JP2016060899A - Polyolefin resin aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin aqueous dispersion realizing a dry coat excellent in mechanical strength, solvent resistance and water resistance, as well as having excellent dispersion stability without a dispersant.SOLUTION: A polyolefin resin aqueous dispersion contains an aqueous medium (M), and a polyolefin resin (P3) obtained by reacting a polyamine (A) represented by the general formula (1) with a polyolefin resin (P2) having a carboxylic acid anhydride group. [Rand Rare each independently a C2-10 alkylene group; a is an integer from 1 to 5; and X is a monovalent polyoxyalkylene group (where the alkylene has 2-12 carbon atoms) including an oxyethylene group as an essential constitutional unit.]SELECTED DRAWING: None

Description

  The present invention relates to aqueous dispersions of polyolefin resins, especially binders, primers, coating agents, adhesives and glass fibers for paints and inks used in various fields such as automobiles, electrical / electronic products, construction and packaging materials. The present invention relates to an aqueous polyolefin resin dispersion that can be suitably used as a sizing agent or the like.

Polyolefin resin aqueous dispersions have excellent adhesion to polypropyne substrates, electrical properties, mechanical properties, and chemical properties. Therefore, adhesives, binders and primers for paints and inks are used in various fields such as automobiles and home appliances. It is expected to be applied to
For example, an aqueous emulsion having a copolymer of ethylene, vinylcyclohexane and unsaturated carboxylic acids as a dispersoid is disclosed (see Patent Document 1).
However, since the aqueous dispersion described in Patent Document 1 uses a surfactant for the purpose of improving the dispersion stability, there is a problem that the water resistance of the coating film decreases and the surfactant bleeds out from the coating film. was there.
Moreover, in patent document 1, the polyolefin-type resin bridge | crosslinked from the viewpoint of emulsification dispersibility cannot be used, but there existed a problem that it was inferior to the mechanical strength of a membrane | film | coat, and solvent resistance.

JP 2005-320400 A

  The present invention has been made in view of the above problems, and an object of the present invention is an excellent polyolefin-based resin aqueous solution having excellent dispersion stability without a dispersant and excellent mechanical strength, solvent resistance and water resistance of a dry film. It is to provide a dispersion.

［式中、Ｒ^１及びＲ^２はそれぞれ独立に炭素数２〜１０のアルキレン基を表し、ａは１〜５の整数を表し、Ｘはオキシエチレン基を必須構成単位とする１価のポリオキシアルキレン（アルキレンの炭素数２〜１２）基を示す。］ The inventor of the present invention has arrived at the present invention as a result of intensive investigations to achieve the above object. That is, the present invention provides a polyolefin resin (P3) and an aqueous medium (M) obtained by reacting the polyamine (A) represented by the general formula (1) with a polyolefin resin (P2) having a carboxylic anhydride group. Is an aqueous polyolefin-based resin dispersion.

[Wherein, R ¹ and R ² each independently represents an alkylene group having 2 to 10 carbon atoms, a represents an integer of 1 to 5, and X represents a monovalent polyoxy having an oxyethylene group as an essential constituent unit. An alkylene (C2-C12 alkylene) group is shown. ]

  The aqueous polyolefin-based resin dispersion of the present invention is excellent in dispersion stability and excellent in mechanical strength, solvent resistance and water resistance.

  The aqueous polyolefin resin dispersion (E2) of the present invention contains a polyolefin resin (P3) and an aqueous medium (M).

    The polyolefin resin (P2) having a carboxylic anhydride group of the aqueous polyolefin resin dispersion (E2) of the present invention is mainly composed of a modifiable polyolefin resin (preferably a content of 50% by weight or more, more preferably May be 75% by weight or more, particularly preferably 80 to 100% by weight) of the polyolefin resin (P1) into which a carboxylic acid anhydride group has been introduced.

The polyolefin resin (P1) mainly composed of a denatured polyolefin resin is one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). (Co) polymerization [(Co) polymerization means polymerization or copolymerization. The same applies below. ] Obtained by (polymerization method) and degraded polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefin mechanically, thermally or chemically Degraded (degradation method)} is included.
Of these, from the viewpoint of ease of modification and availability in introducing a carboxyl group, preferred is a degraded polyolefin, and more preferred is a thermally degraded polyolefin. According to the thermal degradation, a low molecular weight polyolefin having an average number of double bonds per molecule of 1.5 to 2 can be easily obtained as described later, and the low molecular weight polyolefin introduces a carboxylic anhydride group. It is easy to denature.

Mn of the polyolefin resin in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSKgelGMHXL” [manufactured by Tosoh Corporation] (two)
“TSKgelMultiporeHXL-M” [manufactured by Tosoh Corporation] (1 pc.)
Sample solution: 0.3 wt% orthodichlorobenzene solution solution injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The heat-degraded polyolefin is not particularly limited, and is obtained by heating a high molecular weight polyolefin in an inert gas (at 300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). And those obtained by heat degradation by heating in air.

The high molecular weight polyolefin used in the thermal degradation method is a (co) polymer of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). [Mn is preferably 12,000 to 100,000, more preferably 15,000 to 70,000. The melt flow rate (hereinafter abbreviated as MFR. The unit is g / 10 min) is preferably 0.5 to 150, more preferably 1 to 100. ] Etc. are mentioned. Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. The MFR measurement method conforms to the method defined in JIS K7210. For example, in the case of polypropylene, it is measured under conditions of 230 ° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.
Examples of the α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icocene and 1-icosene. Tetracocene and the like can be mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of molecular weight control, and ethylene, Propylene, C 4-10 α-olefin, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, 1-butene, butadiene and mixtures thereof.

