JP2018111737A - Aqueous dispersion mixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion mixture having sufficient adhesiveness to a base material of polyolefins even at relatively low temperature, exhibiting adhesiveness to a coating film other than polyolefins.SOLUTION: An aqueous dispersion containing a modified polymer obtained by grafting modification of a polyolefin having substantially no melting point peak observed in differential scanning calorimetry (DSC) with α, β-unsaturated carboxylic acids as dispersoid, and an aqueous dispersion including a polyurethane as dispersoid are used in combination.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous dispersion mixture that exhibits excellent adhesiveness, in particular, excellent adhesiveness at low temperatures to substrates made of polyolefins.

  Conventionally, polyolefins such as propylene homopolymers and copolymers of propylene and α-olefins are excellent in mechanical properties, heat resistance, chemical resistance, water resistance and the like, and are inexpensive. It is used in a wide range of fields.

  In general, it is known that the surface of a substrate made of polyolefins has low adhesion to substances other than polyolefins, and it is difficult to form a coating film such as an adhesive or paint. Therefore, attempts have been made to improve paintability and adhesiveness by using modified polyolefins such as chlorinated polyolefin, acid-modified chlorinated polyolefin, and acid-modified polyolefin as a component of a primer or an adhesive. In these primers and adhesives, the modified polyolefin is usually used in the form of a solution in an organic solvent or a dispersion in an aqueous solvent, and is preferably used in the form of an aqueous dispersion in terms of safety and environment. .

  On the other hand, in primers and adhesives containing these modified polyolefin dispersions, in order to improve coating properties such as abrasion resistance and adhesion to substrates and paints made of substances other than polyolefins A dispersion using an acrylic resin, a urethane resin or the like together with a modified polyolefin has been proposed (Patent Documents 1 to 3).

JP 2008-88332 A Japanese Patent No. 4942482 Japanese Patent No. 5601760

  However, in the case of an aqueous dispersion mixture of a conventional aqueous dispersion of modified polyolefin and an aqueous dispersion such as an acrylic resin or a urethane resin, in order to exert adhesion to a substrate or a coating film made of polyolefins, It was necessary to process at a relatively high temperature of ˜100 ° C. For this reason, the aqueous dispersion which exhibits adhesiveness even when it processes at lower temperature from viewpoints, such as a manufacturing cost reduction and a carbon dioxide emission reduction, is desired.

  Therefore, the present invention exhibits sufficient adhesiveness to a substrate made of polyolefins even when used at a relatively low temperature, and to a substrate or coating film made of a substance other than polyolefins. However, an object of the present invention is to provide an aqueous dispersion mixture capable of exhibiting good adhesiveness.

The present invention provides at least the following solutions.
[1]
An aqueous dispersion mixture containing an aqueous dispersion (A) and an aqueous dispersion (B), wherein the aqueous dispersion (A) is a polyolefin (a-1) in which a melting point peak is substantially not observed, α, An aqueous dispersion mixture comprising a modified polymer (a-2) obtained by graft modification with β-unsaturated carboxylic acids as a dispersoid, wherein the aqueous dispersion (B) comprises a polyurethane (b) as a dispersoid. .
[2]
The aqueous dispersion mixture according to [1], containing 65 to 200 parts by mass of the nonvolatile content of the aqueous dispersion (B) with respect to 100 parts by mass of the nonvolatile content of the aqueous dispersion (A).
[3]
The structural unit derived from the α, β-unsaturated carboxylic acids in the modified polymer (a-2) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the structural unit derived from the polyolefin (a-1). The aqueous dispersion mixture according to [1] or [2].
[4]
The aqueous dispersion mixture according to any one of [1] to [3], wherein the modified polymer (a-2) has a weight average molecular weight Mw of 20,000 to 200,000.
[5]
The aqueous dispersion mixture according to any one of [1] to [4], wherein the dispersoid of the aqueous dispersion (A) has a volume-based median diameter of 1 μm or less.
[6]
The aqueous dispersion mixture according to any one of [1] to [5], wherein the dispersoid of the aqueous dispersion (A) is a self-emulsified product of the modified polymer (a-2).
[7]
The aqueous adhesive containing the aqueous dispersion mixture in any one of said [1]-[6].
[8]
The laminated body which has the layer adhere | attached with the water-based adhesive as described in said [7].

  The aqueous dispersion mixture of the present invention not only exhibits excellent adhesion to substrates made of polyolefins, but also exhibits high adhesion to substrates and coatings made of substances other than polyolefins. . The aqueous dispersion mixture of the present invention can exhibit good adhesion even when treated at a low temperature of about 60 ° C. Therefore, the aqueous dispersion mixture of the present invention can be suitably used for a primer, a coating composition, an adhesive and the like.

  The aqueous dispersion mixture of the present invention is an aqueous dispersion mixture containing an aqueous dispersion (A) and an aqueous dispersion (B). In the aqueous dispersion (A), a polyolefin (a-1) (hereinafter referred to as polyolefin (a-1)) in which a melting point peak is not substantially observed by differential scanning calorimetry (DSC) is expressed as α, β- An aqueous dispersion containing, as a dispersoid, a modified polymer (a-2) obtained by graft modification with a saturated carboxylic acid (hereinafter referred to as a modified polymer (a-2)). Moreover, the said aqueous dispersion (B) is an aqueous dispersion which uses a polyurethane (b) as a dispersoid.

