間の剥離強度(N/cm)は5回の試験値の平均値とする。
(評価基準)
◎(実用上特に優れる):8N/cm以上
○(実用上優れる):7N/cm以上8N/cm未満
△(実用可能):6N/cm以上7N/cm未満
×(実用不可能):6N/cm未満 <Evaluation of adhesiveness of laminate>
Based on the test method of ASTM-D1876-61, the peel strength at a tensile speed of 50 mm / min is measured in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation. The peel strength (N / cm) between the metal substrate / polyolefin substrate is the average of five test values.
(Evaluation criteria)
◎ (particularly excellent in practical use): 8 N / cm or more ○ (excellent in practical use): 7 N / cm or more and less than 8 N / cm Δ (practical): 6 N / cm or more and less than 7 N / cm × (impractical): 6 N / less than cm
1Lオートクレーブに、プロピレン-ブテン共重合体(三井化学社製「タフマー(登録商標)XM7080」)100質量部、トルエン300質量部及び無水マレイン酸25質量部を入れ、120℃まで昇温した後、ジ-tert-ブチルパーオキサイド8質量部を加え、1時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性プロピレン-ブテン共重合体とグラフトしていない無水マレイン酸および低分子量物とを分離、精製した。その後、減圧下70℃で5時間乾燥させることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-1、無水マレイン酸の変性量2.0質量%、重量平均分子量50,000)を得た。 Production Example 1
A 1 L autoclave was charged with 100 parts by weight of a propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals), 300 parts by weight of toluene and 25 parts by weight of maleic anhydride, and the temperature was raised to 120 ° C. 8 parts by mass of di-tert-butyl peroxide was added and stirred for 1 hour. Then, after cooling the obtained reaction liquid, it poured into the container containing a lot of methyl ethyl ketone, and resin was deposited. Thereafter, the resin-containing liquid was centrifuged to separate and purify the acid-modified propylene-butene copolymer grafted with maleic anhydride and the ungrafted maleic anhydride and low molecular weight substances. Thereafter, it is dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-butene copolymer (PO-1, modified amount of maleic anhydride is 2.0 mass%, weight average molecular weight is 50,000). It was.
無水マレイン酸の仕込み量を15質量部に変更した以外は製造例1と同様にすることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-2、無水マレイン酸の変性量1.0質量%、重量平均分子量80,000)を得た。 Production Example 2
A maleic anhydride modified propylene-butene copolymer (PO-2, modified amount of maleic anhydride 1.0 mass), except that the amount of maleic anhydride charged was changed to 15 parts by mass. %, Weight average molecular weight 80,000).
無水マレイン酸の仕込み量を21質量部に変更した以外は製造例1と同様にすることにより、無水マレイン酸変性プロピレン-ブテン共重合体(PO-3、無水マレイン酸の変性量1.5質量%、重量平均分子量70,000)を得た。 Production Example 3
A maleic anhydride-modified propylene-butene copolymer (PO-3, modified amount of maleic anhydride: 1.5 mass), except that the amount of maleic anhydride charged was changed to 21 parts by mass. %, Weight average molecular weight 70,000).