Mn of the polyolefin resin (P1) is preferably 800 to 20,000, more preferably 900 to 10,000, and particularly preferably 1,000 to 10,000 from the viewpoint of emulsification dispersibility and mechanical strength of the dry film. 6,000.
The number of double bonds in (P1) is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 20 from the viewpoint of viscosity during reaction and mechanical strength of the dry film. Especially preferably, it is 3-10 pieces.

(P1) The average number of double bonds per molecule is preferably 1.5 to 2.5, more preferably 1.8 to 2.1, from the viewpoints of viscosity during reaction and mechanical strength of the dried film. 2, particularly preferably 1.9 to 2.1, most preferably 2.
When a method for obtaining a low molecular weight polyolefin by a thermal degradation method is used, (P1) having an average number of double bonds per molecule of 1.5 to 2 can be easily obtained in the range of Mn 800 to 6,000. [Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].
As the polyolefin resin (P2) having a carboxylic acid anhydride group, a polyolefin having a structure obtained by modifying (P1) with an α, β-unsaturated dicarboxylic acid anhydride can be used.

Examples of the α, β-unsaturated dicarboxylic acid anhydride used for modification include maleic acid anhydride, itaconic acid anhydride, and citraconic acid anhydride. Of these, maleic anhydride is preferred from the viewpoint of ease of modification.

The amount of the α, β-unsaturated carboxylic acid anhydride used for modification is preferably 0.5 to 40 based on the weight of the polyolefin resin (P1), from the viewpoint of adhesion to a polypropylene substrate and emulsification dispersibility. % By weight, more preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight.

Modification by α, β-unsaturated carboxylic acid anhydride is, for example, addition reaction of α, β-unsaturated carboxylic acid anhydride to the double bond of (P1) by either the solution method or the melting method. (Ene reaction), and the reaction temperature is preferably 170 to 230 ° C.

Mn of the polyolefin resin (P2) having a carboxylic acid anhydride group is preferably 900 to 25,000, more preferably 1,000 to 20, from the viewpoints of emulsifying dispersibility and mechanical strength of the dry film. 000, particularly preferably 1,100 to 10,000.
The acid value of (P2) is preferably 4 to 280 mgKOH / g, more preferably 10 to 100 mgKOH / g, particularly preferably from the viewpoint of the reactivity with (b) and the thermoplasticity of the block polymer (A). 15-80 mg KOH / g.

The polyolefin-based resin (P3) having an amino group is a polyolefin-based resin obtained by reacting the polyolefin-based resin (P2) having a carboxylic acid anhydride group with the polyamine (A) represented by the general formula (1). .

R ¹ and R ² in the general formula (1) each independently represent an alkylene group having 2 to 10 carbon atoms, a represents an integer of 1 to 5, and X represents a monovalent having oxyethylene as an essential constituent unit. A polyoxyalkylene (alkylene having 2 to 12 carbon atoms) chain is shown.

R ¹ and R ² are preferably an ethylene group, a 1,3-propylene group, a 1,4-butylene group, and a 1,5-pentylene group from the viewpoint of emulsion dispersibility.

  a usually represents an integer of 1 to 5, preferably 1 to 3, more preferably 1 from the viewpoint of water resistance of the dry film.

  X is preferably a structure represented by the general formula (2) from the viewpoint of the emulsifying dispersibility of the polyolefin resin (P3) and the mechanical strength of the dry film.

  In general formula (2), b is usually an integer of 5 to 200, and 40 to 200 is preferable from the viewpoint of achieving both emulsifying dispersibility and water resistance. When b is smaller than 5, the emulsifying dispersibility is not sufficiently exhibited. Moreover, when larger than 200, water resistance falls.

  C in General formula (2) is an integer of 0-195 normally, 0-50 are preferable from a viewpoint of emulsification dispersibility, More preferably, it is 0. When it is larger than 195, the emulsifying dispersibility is not sufficiently exhibited.

  b and c satisfy 5 ≦ b + c ≦ 200, and when c is 1 or more, the bonding form of b oxyethylene groups and c oxyalkylene groups (AO) may be random, block, or a combination thereof. From the viewpoint of ensuring emulsification and dispersibility without impairing water resistance, the block format is preferred, and the terminal block, that is, the block farthest from the nitrogen atom in the general formula (2) is more preferably polyoxy It is a block of ethylene.

  AO in the general formula (2) is an oxyalkylene group having 3 to 12 carbon atoms, and when there are a plurality of AOs, they may be the same or different, and the emulsifying dispersibility of the polyolefin-based resin (P3) having an amino group From the viewpoint, an oxyalkylene group having 1 to 5 carbon atoms is preferable.

  Polyamine (A) is, for example, poly (n = 2-6) alkylene (2 to 10 carbon atoms) poly (n = 3-7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepenta Ethylene oxide (hereinafter referred to as EO) as an essential component of the imino group in which the amino group of amine, pentaethylenehexamine and hexaethyleneheptamine is ketiminated with ketones [methyl ethyl ketone (hereinafter abbreviated as MEK) and methyl isobutyl ketone, etc.] And a C3-12 alkylene oxide as an optional component by ring-opening addition, and hydrolyzing the ketiminated moiety to regenerate the amino group.