  In the present invention, a polyolefin whose melting point peak is not substantially observed by differential scanning calorimetry (DSC) is a crystal in a temperature range of −100 ° C. to 200 ° C. in differential scanning calorimetry (DSC) according to JIS K7122. A polyolefin in which a crystal melting peak with a heat of fusion of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more are not observed. Polyolefin is a thermoplastic resin obtained by polymerizing olefin, for example, a polymer and a copolymer having one or more types of structural units derived from olefin. The crystal melting peak and the crystallization peak can be measured, for example, by the method described in Examples described later.

The polyolefin (a-1) is not particularly limited as long as the melting point peak is not substantially observed by differential scanning calorimetry (DSC), but from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples thereof include polyolefins obtained by homopolymerizing or copolymerizing at least one selected olefin.
Examples of the α-olefin having 3 to 20 carbon atoms include linear olefins and branched olefins having 3 to 20 carbon atoms.
Examples of the linear olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Examples include tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and the like.
Examples of the branched olefin include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1- Examples include pentene.

  Specific combinations of at least two olefins selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms include ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / 4-methyl-1-pentene, ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, ethylene / 1-butene / 1-hexene, propylene / 1-butene, propylene / 1- Examples include hexene, propylene / 1-octene, propylene / 4-methyl-1-pentene, and propylene / 1-butene / 1-hexene.

  Polyolefin (a-1) is a copolymer of at least two olefins selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms, and monomers other than ethylene and α-olefins. It may be a polyolefin-based polymer obtained as described above. Examples of monomers other than ethylene and α-olefin include α, β-unsaturated carboxylic acids described later, metal salts of α, β-unsaturated carboxylic acids, vinyl esters, vinyl ester saponified products, cyclic olefins, and vinyl. Aromatic compounds, polyene compounds, (meth) acrylonitrile, halogenated vinyls, halogenated vinylidenes and the like can be mentioned. You may use these individually or in combination of 2 or more types.

  Examples of the metal salt of α, β-unsaturated carboxylic acid include sodium salt and magnesium salt of (meth) acrylic acid.

  Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is preferred.

  Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5 -Phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2, -Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1, , 3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1 , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -Octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4 , 5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphtha 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methylcyclo Examples include hexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinyl. And naphthalene.

  Examples of the polyene compound include a linear or branched aliphatic conjugated polyene compound, an alicyclic conjugated polyene compound, an aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene compound. Can be mentioned. These may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.

  Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, and 2-hexyl. -1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3-dimethyl -1,3-octadiene, 2,3-dimethyl-1,3-decadiene and the like.

  Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, and 2,3-dimethyl. -1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene, Examples include 2-chloro-1,3-cyclopentadiene and 2-chloro-1,3-cyclohexadiene.

  Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9- Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4- Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4- Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, -Methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4-octadiene 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1, -Nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5 -Nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7 -Nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5 -Decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6 -Decadien, 7-methyl- 1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl- 1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl- 1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene, 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7, 14-hexadecat Ene, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like.

  Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, Cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2 -Ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1, 5-divinylcycloocta 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl- 4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, methyltetrahydroindene and the like can be mentioned.

  Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  The amount of the structural unit derived from ethylene contained in the polyolefin (a-1) is usually 70 mol% or less, preferably 50 mol% or less, from the viewpoint of enhancing the adhesive strength of the resulting aqueous dispersion mixture. More preferably, it is 20 mol% or less, More preferably, it is 0 mol%.

  As the olefin used for the production of the polyolefin (a-1), preferably, the total number of carbon atoms of at least two olefins selected is 6 or more from the viewpoint of enhancing the adhesive strength of the resulting aqueous dispersion mixture. Is a combination of olefins.

  From the viewpoint of further enhancing the adhesive strength of the aqueous dispersion mixture obtained, as the polyolefin (a-1), more preferably at least two selected from the group consisting of propylene and α-olefins having 4 to 20 carbon atoms. Is a polyolefin obtained by copolymerizing propylene and at least one α-olefin having 4 to 20 carbon atoms, and more preferably, for example, propylene / 1-butene copolymer, propylene / 1-hexene copolymer, propylene / 1-octene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 1-butene / 1-hexene copolymer Etc.

The amount of the structural unit derived from propylene contained in the polyolefin (a-1) is usually 50 mol% or more, more preferably 60 mol% or more, from the viewpoint of increasing the adhesive strength of the resulting aqueous dispersion mixture. More preferably, it is 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.
Further, the amount of the structural unit derived from propylene contained in the polyolefin (a-1) is usually 99.9 mol% or less from the viewpoint of increasing the adhesive strength at low temperature of the aqueous dispersion mixture obtained, Preferably it is 99 mol% or less, More preferably, it is 98.5 mol% or less, More preferably, it is 98 mol% or less.

  As a manufacturing method of polyolefin (a-1), the method of manufacturing using a well-known Ziegler-Natta type | mold catalyst and a well-known single site catalyst is mentioned. From the viewpoint of further improving scratch resistance and heat resistance, the production method is preferably a method using a known single site catalyst.

  Examples of the single site catalyst include metallocene catalysts and nonmetallocene complex catalysts. Examples of the metallocene catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. JP, JP 61-130314, JP 3-163088, JP 4-268307, JP 9-12790, JP 9-87313, JP 11-80233. And metallocene catalysts described in JP-A-10-508055 and the like.