撹拌機を取り付けた1Lオートクレーブに、プロピレン-エチレン共重合体(230℃雰囲気下のMFR=5g/10分)100質量部、トルエン150質量部及び無水マレイン酸20質量部、ジ-tert-ブチルパーオキサイド5質量部を加え、140℃まで昇温した後、更に3時間撹拌した。その後、得られた反応液を冷却後、多量のメチルエチルケトンが入った容器に注ぎ、樹脂を析出させた。その後、当該樹脂を含有する液を遠心分離することにより、無水マレイン酸がグラフト重合した酸変性プロピレン-エチレン共重合体と(ポリ)無水マレイン酸および低分子量物とを分離、精製した。その後、減圧下70℃で5時間乾燥させることにより、無水マレイン酸変性プロピレン-エチレン共重合体を得た。次いで、2Lのグラスライニング製反応缶に、無水マレイン酸変性プロピレン-エチレン共重合体を100質量部、クロロホルムを1700質量部入れ密閉にした。反応缶内の液を撹拌して分散しながら加温し、缶内温度120℃で1時間溶解した。缶内温度を110℃まで冷却した後に、t-ブチルパーオキシ-2-エチルヘキサエノエートを0.5質量部添加し、塩素を70質量部導入した。缶内温度を60℃まで冷却し、クロロホルム1400質量部を留去した後に、安定剤としてp-t-ブチルフェニルグリシジルエーテルを4質量部添加した。その後、乾燥することにより、無水マレイン酸変性塩素化プロピレン-エチレン共重合体(CPO-1、無水マレイン酸の変性量2.5質量%、塩素含有率20質量%、重量平均分子量80,000)を得た。 Production Example 4
In a 1 L autoclave equipped with a stirrer, 100 parts by mass of propylene-ethylene copolymer (MFR = 5 g / 10 min at 230 ° C. atmosphere), 150 parts by mass of toluene and 20 parts by mass of maleic anhydride, di-tert-butyl per After 5 parts by mass of oxide was added and the temperature was raised to 140 ° C., the mixture was further stirred for 3 hours. Then, after cooling the obtained reaction liquid, it poured into the container containing a lot of methyl ethyl ketone, and resin was deposited. Thereafter, the liquid containing the resin was centrifuged to separate and purify the acid-modified propylene-ethylene copolymer grafted with maleic anhydride, (poly) maleic anhydride and low molecular weight substances. Thereafter, it was dried at 70 ° C. under reduced pressure for 5 hours to obtain a maleic anhydride-modified propylene-ethylene copolymer. Next, 100 parts by mass of maleic anhydride-modified propylene-ethylene copolymer and 1700 parts by mass of chloroform were sealed in a 2 L glass-lined reaction can and sealed. The solution in the reaction can was heated while being stirred and dispersed, and dissolved in the can at a temperature of 120 ° C. for 1 hour. After cooling the internal temperature to 110 ° C., 0.5 parts by mass of t-butylperoxy-2-ethylhexanoate was added, and 70 parts by mass of chlorine was introduced. The temperature inside the can was cooled to 60 ° C., 1400 parts by mass of chloroform was distilled off, and 4 parts by mass of pt-butylphenylglycidyl ether was added as a stabilizer. Thereafter, by drying, maleic anhydride modified chlorinated propylene-ethylene copolymer (CPO-1, modified amount of maleic anhydride 2.5% by mass, chlorine content 20% by mass, weight average molecular weight 80,000) Got.
無水マレイン酸の仕込み量を9質量部、ジ-tert-ブチルパーオキサイドの仕込み量を3質量部、塩素の導入量を160質量部に変更した以外は製造例4と同様にすることにより、無水マレイン酸変性塩素化プロピレン-エチレン共重合体(CPO-2、無水マレイン酸の変性量0.8質量%、塩素含有率40質量%、重量平均分子量100,000)を得た。 Production Example 5
By changing the amount of maleic anhydride charged to 9 parts by mass, the amount of di-tert-butyl peroxide charged to 3 parts by mass, and the amount of chlorine introduced to 160 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-2, maleic anhydride modification amount 0.8 mass%, chlorine content 40 mass%, weight average molecular weight 100,000) was obtained.
無水マレイン酸の仕込み量を35質量部、ジ-tert-ブチルパーオキサイドの仕込み量を6質量部、塩素の導入量を10質量部に変更した以外は製造例4と同様にすることにより、無水マレイン酸変性塩素化プロピレン-エチレン共重合体(CPO-3、無水マレイン酸の変性量3.0質量%、塩素含有率15質量%、重量平均分子量70,000)を得た。 Production Example 6
By changing the amount of maleic anhydride charged to 35 parts by mass, the amount of di-tert-butyl peroxide charged to 6 parts by mass and the amount of chlorine introduced to 10 parts by mass, A maleic acid-modified chlorinated propylene-ethylene copolymer (CPO-3, modified amount of maleic anhydride 3.0% by mass, chlorine content 15% by mass, weight average molecular weight 70,000) was obtained.