  Examples of the alkylene oxide having 3 to 12 carbon atoms include 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran (Hereinafter abbreviated as THF), 3-methyltetrahydrofuran, α-olefin oxide, styrene oxide, epihalohydrin (eg, epichlorohydrin) and the like, and alkylene oxides having 1 to 5 carbon atoms are preferable from the viewpoint of moisture permeability. A C3-C12 alkylene oxide may be used individually by 1 type, or may use 2 or more types together.

  The addition form of EO and the alkylene oxide having 3 to 12 carbon atoms may be random addition, block addition or a combination thereof, but from the viewpoint of ensuring moisture permeability without impairing waterproofness, block addition is more preferable. The block at the end, that is, the block farthest from the nitrogen atom in the general formula (2) is due to the block addition of EO.

  The polyamine (A) of the present invention may be used alone or in combination of two or more.

  The weight of the oxyethylene group in the polyamine (A) is 10 based on the total weight of the polyamine (A) and the polyolefin resin (P2) from the viewpoint of emulsion dispersibility of the polyolefin resin (P3) having an amino group. It is preferably ˜50% by weight, more preferably 15 to 45% by weight, and particularly preferably 17 to 42% by weight.

  The polyamine (A) has a chain extender (a1) and necessary as long as the emulsifying dispersibility of the polyolefin-based resin (P3) having an amino group and the adhesion of the aqueous polyolefin-based resin dispersion to the polypropylene substrate can be secured. The reaction terminator (a2) can be contained. (A1) and (a2) may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of the chain extender (a1) include diamines having 2 to 10 carbon atoms (for example, ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine and piperazine), poly (n = 2 to 6) alkylene (2 to 2 carbon atoms). 6) Poly (n = 3-7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, etc.), hydrazine or its derivatives (dibasic) Acid dihydrazide such as adipic acid dihydrazide).

  The chain extender (a1) is preferably a diamine having 2 to 10 carbon atoms from the viewpoint of synthesis.

  As the reaction terminator (a2), monoamines having 1 to 10 carbon atoms (mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, monoethanolamine, diethanolamine and diisopropanolamine) Mono- or dialkanolamine, etc.) and amino alcohols having 2 to 10 carbon atoms (for example, ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine).

  The amount of the polyamine (A) is preferably such that the number of moles of amino groups in (A) is 1.1 to 3.0 times the number of moles of carboxylic anhydride groups of the polyolefin resin (P2). From the viewpoint of adhesion to a polypropylene base material and emulsifying dispersibility, it is preferably 1.2 to 2.5 times, more preferably 1.3 to 2.4 times, and particularly preferably 1.4 to 2.3. Is double.

Mn of the polyolefin resin (P3) having an amino group is preferably 1,100 to 40,000 from the viewpoint of the emulsifying dispersibility of (P3) and the mechanical strength of the dry film of the polyolefin resin dispersion, More preferably, it is 1,200-30,000, Most preferably, it is 1,300-20,000.

The polyolefin resin (P3) having an amino group needs to have an amino group in order to react with the compound (B) having reactivity with the amino group. The amine value of (P3) is preferably 4 to 280 mgKOH / g, more preferably 10 to 100 mgKOH / g, particularly from the viewpoint of emulsifying dispersibility and the mechanical strength of the dry film of the polyolefin resin aqueous dispersion (E2). Preferably it is 15-80 mgKOH / g.

  The reaction between the polyolefin resin (P2) having a carboxylic acid anhydride group and the polyamine (A) can be carried out by either a solution method or a melting method, and the reaction temperature is preferably 100 to 200 ° C. .

  The apparatus for producing the polyolefin-based resin (P1 to 3) is not particularly limited as long as it can be stirred or kneaded, and includes a Kolben, a simple pressure reactor (autoclave), a uniaxial or biaxial kneader, and the like. Can be used.

  The aqueous polyolefin resin dispersion (E2) is a compound (B) having reactivity with amino groups in the aqueous polyolefin resin dispersion (E1) obtained by dispersing the polyolefin resin (P3) having amino groups in the aqueous medium (M). ) Is added and absorbed in particulate (P3) and then reacted.

  Examples of the aqueous medium (M) in the present invention include water and a mixture of water and an organic solvent (S). Examples of the organic solvent (S) include ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents (ethyl acetate, butyl acetate, γ-butyrolactone, etc.), ether solvents (THF, etc.), amide solvents [ N, N-dimethylformamide (hereinafter abbreviated as DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, etc.], alcohol solvents (methanol, ethanol, isopropyl alcohol, etc.) and aroma Group hydrocarbon solvents (toluene, xylene, etc.). These organic solvents may be used individually by 1 type, or may use 2 or more types together. Among these, a water-soluble organic solvent is preferable from the viewpoint of dispersibility.

The polyolefin resin aqueous dispersion (E1) can be produced by neutralizing the polyolefin resin (P3) having an amino group with a neutralizing agent as necessary and dispersing it in the aqueous medium (M). Specifically, a method of dispersing in water using a rotary dispersion mixing apparatus as the dispersion mixing apparatus can be mentioned. By using the above method, it is possible to obtain an aqueous polyolefin resin dispersion (E1) having excellent dispersion stability without using a surfactant.
In addition, in manufacture, the said organic solvent (S) and other additives which are arbitrary components are used together as needed.