  Examples of the nonmetallocene complex catalyst include, for example, JP-A-10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, and JP-T-10-513289. Non-metallocene complex catalysts described in JP-A-10-338706, JP-A-11-71420 and the like can be mentioned.

The single site catalyst is preferably a metallocene catalyst from the viewpoint of easy availability, more preferably at least one cyclopentadiene-type anion skeleton, and a periodic table belonging to Group 3 to C1 having a C1 enantiomeric structure. It is a catalyst obtained by using a Group 12 transition metal complex.
Moreover, as an example of the manufacturing method using a metallocene catalyst, the method of European Patent Application Publication No. 1211287 is exemplified.

  Graft modification is a method in which after polyolefin (a-1) is melted, α, β-unsaturated carboxylic acids are added to perform graft modification, after polyolefin (a-1) is dissolved in a solvent such as toluene or xylene. , Α, β-unsaturated carboxylic acids can be added by known methods such as a method of graft modification.

  The α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids and derivatives thereof. Examples include α, β-unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, citraconic acid and the like; α, β-unsaturated carboxylic acid anhydrides such as anhydrous Maleic acid, itaconic anhydride, citraconic anhydride, etc .; α, β-unsaturated carboxylic acid esters such as methyl maleate, methyl itaconate, methyl citraconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth ) Acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (2-isocyanato) ethyl (meth) acrylate, (dimethylamino) (meth) ) Acrylate, (meth) acrylamide, methacryl Esterified product of alcohol and alcohol, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc .; unsaturated carboxylic acid amides and imides such as (meth) acrylic acid amides, Maleic acid monoamide, maleimide and the like can be mentioned. As α, β-unsaturated carboxylic acids, two or more of these may be used in combination. Among these, α, β-unsaturated carboxylic acid anhydride is preferable, and maleic anhydride is more preferable. In the present invention, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid. Also, acrylate and methacrylate are collectively referred to as (meth) acrylate.

  The structural unit derived from the α, β-unsaturated carboxylic acid in the modified polymer (a-2) (hereinafter referred to as unsaturated carboxylic acid unit) is a structural unit derived from the polyolefin (a-1) (hereinafter referred to as “unsaturated carboxylic acid unit”). The amount is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass (referred to as an olefin unit). The unsaturated carboxylic acid unit in the modified polymer (a-2) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less, relative to 100 parts by mass of the olefin unit. It is. If the unsaturated carboxylic acid unit is 0.1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the olefin unit, the adhesion with the coating film and the stability when dispersed in a solvent are improved. In addition, the unsaturated carboxylic acid unit in the modified polymer (a-2) may be one in which an acid anhydride group is retained or may be ring-opened. It may be both.

  The modified polymer (a-2) preferably has a weight average molecular weight Mw measured by GPC (Gel Permeation Chromatography) and converted by a calibration curve of each polystyrene, preferably 20,000 or more, more preferably 25,000 or more, and further preferably. Is over 30,000. The modified polymer (a-2) has a weight average molecular weight Mw of preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less. If the weight average molecular weight Mw is 20,000 or more and 200,000 or less, the adhesiveness with a base material and a coating film will become favorable.

  The aqueous dispersion (A) is prepared by a method known in the art, for example, a post-emulsification method (for example, forced emulsification) in which a modified polymer (a-2) that is a resin to be emulsified is produced and then the resin is dispersed in an aqueous medium. Method, self-emulsification method, phase inversion emulsification method, etc.). It is also possible to obtain an aqueous dispersion directly if emulsion polymerization or suspension polymerization is used in the production of each resin.

  Specific examples thereof include (1) a method of preparing an aqueous dispersion by preparing a mixture of a resin to be emulsified and water and a solvent other than water in a reactor, and then removing the solvent other than water from the mixture. (2) A method in which the resin to be emulsified is melted at a temperature equal to or higher than the temperature at which the resin to be emulsified is melted in a kneader, and water is added to form a dispersion. (3) An emulsion polymerization method or a suspension polymerization method. Moreover, when preparing a mixture, you may heat and / or stir as needed. Heating is usually performed at 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 70 to 100 ° C. The rotation speed of the stirrer can be performed, for example, at a rotation speed of about 50 to 10000 rpm.

  In the production method of (1) described above, as the reactor, a container (preferably sealed and / or sealed) provided with a heating device capable of being heated and a stirrer capable of applying a shearing force or the like to the contents. Pressure vessel) is used.

  In the production method (2) described above, examples of the kneader include a roll mill, a kneader, an extruder, an ink roll, and a Banbury mixer. In particular, an extruder or a multi-screw extruder having one or more screws in the casing may be used.

  As a method of emulsifying using an extruder, a resin to be emulsified and a surfactant are mixed, and this is continuously fed from the hopper or feed port of the extruder, and this is heated, melted and kneaded, and further compressed by the extruder. Water is supplied from at least one supply port provided in a zone, a metering zone, a degassing zone, and the like, and after kneading with a screw, the water is continuously extruded from a die.

  In general, tap water, ion-exchanged water, or the like is used as water used in the manufacturing method. The water content in the aqueous dispersion (A) is, for example, 30% by weight or more, preferably 35% by weight or more, more preferably 40% by weight or more, and further preferably 45% by weight or more based on the total amount of each aqueous dispersion. is there.