イオン交換水を210質量部、PO-1を100質量部、テトラヒドロフランを110質量部、イソプロピルアルコールを45質量部、およびトルエンを55質量部、撹拌機付きフラスコに入れ、70℃に昇温した後、同温度で1時間、加熱溶解した。次に、N,N-ジメチルエタノールアミン3.6質量部(2化学当量)を添加し、1時間かけて徐々に40℃まで冷却した後、約10kPa(絶対圧力)の減圧度で有機溶剤を留去し、白濁した水性分散体組成物(a1-1)を得た。この水性分散体組成物にジョンクリル(登録商標)PDX-6137Aを5質量部(固形分)添加して、水性分散体組成物(a2-1)を得た。水性分散体組成物(a2-1)の固形分濃度は30質量%、25℃での粘度は64mPa・s、pHは9.0、平均粒子径は92nmであった。 Example 1
After 210 parts by weight of ion-exchanged water, 100 parts by weight of PO-1, 110 parts by weight of tetrahydrofuran, 45 parts by weight of isopropyl alcohol, and 55 parts by weight of toluene were placed in a flask equipped with a stirrer and heated to 70 ° C. And dissolved at the same temperature for 1 hour. Next, 3.6 parts by mass (2 chemical equivalents) of N, N-dimethylethanolamine was added, and after gradually cooling to 40 ° C. over 1 hour, the organic solvent was removed at a reduced pressure of about 10 kPa (absolute pressure). The aqueous dispersion composition (a1-1) which was distilled off and became cloudy was obtained. To this aqueous dispersion composition, 5 parts by mass (solid content) of Jonkrill (registered trademark) PDX-6137A was added to obtain an aqueous dispersion composition (a2-1). The aqueous dispersion composition (a2-1) had a solid content concentration of 30% by mass, a viscosity at 25 ° C. of 64 mPa · s, a pH of 9.0, and an average particle size of 92 nm.
水性分散体組成物(a1-1)、(a2-1)と同様にして、組成が表1~4に示される水性分散体組成物(a1-1)~(a1-28)、(a2-1)~(a2-28)を得た。物性等を表1~4に示す。 Examples 2 to 22, Comparative Examples 1 to 6
Similarly to the aqueous dispersion compositions (a1-1) and (a2-1), the aqueous dispersion compositions (a1-1) to (a1-28), (a2- 1) to (a2-28) were obtained. The physical properties are shown in Tables 1 to 4.
ビーカーに水性分散体組成物(a1-1)100質量部を採取し、ホモディスパーで撹拌しながらアルカリ膨潤型粘度調整剤(プライマル(登録商標)ASE60、ローム・アンド・ハース社製)8質量部を徐々に滴下して、10分間撹拌した。撹拌後、25℃の恒温槽に一晩静置し、ホモディスパーで再度撹拌し、ブルックフィールド型粘度計で粘度を測定した。水性分散体組成物(a1-2)~(a1-28)、(a2-1)~(a2-28)も(a-1)と同様に測定した。結果を表1~4に示す。 Evaluation of effect on viscosity modifier (measurement of viscosity of aqueous dispersion composition)
100 parts by weight of the aqueous dispersion composition (a1-1) was collected in a beaker, and 8 parts by weight of an alkali swelling viscosity modifier (Primal (registered trademark) ASE 60, manufactured by Rohm and Haas) while stirring with a homodisper. Was gradually added dropwise and stirred for 10 minutes. After stirring, it was left overnight in a thermostatic bath at 25 ° C., stirred again with a homodisper, and the viscosity was measured with a Brookfield viscometer. The aqueous dispersion compositions (a1-2) to (a1-28) and (a2-1) to (a2-28) were also measured in the same manner as (a-1). The results are shown in Tables 1 to 4.