  Examples of the neutralizing agent for neutralizing (P3) include monocarboxylic acids having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propanoic acid, and lactic acid), carbonic acid, hydrochloric acid, phosphoric acid, sulfuric acid, dimethyl carbonate, dimethyl sulfate, and methyl. Examples include chloride and benzyl chloride.

  Among these, carbonic acid and phosphoric acid are preferable from the viewpoint of the odor of the aqueous polyolefin resin dispersion (E2).

  When using a neutralizing agent, it may be added at any time before the water dispersion step, during the water dispersion step, or after the water dispersion, but from the viewpoint of emulsification dispersibility of the polyolefin resin (P3) having an amino group Therefore, it is preferably added before or during the water dispersion step.

  When using the above method, it is preferable that the shape of the polyolefin-based resin (P3) having an amino group is 0.2 to 50 mm in the form of granules or blocks from the viewpoint of easy supply to the rotary dispersion mixing apparatus, and the size thereof. Is more preferably 0.5 to 30 mm, particularly preferably 1 to 10 mm.

  By using the organic solvent (S) when the amino group-containing polyolefin resin (P3) is dispersed in the aqueous medium (M), the emulsification dispersibility can be improved.

  When the organic solvent (S) is used, the amount used is usually 50% by weight or less, preferably 20% by weight or less. In addition, when the organic solvent (S) is used including the production of the above-mentioned polyolefin resin (P3), this is preferably 1000 ppm or less after the polyolefin resin aqueous dispersion is produced from the viewpoint of environmental pollution. More preferably, it is preferably distilled off to 500 ppm or less, particularly preferably 100 ppm or less, and most preferably, no organic solvent (S) is used and no organic solvent is substantially contained.

  Examples of other additives include pH adjusters, foam breakers, foam suppressors, defoamers, antioxidants, anti-coloring agents, plasticizers and mold release agents.

  Examples of the dispersion mixing device for dispersing the polyolefin-based resin (P3) having an amino group or these organic solvent solutions in the aqueous medium (M) include (1) vertical stirring method and (2) rotor-stator. [3] Line mill method [eg line flow mixer], (4) Static tube mixing type [eg static mixer], (5) Vibration type [eg “VIBRO” MIXER "(manufactured by Chilling Industries Co., Ltd.)], (6) Ultrasonic impact type [for example, ultrasonic homogenizer], (7) High pressure impact type [for example, Gaurin homogenizer (Gaurin)], (8) Membrane emulsification type [for example, membrane Emulsification module], and (9) centrifugal thin film contact type [for example, “Fillmix” (manufactured by Primemix)].

  The temperature of the dispersion when the polyolefin resin (P3) having amino groups or these organic solvent solutions is dispersed in the aqueous medium (M) is from the viewpoint of emulsifying dispersibility and the stability of the polyolefin resin having amino groups. The temperature is preferably 20 to 180 ° C, more preferably 40 to 170 ° C, particularly preferably 50 to 160 ° C, and most preferably 60 to 150 ° C.

The weight ratio of the supplied (P3) to the aqueous medium (M) when the polyolefin-based resin (P3) having an amino group or an organic solvent solution thereof is dispersed in the aqueous medium (M) is the target aqueous dispersion. Although it is suitably selected depending on the resin component content, (P3) / aqueous medium (M) = 10/2 to 10/100, more preferably 10/5 to 10/50.
Moreover, the residence time in the dispersion | distribution mixing apparatus of (P3) and an aqueous medium (M) becomes like this. Preferably it is 0.1-60 minutes, More preferably, it is 10-30 minutes.

The polyolefin resin (P3) is preferably a polyolefin resin (P4) obtained by reacting (P3) with a compound (B) having reactivity with an amino group. The aqueous polyolefin resin dispersion (E1) is preferably an aqueous resin dispersion (E2) containing the polyolefin resin (P4) and an aqueous medium (M).

  Examples of the compound (B) having reactivity with an amino group include epoxy compounds, aziridine compounds, oxazoline compounds, isocyanate compounds, block isocyanate compounds, and melamine compounds.

  When the compound (B) has one functional group having reactivity with an amino group in the molecule, a coating film excellent in water resistance can be formed from (E2). In addition, when the compound (B) has two or more functional groups having reactivity with amino groups in the molecule, a crosslinked structure can be introduced into the molecule, and in addition to water resistance from (E2) A coating film excellent in solvent resistance can be formed.

  Examples of the epoxy compound include those having 4 to 40 carbon atoms (methyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, glycerol polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, polypropylene glycol diglycidyl ether and 3-glycidoxypropyltrimethoxysilane) Can be mentioned. These may be used alone or in combination of two or more.

  From the viewpoint of mechanical strength, water resistance, and solvent resistance of the dry film of the polyolefin resin aqueous dispersion, the epoxy compound preferably has 4 to 30 carbon atoms, and more preferably 4 to 25 carbon atoms.

  Examples of the aziridine compounds include C3-C30 aziridine compounds [1-aziridinemethanol, 1-aziridineethanol, tetramethylolmethanetris (β-aziridinylpropionate), 2,2-bishydroxymethylbutanol- Tris {3- (1-aziridinyl) propionate} and trimethylolpropane tris (β-aziridinylpropionate) and the like].