  Examples of the solvent other than water include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and methylene chloride. , Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone and cyclohexanone, methanol, Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, dipropyl ether, dibutyl ether Ethers such as tellurium and tetrahydrofuran, organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol, dimethylformamide And polar solvents such as dimethyl sulfoxide.

  Among these, a solvent that dissolves 1% by mass or more in water is preferable, and more preferably 5% by mass or more. For example, methyl ethyl ketone, methyl propyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, 2- Butanol, isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol are preferred.

  In the aqueous dispersion (A), the ratio of the solvent other than water to water is preferably 50% or less, more preferably 20% or less, still more preferably 10% or less, still more preferably 1% or less, and particularly preferably 0%. It is.

  The volume-based median diameter of the dispersoid contained in the aqueous dispersion (A) thus obtained is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. . Moreover, the lower limit of the volume-based median diameter of the dispersoid contained in the aqueous dispersion (A) is not particularly limited. In the present invention, the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis, and can be measured using, for example, a particle size distribution measuring apparatus.

  The aqueous dispersion (A) preferably has a non-volatile content of 5% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, and usually 60% by mass with respect to the entire aqueous dispersion (A). Contains below. In the present invention, the nonvolatile content is a value obtained by measuring the mass of a residue obtained by removing the solvent from the aqueous dispersion according to JIS K 6828-1.

The polyurethane (b) is a polymer containing a urethane bond in the main chain, and is obtained, for example, by a reaction between a polyol compound and a polyisocyanate compound.
In the present invention, the polyol compound is not particularly limited, and examples thereof include water, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, , 3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexane Low molecular weight glycols such as diol, diethylene glycol, triethylene glycol and dipropylene glycol, low molecular weight polyols such as trimethylolpropane, glycerin and pentaerythritol, polyols having ethylene oxide and propylene oxide units Compounds, polyether diols, high molecular weight diols such as polyester diols, bisphenols such as bisphenol A, bisphenol F, dimer diol or the like carboxyl group was converted to a hydroxyl group of the dimer acid.

  In addition, as the polyisocyanate compound, one or a mixture of two or more known aromatic, aliphatic and alicyclic diisocyanates can be used. Specific examples of diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, dimethyl diisocyanate, lysine diisocyanate. , Hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and adducts, biurets, and isocyanurates thereof. As the diisocyanates, trifunctional or higher functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate may be used.

  Further, in the production of the polyurethane (b), an active hydrogen which is a compound different from the hydrophilic group-containing compound and can react with an isocyanate compound in the molecule for the purpose of chain extension, molecular weight adjustment, etc., if necessary. You may use the compound containing this. Examples of such compounds include polyvalent amine compounds such as ethylenediamine, 1,4-butanediamine, and 1,6-hexanediamine; tertiary amine-containing polyhydric alcohols such as triethanolamine, methanol, ethanol, and butanol. Examples include monoalcohols.

  A commercially available product can be used as the aqueous polyurethane dispersion (B) suitable for the present invention. Examples of such commercially available aqueous dispersions of polyurethane include Adekabon titer HUX series manufactured by ADEKA Co., Ltd., Dispacol series manufactured by Sumika Bayer Urethane Co., Ltd., and Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. It is done.

  The volume-based median diameter of the dispersoid contained in the aqueous dispersion (B) thus obtained is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. . Further, the lower limit of the volume-based median diameter of the dispersoid contained in the aqueous dispersion (B) is not particularly limited.

  The aqueous dispersion (B) preferably contains a nonvolatile content of 15 to 70% by weight, more preferably 25 to 60% by weight.

  In the production process of the aqueous dispersion (A) or (B), in addition to the resin, water and a solvent other than water, additional resins, surfactants, basic compounds, thickeners, dispersants, curing agents, pigments, Appropriate amounts of optional components such as viscosity modifiers and additional solvents can be added at any time. These components can also be added after mixing the aqueous dispersions (A) and (B).

  Further resins include, for example, polyolefin resins different from polyolefin (a-1), acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate ( Examples thereof include polymers such as PVAc), polytetrafluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), AS resin, copolymers, and modified products thereof. These may be used alone or in combination of two or more. As the polyolefin-based resin different from the polyolefin (a-1), a crystalline polyolefin-based resin can be used as long as the content of the polyolefin (a-1) in the aqueous dispersion mixture of the present invention is not exceeded. . Moreover, you may use resin which exhibits the function as an adhesive resin or a tackifier. Examples of such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins and indene resins, and polyurethane resins of a type different from polyurethane (b).

  Specifically, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and ester thereof Terpenes such as terpenes; terpene polymers, terpene phenols, β-pinene polymers, aromatic-modified terpene polymers, α-pinene polymers, terpene-based hydrogenated resins, etc .; petroleum fractions having 5 carbon atoms Petroleum resins obtained by polymerizing petroleum resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms and hydrogenated resins thereof; petroleum resins such as maleic acid-modified products and fumaric acid-modified products

  Examples of the surfactant include cationic, anionic, amphoteric and nonionic surfactants. Among them, anionic or nonionic surfactants are preferable. Surfactants may be used alone or in combination of two or more.

  Examples of anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyls. Examples include sulfosuccinate.

  Examples of cationic surfactants include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkyl Examples include ammonium salts, allyltrialkylammonium salts, diallyldialkylammonium salts, and the like.

  Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, Examples thereof include a compound having a polyoxyethylene structure such as an ethylene oxide-propylene oxide copolymer, and a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester.

  Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.

  As a basic compound, what can neutralize a carboxyl group is preferable, for example, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned. Preferably, it is ammonia or an organic amine compound. In particular, organic amine compounds having a boiling point of 200 ° C. or less can be easily dispersed by ordinary drying, and maintain the water resistance and alkali resistance of the coating film when an aqueous dispersion mixture is used to form the coating film. Can be improved. Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. Of these, N, N-dimethylethanolamine and the like are preferable. Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.

  As a thickener, it can be used to adjust the viscosity of the formulation. As a thickener, manufactured by ADEKA Corporation; Adecanol UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH-541VF , UH-550, UH-752, H-756VF, manufactured by San Nopco; SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-818 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050 and the like.

  As a dispersant, it can be used for improving the wettability of the coated substrate. As the dispersant, manufactured by ADEKA Corporation; Adeka Coal W-193, W-287, W-288, W-304, manufactured by BYK; BYK-333, BYK-345, BYK-346, BYK-347, BYK- 348, BYK-349, BYK-378, manufactured by San Nopco; Nopco wet 50, SN wet 366, Nopco 38-C, SN disperse sand 5468, 5034, 5027, 5040, 5020 and the like.

  As the curing agent, an isocyanate-based and / or carbodiimide-based curing agent can be used. Examples thereof include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and oligomers or polymers thereof, which are isocyanate-based curing agents. Specifically, Sumika Bayer Urethane Sumidur 44V20, Sumidur N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and the like can be mentioned. . Examples of the carbodiimide-based curing agent include a carbodilite series (Nisshinbo Chemical Co., Ltd.). 0.1-20 weight part is preferable with respect to 100 weight part of resin which comprises an aqueous dispersion mixture, and, as for a hardening | curing agent, 0.1-10 weight part is more preferable. The curing agent may be added after being dissolved in an organic solvent.

  Examples of the pigment include inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, perinone pigments, perylene pigments, and quinacridone pigments. Color pigments such as organic pigments such as pigments, isoindolinone pigments, indigo pigments, phthalocyanine pigments; extender pigments such as talc, calcium carbonate, clay, kaolin, silica, precipitated barium sulfate; conductive carbon, antimony-doped Examples include conductive pigments such as whiskers coated with tin oxide; non-colored or colored metallic luster such as metals or alloys such as aluminum, copper, zinc, nickel, tin, and aluminum oxide. Two or more kinds may be used in combination.

  When a pigment is used, a pigment dispersant may be used. For example, an aqueous acrylic resin such as John Kuril manufactured by BASF Japan; an acidic block copolymer such as BYK-190 manufactured by BYK; a styrene-maleic acid copolymer; Surfynol manufactured by Air Products (Air Products) Examples thereof include acetylene diol derivatives such as T324; water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Co., Ltd. By using these pigment dispersants, a pigment paste in which pigment dispersion is stable can be prepared.

  The viscosity modifier is an agent added to appropriately adjust the viscosity of the aqueous dispersion, and can be used within a range that does not significantly reduce the performance of the present invention. Although it does not restrict | limit especially as an example of a viscosity modifier (D), For example, BYK-420, BYK-425 (made by BYK company) etc. are mentioned.

  Further solvents include, for example, aromatic hydrocarbons such as water, toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and methylene chloride. , Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone and cyclohexanone, methanol, Ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol and other alcohols, dipropyl ether, dibutyl ether And ethers such as tetrahydrofuran and tetrahydrofuran, organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, dimethylformamide And polar solvents such as dimethyl sulfoxide.

  In addition to the above components, a phenol-based stabilizer, a phosphite-based stabilizer, an amine-based stabilizer, an amide-based stabilizer, and an anti-aging agent are added as necessary as long as the intended properties of the aqueous dispersion mixture of the present invention are not impaired. Stabilizers such as weathering stabilizer, anti-settling agent, antioxidant, heat stabilizer, light stabilizer; thixotropic agent, thickener, dispersant, antifoaming agent, weathering agent, antistatic agent, lubricant, nucleus Additives, flame retardants, oils, dyes, curing agents, crosslinking agents, etc .; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, Responsible for inorganic and organic fillers such as kaolin, finely divided silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, and celite It may contain a component.

  In the aqueous dispersion mixture of the present invention, the aqueous dispersion (B) preferably has a nonvolatile content of 65 parts by mass or more, more preferably 75 parts by mass or more, with respect to 100 parts by mass of the nonvolatile content of the aqueous dispersion (A). More preferably, the content is 85 parts by mass or more. The aqueous dispersion (B) preferably has a nonvolatile content of 200 parts by mass or less, more preferably 160 parts by mass or less, and still more preferably 120 parts by mass with respect to 100 parts by mass of the nonvolatile content of the aqueous dispersion (A). Contains the following.

  In the present invention, the dispersoid of the aqueous dispersion (A) is preferably a self-emulsified product of the modified polymer (a-2). Therefore, the modified polymer (a-2) preferably has self-emulsifying properties. When the modified polymer (a-2) has self-emulsifying properties, it is advantageous because the aqueous dispersion (A) can be produced without using an emulsifier or a dispersant.