水性分散体組成物(a2-1)100重量部に成膜助剤(ブチルセロソルブ)10重量部および濡れ剤(エンバイロジェム(登録商標)AD01、日信化学工業(株)製)1重量部を添加してフラッシュプライマーを作製した。フラッシュプライマーをポリプロピレン板((株)矢島製作所製)にバーコーターを用いて塗布した。塗布面を温風乾燥機で80℃雰囲気下10分間予備乾燥させた後、二液ウレタン塗料をスプレーガンで塗布し、温風乾燥機で80℃雰囲気下35分間乾燥させて塗膜サンプル1を得た。塗膜サンプル2~28についても塗膜サンプル1と同様に、水性分散体組成物(a2-2)~(a2-28)を用いて作製した。 Preparation of coating film sample: 100 parts by weight of aqueous dispersion composition (a2-1), 10 parts by weight of film-forming aid (butyl cellosolve) and wetting agent (Enviromem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.) A flash primer was prepared by adding 1 part by weight. The flash primer was applied to a polypropylene plate (manufactured by Yajima Seisakusho Co., Ltd.) using a bar coater. The coated surface was pre-dried for 10 minutes in an 80 ° C. atmosphere with a warm air dryer, and then a two-component urethane coating was applied with a spray gun, and dried for 35 minutes in an 80 ° C. atmosphere with a warm air dryer to form a coating sample 1 Obtained. Coating film samples 2 to 28 were prepared using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the coating film sample 1.
前記塗膜サンプル1を25℃雰囲気下で36時間静置後、塗装面にカッターナイフにて1mm間隔で100個の碁盤目を作り、その上にセロハン粘着テープを密着させて60°の角度で引き剥がす。新しいセロハン粘着テープを使用して引き剥がしを10回繰り返す。10回繰り返しても塗装面に変化がなかった場合を10点とし、10回目で剥がれが生じた場合は9点、以下8,7,6点となり1回目で剥がれが生じた場合を0点とした。塗膜サンプル2~28も塗膜サンプル1と同様に測定した。結果を表1~4に示す。 Adhesiveness of coating film The coating film sample 1 was allowed to stand for 36 hours in an atmosphere of 25 ° C., and 100 grids were made on the painted surface with a cutter knife at intervals of 1 mm, and a cellophane adhesive tape was adhered thereon. Peel off at an angle of 60 °. Repeat the stripping 10 times using new cellophane adhesive tape. 10 points when the coating surface did not change after 10 repetitions, 9 points when peeling occurred at the 10th time, 8 points below, 7, 6 points, and 0 points when peeling occurs at the first time did. Coating film samples 2 to 28 were also measured in the same manner as coating film sample 1. The results are shown in Tables 1 to 4.
前記塗膜サンプル1を25℃雰囲気下で36時間静置後、40℃の温水に10日間浸漬させた。塗膜の変化を確認した後、接着性の評価を実施した。塗膜に変化が無く、接着性の評価で10点となった場合を良好で○とした。塗膜に変化が無く、接着性の評価で9点となった場合を△とした。塗膜にブリスターが発生したり、接着性の評価で8点以下となった場合を不良で×とした。塗膜サンプル2~28も塗膜サンプル1と同様に測定した。結果を表1~4に示す。 Water resistance of coating film The coating film sample 1 was allowed to stand for 36 hours in a 25 ° C. atmosphere and then immersed in warm water at 40 ° C. for 10 days. After confirming the change of the coating film, the adhesiveness was evaluated. The case where there was no change in the coating film and the adhesive evaluation was 10 points was evaluated as good and good. The case where there was no change in the coating film and the adhesive evaluation was 9 points was evaluated as Δ. A case where blisters were generated in the coating film or the adhesive evaluation was 8 points or less was evaluated as x. Coating film samples 2 to 28 were also measured in the same manner as coating film sample 1. The results are shown in Tables 1 to 4.