  Of these, compounds having two or more aziridinyl groups in the molecule are preferred from the viewpoints of mechanical strength, water resistance and solvent resistance of the dried film of the aqueous polyolefin resin dispersion.

  Examples of the oxazoline compound include a compound having one oxazoline group such as 2-ethyloxazoline, a compound having two oxazoline groups such as 2,2′-isopropylidenebis (4-phenyl-2-oxazoline); (Co) polymers of polymerizable oxazoline compounds such as propenyl-2-oxazoline, 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2-oxazoline; the polymerizable oxazoline compound and methyl (meth) acrylate , (Meth) acrylic esters such as ethyl (meth) acrylate, hydroxyethyl (meth) acrylate and polyethylene glycol (meth) acrylate, (meth) acrylic acid amide vinyl acetate, styrene and α-methylstyrene styrene sulfonic acid Do not react with oxazoline groups such as sodium. Copolymers of copolymerizable monomers; and the like. These may be used alone or in combination of two or more.

  Among these, a compound having two or more oxazoline groups in the molecule is preferable from the viewpoints of mechanical strength, water resistance and solvent resistance of the dry film of the polyolefin resin aqueous dispersion (E2).

  As the isocyanate compound, an aromatic polyisocyanate having 8 to 26 carbon atoms having 2 to 3 or more isocyanate groups, an aliphatic polyisocyanate having 4 to 22 carbon atoms, and an alicyclic polyisocyanate having 8 to 18 carbon atoms. And C10-18 araliphatic polyisocyanates and modified products of these polyisocyanates. The isocyanate compound organic isocyanate component may be used alone or in combination of two or more.

  Examples of the aromatic polyisocyanate having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is abbreviated as TDI), Crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′- Dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate And m- or p-isocyanatophenylsulfonylisocyanate Door and the like.

  Examples of the aliphatic polyisocyanate having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2, and the like. 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6 -Diisocyanatohexanoate.

  Examples of the alicyclic polyisocyanate having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene. Examples include diisocyanates, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  Examples of modified polyisocyanates include modified polyisocyanates (urethane groups, carbodiimide groups, allohanate groups, urea groups, biuret groups, uretdione groups, uretoimine groups, isocyanurate groups, or oxazolidone group-containing modified products; free isocyanate groups The content is usually 8 to 33% by weight, preferably 10 to 30% by weight, particularly 12 to 29% by weight), such as modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified Examples thereof include modified polyisocyanates such as TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.

Of these, aliphatic polyisocyanates having 4 to 22 carbon atoms and alicyclic polyisocyanates having 8 to 18 carbon atoms are preferred from the viewpoint of absorption into the polyolefin resin (P3) having an amino group and reactivity.

  The blocked isocyanate compound is not particularly limited. For example, the polyisocyanate (b) is blocked with a blocking agent (phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amyl. Phenols such as phenol, p-octylphenol and p-nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol and tert-butyl alcohol; oximes such as acetoxime, methylethylketoxime and cyclohexanone oxime; dimethylamine, diethylamine, Secondary amine bonded to primary carbon such as di-n-propylamine, ethylmethylamine, diisopropylamine, di-sec-butylamine, dicyclohexyl Carbon number of secondary amines bonded to secondary carbon such as amine and isopropylcyclohexylamine, secondary amines bonded to tertiary carbon such as di-t-butylamine, and other secondary amines such as isopropylethylamine 2 to 15 aliphatic secondary amines; aromatic secondary amines such as diphenylamine and xylidine; phthalic imides; lactams such as ε-caprolactam and δ-valerolactam; malonic acid dialkyl ester, acetylacetone and acetoacetate Active methylene compounds such as alkyl acetates; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3 , 5-dimethylpyrazole and 3-methyl-5-phenylpyrazo Pyrazole compounds such as Le; those blocks and the like in an acidic sodium sulfite, etc.) and the like.

  As commercial products of block isocyanate, Duranate series (Duranate 22A-75P, 24A-100, 21S-75E, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100, manufactured by Asahi Kasei Co., Ltd., TSA-100, TSS-100, TSE-100, P301-75E, E402-80B, E405-70B, AE700-100, D101, D201 and A201H) and Takenate series (Takenate D-) manufactured by Mitsui Chemicals, Inc. 103N, D-160N, D-140N, D-110N, D-181N, D-120N, D-165N90CX, D-204, D-170N, PW series and B series).

  The blocking agent used in the blocked isocyanate is preferably methyl ethyl ketoxime in oximes and secondary carbon in aliphatic secondary amines having 2 to 15 carbon atoms from the viewpoint of both reactivity and storage stability. Secondary amines (especially diisopropylamine) bound to dimethyl ether, diethyl malonate among active methylene compounds and 3,5-dimethylpyrazole among pyrazole-based compounds.

  The content of the blocked isocyanate compound is preferably 0.01 to 25% by weight, more preferably 0.1%, based on the polyolefin resin (E1) having an amino group, from the viewpoint of film forming properties and water resistance. -20% by weight.

  The melamine compound is not particularly limited as long as it is a methylolated melamine compound or a methoxymethylolated melamine compound having two or more methylol groups or methoxymethylol groups in the molecule. For example, a Uban series (Uban 120, manufactured by Mitsui Chemicals, Inc.) 20HS, 2021, 2028, 228, 2860 and 22R, etc.), Cymel series manufactured by Nippon Cytec Co., Ltd. (Symel 202, 232, 235, 238, 254, 266, 267, 272, 285, 301, 303, 325, 327, 350, 370, 701, 703, 736, 738, 771, 114, 1156 and 1158, etc.) and Sumitomo Chemical Co., Ltd. Sumimar series (Sumimar M-30W, M-50W, M-55, M- 66B and 50B).