  The aqueous dispersion mixture of the present invention is obtained by mixing the aqueous dispersions (A) and (B). It does not specifically limit as a mixing method, A conventionally well-known method can be used. For example, the aqueous dispersions (A) and (B) can be charged into a container equipped with a stirrer and stirred. At this time, components other than the resin, water, and a solvent other than water may be added. Further, water may be further added.

  The aqueous dispersion mixture of the present invention thus obtained is dried and / or at a relatively low temperature, for example at a temperature of 20 ° C to 140 ° C, preferably 40 ° C to 120 ° C, more preferably 60 ° C to 100 ° C. Even when treatment such as curing is performed, excellent adhesion to various substrates and various paints can be exhibited. Therefore, it is useful for various applications. For example, it can be used as it is as a water-based adhesive or primer, and it can also be used together with other components in a water-based coating composition, water-based adhesive, or primer composition.

  For example, in the case of an aqueous coating composition, the aqueous coating composition is applied to a substrate, and the temperature is 20 ° C to 140 ° C, preferably 40 ° C to 120 ° C, more preferably 60 ° C to 100 ° C, for 1 minute to 1 hour. Preferably, the coating film can be formed on the substrate by heating for 3 minutes to 30 minutes.

  For example, in the case of a primer and a primer composition, after forming a coating film of the primer and the primer composition by drying and curing at a temperature of room temperature to 100 ° C. as necessary, another paint or the like is applied on the coating film. The coating is applied by heating at a temperature of 20 ° C. to 140 ° C., preferably 40 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C. for 1 minute to 1 hour, preferably 3 minutes to 30 minutes. A film can be formed.

  For example, in the case of a water-based adhesive, the water-based adhesive is applied to one or both surfaces of the base material, and after drying and curing at a temperature of room temperature to 100 ° C. as necessary, the two base materials are bonded together. The substrate can be bonded by treating at an appropriate temperature.

  Examples of the substrate include polyolefins such as olefin polymers, polyamide, unsaturated polyester, polybutylene terephthalate, polycarbonate, vinyl chloride, polyester, polyurethane, paper, synthetic paper, wood, woven fabric, knitted fabric, and non-woven fabric. Widely popular base materials made of metal components (including iron, aluminum, copper, nickel, silver, gold, platinum, various alloys, etc.), wood (including pulp, paper, etc.), stones, etc. Can be mentioned. Examples of the polyolefins include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, ethylene / propylene copolymer, ethylene / butene copolymer, propylene / ethylene. Examples thereof include copolymers and propylene / butene copolymers, and polyolefins having a polypropylene crystal structure are preferred.

  Further, the shape of the substrate is not particularly limited, such as a film, a sheet, or a plate-like body. Further, it may be a molded body obtained by a known molding method such as injection molding, compression molding, hollow molding, extrusion molding, or rotational molding. Moreover, the molded object may contain the inorganic filler component, the pigment, etc. Examples include plate fillers such as talc, mica, and montmorillonite; fiber fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, and zonolite; potassium titanate, magnesium Needle-shaped fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Examples include granular fillers; balun fillers such as glass balloons; and inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate.

  Furthermore, when the substrates are bonded using the aqueous dispersion mixture of the present invention, excellent adhesion is exhibited whether the substrates are made of the same material or substrates of different materials. To do. In particular, it is suitable for lamination of a polyurethane resin film and a polyolefin resin film, lamination of a polyurethane resin film and a polyester resin film, lamination of a polyurethane resin film and a metal, and the like.

  Examples of the paint include a colored base paint and a clear paint. These may be aqueous or organic solvent-based, and may contain various resins such as olefin polymers and various pigments.

  The method for applying the aqueous dispersion mixture to the substrate is not particularly limited, and any known method can be used. For example, air spray method, airless spray method, gravure roll coating, reverse roll coating, wire bar Examples thereof include coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, and brush coating.

  Drying, curing, and heating can be performed by, for example, a conventionally used method and apparatus, for example, using nichrome wire, infrared rays, high frequency, or the like.

  The thickness (after curing) of the coating film to be formed is appropriately selected depending on the material and shape of the base material, the composition of the paint used, etc., and is usually 0.1 μm to 500 μm, preferably 1 μm to 300 μm, more preferably 5 μm to 200 μm. It is.

  The aqueous dispersion mixture of the present invention is particularly suitable for production of a laminate because it is excellent in adhesion between substrates.

  Coating films, laminates and coated articles using the aqueous dispersion mixture of the present invention can be used for various industrial parts such as automobiles, home appliances, and building materials, and in particular, thin parts, highly functional parts, and large-sized parts / It has sufficient performance for practical use as a material. For example, automotive parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tubs, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, toilet seat lids, toiletries such as water tanks, bathtubs It can be used as molding materials for various industrial parts such as bathroom walls, ceilings, drain pans and other parts around the bathroom.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example.

(1) Content of unsaturated carboxylic acid unit The graft amount of maleic anhydride in the modified polymer was determined by dissolving 1.0 g of a sample in 20 ml of xylene and dropping the sample solution into 300 ml of methanol while stirring. After collecting by precipitation, the collected sample was vacuum-dried (80 ° C., 8 hours), then a film having a thickness of 100 μm was prepared by hot pressing, and an infrared absorption spectrum of the obtained film was measured, and 1780 cm ^{− The} amount of maleic anhydride graft was quantified from the absorption near ¹ .
For the modified species other than maleic anhydride, which could not be measured by infrared absorption spectrum, the graft amount was quantified by ¹ H-NMR.