水性分散体組成物(a2-1)100質量部に成膜助剤(ブチルセロソルブ)10重量部および濡れ剤(エンバイロジェム(登録商標)AD01、日信化学工業(株)製)1重量部を添加して、接着剤1を作製した。接着剤1を無延伸ポリプロピレンフィルム(東洋紡社製パイレン(登録商標)フィルムCT、厚さ40μm)にバーコーターを用いて乾燥後の接着剤層の膜厚が3μmになるように調整して塗布した。塗布面を温風乾燥機で80℃雰囲気下10分間乾燥させ、前記接着剤層表面にアルミニウム箔(住軽アルミ箔社製、8079-0、厚さ40μm)を重ね合わせ、120℃、0.1MPaで2分間熱圧着することで積層体サンプル1を得た。積層体サンプル2~28についても積層体サンプル1と同様に、水性分散体組成物(a2-2)~(a2-28)を用いて作製した。 Preparation of Laminate Sample Aqueous dispersion composition (a2-1) 100 parts by weight 10 parts by weight of a film-forming aid (butyl cellosolve) and a wetting agent (Envirogem (registered trademark) AD01, manufactured by Nissin Chemical Industry Co., Ltd.) 1 part by weight was added to produce an adhesive 1. Adhesive 1 was applied to an unstretched polypropylene film (Toyobo Pyrene (registered trademark) film CT, thickness 40 μm) using a bar coater so that the thickness of the adhesive layer after drying was adjusted to 3 μm. . The coated surface was dried with a hot air dryer for 10 minutes in an atmosphere at 80 ° C., and an aluminum foil (8079-0, 40 μm in thickness) was superimposed on the surface of the adhesive layer. Laminate sample 1 was obtained by thermocompression bonding at 1 MPa for 2 minutes. Laminate samples 2 to 28 were prepared using the aqueous dispersion compositions (a2-2) to (a2-28) in the same manner as the laminate sample 1.
ASTM-D1876-61の試験法に準拠し、オリエンテックコーポレーション社製のテンシロンRTM-100を用いて、25℃環境下で、引張速度50mm/分における積層体サンプル1の剥離強度を測定した。積層体サンプル2~28も積層体サンプル1と同様に測定した。結果を表1~4に示す。 <Evaluation of adhesiveness of laminate>
In accordance with the test method of ASTM-D1876-61, the peel strength of the laminate sample 1 at a tensile speed of 50 mm / min was measured in a 25 ° C. environment using Tensilon RTM-100 manufactured by Orientec Corporation. The laminate samples 2 to 28 were measured in the same manner as the laminate sample 1. The results are shown in Tables 1 to 4.
アニオン性基含有水溶性高分子(c-1):ジョンクリル(登録商標)PDX-6137A(スチレン-アクリルモノマー共重合物)、不揮発分28.0重量%、固形分酸価240mgKOH/g-resin、重量平均分子量16,500、BASF社製。
アニオン性基含有水溶性高分子(c-2):ジョンクリル(登録商標)57J(スチレン-アクリルモノマー共重合物)、不揮発分37.0重量%、固形分酸価215mgKOH/g-resin、重量平均分子量4,900、BASF製。
アニオン性基含有水溶性高分子(c-3):ジョンクリル(登録商標)HPD-196(スチレン-アクリルモノマー共重合物)、不揮発分36.0重量%、固形分酸価200mgKOH/g-resin、重量平均分子量9,200、BASF製。
アニオン性基含有水溶性高分子(c-4):ジョンクリル(登録商標)52J(スチレン-アクリルモノマー共重合物)、不揮発分60.0重量%、固形分酸価238mgKOH/g-resin、重量平均分子量1,700、BASF製。
アニオン性基含有水溶性高分子(c-5):ジョンクリル(登録商標)JDX-6500(スチレン-アクリルモノマー共重合物)、不揮発分29.5重量%、固形分酸価85mgKOH/g-resin、重量平均分子量10,000、BASF製。 The anionic group-containing water-soluble polymer (C) used in Tables 1 to 4 is as follows.