  Among these compounds (B), an epoxy compound is preferable from the viewpoints of water resistance and cost of the dry film of the polyolefin resin aqueous dispersion (E2). A compound (B) may be used individually by 1 type, or may use 2 or more types together.

  Although the usage-amount of a compound (B) can be suitably selected according to the kind of compound to be used, it is the quantity which reacts with 1-200 mol% of the amino group which the polyolefin-type resin (P3) which has an amino group has. Is preferable, more preferably 5 to 190 mol%, and particularly preferably 20 to 180 mol%. In addition, even if the amino group which (P3) has is neutralized with the neutralizing agent, reaction of this amino group and compound (B) advances.

  In order to mix the compound (B) and the aqueous polyolefin resin dispersion (E1) and absorb it in the polyolefin resin (P3) having an amino group, the compound (B) is water-soluble or (P3 ) Must be liquid at the temperature at which it is absorbed. The melting point of the compound (B) is preferably 120 ° C. or lower, more preferably 100 ° C. or lower. When the compound (B) is solid at room temperature, the compound (B) is mixed with the aqueous dispersion of the polyolefin resin (P3) in order to allow the compound (B) to be absorbed by the (P3). Thus, it is preferable to make the compound (B) liquid.

  As an apparatus used for mixing the compound (B) and the aqueous polyolefin resin dispersion (E1) and absorbing (B) into the polyolefin resin (P3) particles having an amino group, an apparatus having a stirring ability is used. Can be used, for example, a known mixing device, for example, a dispersion mixing device exemplified as a device for emulsifying and dispersing the polyolefin-based resin (P3) having the amino group or an organic solvent solution thereof in an aqueous medium (M) is used. it can.

  The temperature and time at which the compound (B) and the polyolefin resin aqueous dispersion (E1) are mixed and the compound (B) is absorbed by the particles of the polyolefin resin (P3) having an amino group are the same as the compound (B) used. Although depending on the type of polyolefin resin (P3) having an amino group, the temperature is preferably 10 to 80 ° C., the time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 3 hours, and particularly preferably 15 minutes. ~ 60 minutes.

  The absorption of the compound (B) by the polyolefin resin (P3) means that a sample collected by sampling every certain time after starting the mixing of the compound (B) and the aqueous polyolefin resin dispersion (PE1) for 30 minutes. It can be confirmed by a method of allowing it to stand and confirming that it has not been visually separated.

  The apparatus for reacting (P3) and (B) by absorbing the compound (B) in the polyolefin-based resin (P3) having an amino group and then heating it may be an apparatus capable of stirring and heating. For example, a dispersion mixing apparatus exemplified as an apparatus for emulsifying and dispersing the polyolefin resin (P3) having an amino group or an organic solvent solution thereof in the aqueous medium (M) can be used.

The temperature at which the polyolefin-based resin (P3) having an amino group and the compound (B) are reacted is preferably 80 to 140 ° C, more preferably 90 to 120 ° C, and particularly preferably 90 to 110 ° C.
The reaction time can be appropriately selected depending on the apparatus to be used, the type of the compound (B), etc., but is generally preferably 10 minutes to 100 hours, more preferably 30 minutes to 30 hours, particularly preferably. 60 minutes to 10 hours.

  The solid content concentration of the aqueous polyolefin resin dispersion (E1) and the aqueous polyolefin resin dispersion (E2) of the present invention is preferably from 10 to 65% by weight, more preferably from the viewpoint of dispersion stability and transportation cost. ~ 55% by weight.

  The viscosity of the aqueous polyolefin resin dispersion (E1) and the aqueous polyolefin resin dispersion (E2) of the present invention is preferably 10 to 100,000 mPa · s, more preferably 10 to 5,000 mPa · s. The viscosity can be measured at a constant temperature of 25 ° C. using a BL type viscometer.

  The volume average particle diameter (Dv) of the aqueous polyolefin resin dispersion (E1) and the aqueous polyolefin resin dispersion (E2) of the present invention is preferably from 0.01 to 1 μm, more preferably from the viewpoint of dispersion stability. It is 0.02 to 0.7 μm, particularly preferably 0.03 to 0.4 μm.

  In addition, the volume average particle diameter (Dv) in the present invention is obtained by diluting an aqueous resin dispersion with ion-exchanged water so that the solid content of the resin becomes 0.01% by weight, and then measuring a laser diffraction particle size distribution analyzer [for example, LA-750 (manufactured by Horiba Seisakusho)] or a light scattering particle size distribution analyzer [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}].

  The aqueous polyolefin resin dispersion (E1) and aqueous polyolefin resin dispersion (E2) of the present invention include an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a pigment printing binder composition, Non-woven fabric binder composition, reinforcing fiber sizing agent composition, antibacterial agent binder composition and artificial leather / synthetic leather raw material composition, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, and prevention) Stain coating compositions, etc.), water-based paper treating agent compositions, water-based ink compositions, etc., but because of their excellent film-forming properties and water resistance, in particular, water-based coating compositions, water-based adhesive compositions and It can be suitably used as an aqueous fiber processing agent composition.