(2) Crystal melting peak and crystallization peak It measured on condition of the following using the differential scanning calorimeter (Seiko Electronics Co., Ltd. DSC220C: input compensation DSC).
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. Whether or not a crystallization peak was observed at this time, and if it was observed, the presence or absence of a crystallization peak having a peak area, that is, a crystallization heat amount of 1 J / g or more was confirmed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. At this time, whether or not a melting peak of the crystal was observed, and if it was observed, the presence or absence of a crystal melting peak having a peak area, that is, a crystal melting heat amount of 1 J / g or more was confirmed.

(2) Weight average molecular weight Mw
The measurement was carried out by the gel permeation chromatograph (GPC) method under the following conditions.
Device: HLC-8121GPC / HT manufactured by Tosoh Corporation
Column: Tosoh Corporation TSKgel GMHHR-H (S) HT 4 temperature: 145 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 300 μl
Molecular weight standard: Standard polystyrene Detector: Differential refraction

  When calculating the weight average molecular weight (Mw) and the number average molecular weight (Mn), a commercially available monodisperse polystyrene standard sample is measured as a standard sample, and a calibration curve is created from the retention time and molecular weight of the standard sample. It was.

(3) Volume-based median diameter
The volume-based median diameter is a particle diameter corresponding to a cumulative particle diameter distribution value of 50% on a volume basis, and means a median diameter measured on a volume basis unless otherwise specified. The volume-based median diameter of the dispersoid can be measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation.

(4) Nonvolatile content The solvent was removed from the aqueous dispersion, and the mass of the residue was measured as the nonvolatile content (according to JIS K 6828-1).

(5) Peel strength The test coating was cut out with a width of 10 mm, and the peel strength of the coating film was measured at a tensile speed of 50 mm / min and a tensile angle of 180 degrees using a tensile tester (manufactured by Shimadzu Corporation).

[Preparation of Aqueous Dispersion A-1]
In a 3000 ml separable flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, an amorphous polyolefin [propylene / 1-butene copolymer (propylene: 1-butene = 96 mol%: 4 mol%), Mw = 400,000, a crystal melting peak with a heat of crystal melting of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more are not observed in the temperature range of −100 ° C. to 200 ° C. by DSC. The mixture was melted in an oil bath maintained at 140 ° C. under a nitrogen atmosphere, and the temperature of the oil bath was adjusted so that the temperature in the system was 140 ° C. while stirring. After the system melted, 40 g of dodecyl methacrylate and 20 g of maleic anhydride were added while stirring to obtain a uniform state, and then 2 g of perbutyl D was added. The reaction was carried out for 5 hours while maintaining the system at 140 ° C., and then low-molecular volatile substances such as xylene, unreacted dodecyl methacrylate and maleic anhydride were removed while reducing the pressure in the flask with an aspirator. After completion of the decompression, the reaction product was taken out and cooled to obtain a modified polyolefin solid product.

  100 g of the modified polyolefin obtained above was put in a separable flask equipped with a stirrer, a thermometer and a reflux condenser and melted in an oil bath maintained at 100 ° C., and then 20 g of 2-butanol and 5 g of dimethylaminoethanol. Was added and stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (A-1) having a modified polyolefin as a dispersoid.

[Preparation of Aqueous Dispersion A-2]
In a 3000 ml separable flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, a crystalline polyolefin [ethylene / propylene copolymer (ethylene: propylene = 15 mol%: 85 mol%), Mw = 55,000, Melting point = 70 ° C.] 200 g and 200 g of xylene were added, melted in an oil bath maintained at 170 ° C. in a nitrogen atmosphere, and the temperature of the oil bath was adjusted to 140 ° C. while stirring. . After the system was melted, 20 g of dodecyl methacrylate and 10 g of maleic anhydride were added while stirring to obtain a uniform state, and then 2 g of perbutyl D was added. The reaction was carried out for 5 hours while maintaining the system at 140 ° C., and then low-molecular volatile substances such as xylene, unreacted dodecyl methacrylate and maleic anhydride were removed while reducing the pressure in the flask with an aspirator. After completion of the decompression, the reaction product was taken out and cooled to obtain a modified polyolefin solid product.

100 g of the modified polyolefin obtained above was put in a separable flask equipped with a stirrer, a thermometer, and a reflux condenser and melted in an oil bath maintained at 100 ° C., and then 20 g of 2-butanol and 5 g of dimethylaminoethanol. Was added and stirred and mixed. After melt mixing, ion exchange water at 80 ° C. was added little by little with vigorous stirring. When 200 g of ion-exchanged water was added, the contents were taken out and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (A-2) having a modified polyolefin as a dispersoid.

[Aqueous Dispersion B-1]
Dispacol U-54 commercially available from Sumika Bayer Urethane Co., Ltd. (non-volatile content 50% by mass, moisture 50% by mass).

[Aqueous dispersion B-2]
Dispacol U-42 (nonvolatile content 50 mass%, moisture 50 mass%) commercially available from Sumika Bayer Urethane Co., Ltd.

[Aqueous dispersion B-3]
Buy Bond PU-407 (nonvolatile content concentration 40 mass%, moisture 60 mass%) commercially available from Sumika Bayer Urethane Co., Ltd.