Anionic group-containing water-soluble polymer (c-1): Joncryl (registered trademark) PDX-6137A (styrene-acrylic monomer copolymer), nonvolatile content 28.0 wt%, solid content acid value 240 mgKOH / g-resin , Weight average molecular weight 16,500, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-2): Joncryl (registered trademark) 57J (styrene-acrylic monomer copolymer), non-volatile content 37.0% by weight, solid content acid value 215 mg KOH / g-resin, weight Average molecular weight 4,900, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-3): Joncryl (registered trademark) HPD-196 (styrene-acrylic monomer copolymer), non-volatile content 36.0% by weight, solid content acid value 200 mgKOH / g-resin , Weight average molecular weight 9,200, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-4): Joncryl (registered trademark) 52J (styrene-acrylic monomer copolymer), non-volatile content 60.0% by weight, solid content acid value 238 mgKOH / g-resin, weight Average molecular weight 1,700, manufactured by BASF.
Anionic group-containing water-soluble polymer (c-5): Joncrill (registered trademark) JDX-6500 (styrene-acrylic monomer copolymer), non-volatile content 29.5 wt%, solid content acid value 85 mgKOH / g-resin , Weight average molecular weight 10,000, manufactured by BASF.
Claims (6)
- 変性ポリオレフィン(A)および塩基性物質(B)を含有し、さらに酸価が150~500mgKOH/g-resinであるアニオン性基含有水溶性高分子(C)および電解質(D)の少なくとも一方を含有する水性分散体組成物。 Contains a modified polyolefin (A) and a basic substance (B), and further contains at least one of an anionic group-containing water-soluble polymer (C) having an acid value of 150 to 500 mgKOH / g-resin and an electrolyte (D) An aqueous dispersion composition.
- 変性ポリオレフィン(A)が、酸変性ポリオレフィン(A1)および/または酸変性塩素化ポリオレフィン(A2)である請求項1に記載の水生分散体組成物。 The aquatic dispersion composition according to claim 1, wherein the modified polyolefin (A) is an acid-modified polyolefin (A1) and / or an acid-modified chlorinated polyolefin (A2).
- 変性ポリオレフィン(A)100質量部に対して、塩基性物質(B)を0.5~10質量部含有し、アニオン性基含有水溶性高分子(C)と電解質(D)の合計量を0.1~20質量部含有する請求項1に記載の水性分散体組成物。 0.5 to 10 parts by mass of the basic substance (B) per 100 parts by mass of the modified polyolefin (A), and the total amount of the anionic group-containing water-soluble polymer (C) and the electrolyte (D) is 0. The aqueous dispersion composition according to claim 1, containing 1 to 20 parts by mass.
- 請求項1~3のいずれかに記載の水性分散体組成物を含有する塗料、インキ、シール剤、プライマーまたは接着剤。 A paint, ink, sealant, primer or adhesive containing the aqueous dispersion composition according to any one of claims 1 to 3.
- 請求項4に記載の接着剤で接着されたポリオレフィン基材と、樹脂基材または金属基材との積層体。 A laminate of a polyolefin substrate bonded with the adhesive according to claim 4 and a resin substrate or a metal substrate.
- 請求項4に記載の塗料で塗装されたポリオレフィン基材。
A polyolefin substrate coated with the paint according to claim 4.