  When used in these applications, other additives such as coating forming auxiliary resins, crosslinking agents, catalysts, pigments, pigment dispersants, viscosity modifiers, antifoaming agents, leveling agents, preservatives, anti-degradation are necessary. One, two or more agents, stabilizers, antifreezing agents and the like can be added.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Hereinafter, the part means part by weight.

<Production Example 1>
In a stainless pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube, and a decompression device, low molecular weight polypropylene obtained by a thermal degradation method [polypropylene (MFR: 10 g / 10 min) is 410 ± 0. Obtained by heat degradation for 16 minutes at 1 ° C. under nitrogen flow (80 mL / min). Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8] 90 parts by weight, maleic anhydride 10 parts by weight and xylene 30 parts by weight was added, mixed uniformly, purged with nitrogen, melted by heating to 200 ° C. while stirring, and allowed to react at the same temperature for 10 hours. Subsequently, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin resin (P2-1) having a carboxylic anhydride group. . The acid value of (P2-1) was 27.5, and Mn was 3,600.

<Production Example 2>
A low-molecular-weight polypropylene [poly (propylene-butene) copolymer (MFR: MFR) obtained by a thermal degradation method in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube, and a decompression device. 7 g / 10 min) obtained by heat degradation for 16 minutes at 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min). Mn: 3,300, number of double bonds per 1,000 carbon atoms: 7.1, average number of double bonds per molecule: 1.8] 90 parts by weight, maleic anhydride 10 parts by weight and xylene 30 parts by weight was added, mixed uniformly, purged with nitrogen, melted by heating to 200 ° C. while stirring, and allowed to react at the same temperature for 10 hours. Next, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (P2-2) having a carboxyl group. The acid value of (P2-2) was 27.8, and Mn was 3,500.

<Production Example 3>
A stainless steel reaction kettle equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube and pressure reducing device was charged with 386 parts of diethylenetriamine and 1124 parts of methyl isobutyl ketone, and the produced water was distilled off from the reaction system at 120 ± 5 ° C. Then, the reaction was carried out for 10 hours to obtain a ketimine compound in which the amino groups at both ends of diethylenetriamine were ketiminated with methyl isobutyl ketone. Subsequently, 100 parts of the ketimine compound and 2 parts of potassium hydroxide were charged into a stainless steel autoclave equipped with a stirrer and a temperature controller, and the pressure in the reaction vessel was reduced to 0.01 MPa. Subsequently, 817 parts of EO was blown in over 21 hours at 120 ± 10 ° C. to obtain a compound in which EO was added to the imino group of the ketimine compound. Subsequently, 2 parts of ion-exchanged water was added to 100 parts of a compound in which EO was added to the imino group of the ketimine compound in a stainless steel reaction kettle equipped with a stirrer and a temperature controller, and stirred at 90 ° C. for 1 hour. Transfer to a stainless steel reaction kettle equipped with a temperature controller, charge 15 parts of ion-exchanged water and react for 10 hours while distilling off methyl isobutyl ketone produced at 90 ± 5 ° C from the reaction system. A polyamine (a1-1) in which EO was added only to the imino group was obtained.

<Production Example 4>
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 379 parts of a ketimine compound obtained by ketiminating the amino groups at both ends of diethylenetriamine obtained in Production Example 1 with methyl isobutyl ketone, and 1 part of potassium hydroxide. Was reduced to 0.01 MPa. Next, 620 parts of EO was blown in at 10 ± 10 ° C. over 10 hours to obtain a compound in which EO was added to the imino group of the ketimine compound. Subsequently, the same treatment as in Production Example 1 was performed to obtain polyamine (a1-2) in which EO was added only to the imino group of diethylenetriamine.

<Production Example 5>
100 parts of polyolefin resin (P2-1), 100 parts of xylene and 55.9 parts of polyamine (a1-1) were added to a stainless steel reaction kettle equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube and decompression device. The temperature was raised to 170 ° C. and the mixture was melted and reacted at the same temperature for 1 hour. Next, xylene was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin resin (P3-1) having an amino group. The amine value of (P3-1) was 28.1, and Mn was 8,000.

<Production Example 6>
100 parts of polyolefin resin (P2-2), 100 parts of xylene, 55.8 parts of polyamine (a1-1) were added to a stainless steel reaction kettle equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction pipe and decompression device. The temperature was raised to 170 ° C. and the mixture was melted and reacted at the same temperature for 1 hour. Subsequently, xylene was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin resin (P3-2) having an amino group. The amine value of (P3-2) was 28.0, and Mn was 7,900.

<Production Example 7>
100 parts of polyolefin resin (P2-2), 100 parts of xylene, and 13.4 parts of polyamine (a1-2) are added to a stainless steel reaction kettle equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction pipe and decompression device. The temperature was raised to 170 ° C. and the mixture was melted and reacted at the same temperature for 1 hour. Subsequently, xylene was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin resin (P3-2) having an amino group. The amine value of (P3-2) was 47.2, and Mn was 4,200.

<Example 1>
A stainless steel autoclave equipped with a stirrer and a temperature controller is charged with 50 parts of an amino group-containing polyolefin resin (P3-1), 50 parts of tetrahydrofuran and 117 parts of water, and stirred at 120 ° C. for 1 hour for aqueous polyolefin resin. A dispersion (E1-1) was obtained. Subsequently, 3.0 parts of polypropylene glycol diglycidyl ether [“Denacol EX-931” manufactured by Nagase ChemteX Corp.] was added, stirred for 30 minutes at room temperature, and then heated to 100 ° C. and reacted for 3 hours. Thereafter, tetrahydrofuran was distilled off at 70 ° C. under reduced pressure to obtain a polyolefin resin aqueous dispersion (E2-1).