Examples 1 to 3 and Comparative Example 1
Each aqueous dispersion was mixed at room temperature so that the non-volatile content of each aqueous dispersion obtained as described above was in parts by mass shown in Table 1 below, to obtain an aqueous dispersion mixture.

Example 4
The aqueous dispersion mixture prepared in Example 1 above was applied to a polypropylene substrate (after degreasing treatment) with a wire bar so that the dry film thickness was about 10 μm, and dried by heating at 50 ° C. for 5 minutes. Thereafter, an acrylic urethane paint “Polynal No. 800” (manufactured by Ohashi Chemical Industry Co., Ltd.) is spray-coated on the film so as to have a dry film thickness of about 100 μm, and dried by heating at 60 ° C. for 30 minutes. Was made.

Examples 5 to 6 and Comparative Example 2
Instead of the aqueous dispersion mixture used in Example 4 above, each test paint was treated in the same manner as in Example 4 except that the aqueous dispersion mixture prepared in Examples 2-3 and Comparative Example 1 was used. Produced.

  The peel strength of the test paints obtained in Examples 4 to 6 and Comparative Example 2 was measured according to the measurement method and the evaluation method described above. The results are shown in Table 2 below.

  As shown in Table 2, it is understood that the aqueous dispersion mixture of the present invention exhibits high peel strength even when baked at 60 ° C. and is excellent in adhesiveness at low temperatures.

  Instead of the aqueous dispersion B-1 used in Example 1, an aqueous dispersion mixture can be prepared using the following aqueous dispersions B-4 to B-13, and the resulting aqueous dispersion mixture is used. When coated in the same manner as in Example 4, excellent adhesiveness is exhibited at low temperatures.

[Aqueous dispersion B-4] Adekabon titer HU-320 (nonvolatile content: 32% by mass) commercially available from ADEKA Corporation
[Aqueous dispersion B-5] Adekabon titer HU-350 (nonvolatile content concentration 30% by mass) commercially available from ADEKA Corporation
[Aqueous Dispersion B-6] Adekabon titer HU-386 (nonvolatile content concentration 30% by mass) commercially available from ADEKA Corporation
[Aqueous Dispersion B-7] Adekabon titer HU-401 (nonvolatile content concentration: 37% by mass) commercially available from ADEKA Corporation
[Aqueous Dispersion B-8] Superflex 130 (nonvolatile content 35% by mass) commercially available from Daiichi Kogyo Seiyaku Co., Ltd.
[Aqueous Dispersion B-9] Superflex 150 (Non-volatile content: 30% by mass) commercially available from Daiichi Kogyo Seiyaku Co., Ltd.
[Aqueous Dispersion B-10] Superflex 170 (nonvolatile content concentration 33% by mass) commercially available from Daiichi Kogyo Seiyaku Co., Ltd.
[Aqueous Dispersion B-11] Superflex 210 (nonvolatile content 35% by mass) commercially available from Daiichi Kogyo Seiyaku Co., Ltd.
[Aqueous dispersion B-12] Superflex 470 (nonvolatile content concentration 38% by mass) commercially available from Daiichi Kogyo Seiyaku Co., Ltd.
[Aqueous Dispersion B-13] Superflex 500M (nonvolatile content concentration 45% by mass) commercially available from Daiichi Kogyo Seiyaku Co., Ltd.

  The aqueous dispersion mixture of the present invention not only exhibits excellent adhesion to substrates made of polyolefins, but also exhibits high adhesion to substrates and coatings made of substances other than polyolefins. . The aqueous dispersion mixture of the present invention can exhibit good adhesion even when treated at a low temperature of about 60 ° C. Therefore, the aqueous dispersion mixture of the present invention can be suitably used for a primer, a coating composition, an adhesive and the like.

Claims (8)

An aqueous dispersion mixture containing an aqueous dispersion (A) and an aqueous dispersion (B),
The aqueous dispersion (A) is obtained by dispersing a modified polymer (a-2) obtained by graft-modifying a polyolefin (a-1) having substantially no melting point peak with α, β-unsaturated carboxylic acids. Including as
The aqueous dispersion (B) uses polyurethane (b) as a dispersoid.
Aqueous dispersion mixture.   The aqueous dispersion mixture according to [1], containing 65 to 200 parts by mass of the nonvolatile content of the aqueous dispersion (B) with respect to 100 parts by mass of the nonvolatile content of the aqueous dispersion (A).   The structural unit derived from the α, β-unsaturated carboxylic acids in the modified polymer (a-2) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the structural unit derived from the polyolefin (a-1). The aqueous dispersion mixture according to claim 1 or 2, wherein   The aqueous dispersion mixture according to any one of claims 1 to 3, wherein the modified polymer (a-2) has a weight average molecular weight Mw of 20,000 to 200,000.   The aqueous dispersion mixture according to any one of claims 1 to 4, wherein the dispersoid of the aqueous dispersion (A) has a volume-based median diameter of 1 µm or less.   The aqueous dispersion mixture according to any one of claims 1 to 5, wherein the dispersoid of the aqueous dispersion (A) is a self-emulsified product of the modified polymer (a-2).   The aqueous adhesive containing the aqueous dispersion mixture in any one of Claims 1-6.   A laminate having a layer adhered by the aqueous adhesive according to claim 7.