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2017154498A (en) * | 2016-02-26 | 2017-09-07 | ユニチカ株式会社 | Layered film and method for producing the same |
JP2019070092A (en) * | 2017-10-11 | 2019-05-09 | ユニチカ株式会社 | Aqueous dispersion |
JP2019116536A (en) * | 2017-12-27 | 2019-07-18 | ユニチカ株式会社 | Aqueous coat agent |
WO2022209918A1 (en) * | 2021-03-29 | 2022-10-06 | 東洋紡株式会社 | Polyolefin adhesive composition and multilayer body |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03182534A (en) * | 1989-12-13 | 1991-08-08 | Sanyo Chem Ind Ltd | Aqueous resin composition |
JP2003171512A (en) * | 2001-12-05 | 2003-06-20 | Unitika Ltd | Polyolefin resin aqueous dispersion, and its production method |
JP2006225551A (en) * | 2005-02-18 | 2006-08-31 | Unitika Ltd | Aqueous dispersion and laminate |
WO2006129804A1 (en) * | 2005-06-03 | 2006-12-07 | Mitsubishi Chemical Corporation | Aqueous resin dispersion, method for producing same, coating material, and multilayer body |
WO2007011033A1 (en) * | 2005-07-22 | 2007-01-25 | Toyo Kasei Kogyo Co., Ltd. | Aqueous resin composition and method for producing same |
WO2007011034A1 (en) * | 2005-07-22 | 2007-01-25 | Toyo Kasei Kogyo Co., Ltd. | Aqueous resin composition and method for producing same |
JP2009286918A (en) * | 2008-05-30 | 2009-12-10 | Unitika Ltd | Aqueous dispersion and laminate |
JP2011184593A (en) * | 2010-03-09 | 2011-09-22 | Mitsui Chemicals Inc | Aqueous dispersion |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993003104A1 (en) * | 1991-08-05 | 1993-02-18 | Eastman Kodak Company | Aqueous coating composition |
JP5019693B2 (en) | 2002-06-14 | 2012-09-05 | 東洋紡績株式会社 | Aqueous resin dispersion composition and method for producing the same |
JP2005126482A (en) | 2003-10-21 | 2005-05-19 | Unitika Ltd | Aqueous dispersion of polyolefin resin and method for producing the same |
JP4313263B2 (en) * | 2004-07-08 | 2009-08-12 | 大成建設株式会社 | Continuous underground wall and mountain retaining method |
CN101589101B (en) * | 2006-12-13 | 2013-07-17 | 日本制纸化学株式会社 | Polyolefin resin dispersion composition and process for producing the same |
JP5200475B2 (en) | 2007-09-25 | 2013-06-05 | 東洋紡株式会社 | Method for producing aqueous resin dispersion composition |
-
2014
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03182534A (en) * | 1989-12-13 | 1991-08-08 | Sanyo Chem Ind Ltd | Aqueous resin composition |
JP2003171512A (en) * | 2001-12-05 | 2003-06-20 | Unitika Ltd | Polyolefin resin aqueous dispersion, and its production method |
JP2006225551A (en) * | 2005-02-18 | 2006-08-31 | Unitika Ltd | Aqueous dispersion and laminate |
WO2006129804A1 (en) * | 2005-06-03 | 2006-12-07 | Mitsubishi Chemical Corporation | Aqueous resin dispersion, method for producing same, coating material, and multilayer body |
WO2007011033A1 (en) * | 2005-07-22 | 2007-01-25 | Toyo Kasei Kogyo Co., Ltd. | Aqueous resin composition and method for producing same |
WO2007011034A1 (en) * | 2005-07-22 | 2007-01-25 | Toyo Kasei Kogyo Co., Ltd. | Aqueous resin composition and method for producing same |
JP2009286918A (en) * | 2008-05-30 | 2009-12-10 | Unitika Ltd | Aqueous dispersion and laminate |
JP2011184593A (en) * | 2010-03-09 | 2011-09-22 | Mitsui Chemicals Inc | Aqueous dispersion |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017154498A (en) * | 2016-02-26 | 2017-09-07 | ユニチカ株式会社 | Layered film and method for producing the same |
JP2019070092A (en) * | 2017-10-11 | 2019-05-09 | ユニチカ株式会社 | Aqueous dispersion |
JP7132583B2 (en) | 2017-10-11 | 2022-09-07 | ユニチカ株式会社 | aqueous dispersion |
JP2019116536A (en) * | 2017-12-27 | 2019-07-18 | ユニチカ株式会社 | Aqueous coat agent |
WO2022209918A1 (en) * | 2021-03-29 | 2022-10-06 | 東洋紡株式会社 | Polyolefin adhesive composition and multilayer body |
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