<Example 2>
A stainless steel autoclave equipped with a stirrer and a temperature controller is charged with 50 parts of an amino group-containing polyolefin resin (P3-1), 1 part of acetic acid and 75 parts of water, and stirred at 140 ° C. for 2 hours for aqueous polyolefin resin. A dispersion (E1-2) was obtained. Then, 1.7 parts of neopentyl glycol diglycidyl ether [“Denacol EX-211” manufactured by Nagase ChemteX Corporation] was added and stirred at room temperature for 30 minutes, and then heated to 100 ° C. and reacted for 3 hours. Then, tetrahydrofuran was distilled off at 70 ° C. under reduced pressure to obtain a polyolefin resin aqueous dispersion (E2-2).

<Example 3>
A stainless steel autoclave equipped with a stirrer and a temperature controller is charged with 50 parts of an amino group-containing polyolefin resin (P3-2), 50 parts of tetrahydrofuran and 117 parts of water, and stirred at 120 ° C. for 1 hour for aqueous polyolefin resin. A dispersion (E1-2) was obtained. Subsequently, 9.9 parts of polypropylene glycol diglycidyl ether [“Denacol EX-931” manufactured by Nagase ChemteX Corp.] was added and stirred at room temperature for 30 minutes, and then heated to 100 ° C. and reacted for 3 hours. Then, tetrahydrofuran was distilled off at 70 ° C. under reduced pressure to obtain a polyolefin resin aqueous dispersion (E2-3).

<Comparative Production Example 1>
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device, 50 parts by weight of polypropylene (MFR: 3.0 g / 10 min), 0.5 parts of benzoyl peroxide, anhydrous maleic 3 parts by weight of acid and 30 parts by weight of xylene were added and mixed uniformly, then purged with nitrogen, heated up to 200 ° C. with stirring under stirring and melted, and reacted at the same temperature for 10 hours. Subsequently, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin resin (P′3-1). The acid value of (P′3-1) was 9.1, and Mn was 50,000.

<Comparative Example 1>
Into a stainless steel reaction kettle equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube and decompression device, 50 parts of polyolefin resin (P'3-1) and 150 parts of toluene are charged uniformly at 110 ° C. After mixing, the mixture was cooled to 80 ° C., and 1.6 parts of triethylamine was added and mixed uniformly. Under stirring, an aqueous solution prepared by dissolving 10 parts of hexadecyl alcohol EO 14 mol adduct in 140 parts of water was added over 20 minutes, and then toluene was distilled off at 70 ° C. under reduced pressure to obtain an aqueous polyolefin resin dispersion ( E′2-1) was obtained.

<Comparative Example 2>
Into a stainless steel reaction kettle equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube and decompression device, 50 parts of polyolefin resin (P'3-1) and 150 parts of toluene are charged uniformly at 110 ° C. After mixing, the mixture was cooled to 80 ° C., and 1.4 parts of 2-dimethylaminoethanol was added and mixed uniformly. Under stirring, an aqueous solution prepared by dissolving 15 parts of an EO14 molar adduct of hexadecyl alcohol in 140 parts of water was added over 30 minutes, and then toluene was distilled off at 70 ° C. under reduced pressure to obtain an aqueous polyolefin resin dispersion ( E′2-2) was obtained.

  Polyolefin resin aqueous dispersions (E2-1) to (E2-3) obtained in Examples 1 to 3 and polyolefin resin aqueous dispersions (E′2-1) obtained in Comparative Examples 1 and 2 and The evaluation results of (E′2-2) are shown in Table 1. The evaluation method is as follows.

<Water resistance of dry film>
Pour 10 parts of an aqueous polyolefin-based resin dispersion into a polypropylene mold measuring 10 cm long × 20 cm wide × 1 cm deep. After drying for 12 hours at room temperature, air circulation dryer The film obtained by heating and drying at 105 ° C. for 3 hours was immersed in ion-exchanged water at 50 ° C. for 14 days, and then the surface of the coating film was visually evaluated according to the following evaluation criteria.
○: No change in coating film surface before and after immersion.
X: The surface of the coating film is whitened after immersion.

<Solvent resistance of dry film>
The aqueous polyolefin resin dispersion was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 3 minutes to prepare a 20 μm coating film. The coated steel sheet was immersed in dimethylformamide at 25 ° C. for 1 minute, then taken out and lightly wiped, and the surface of the coating film was visually evaluated according to the following evaluation criteria.
○: There is no change in the coating film surface before and after immersion.
X: After immersion, the coating film surface has irregularities.

<Tensile strength of dry film>
A polyolefin-based resin aqueous dispersion was applied on a glass plate so that the film pressure after drying was 0.2 mm, dried for 3 hours with a circulating dryer at 105 ° C., and then peeled off from the glass plate. A film for tensile strength test was prepared.
The obtained film for tensile test was left in a room adjusted to a temperature of 25 ° C. and a humidity of 65% RH for 1 day, and then the tensile strength was measured according to JIS K 6251.

The aqueous polyolefin resin dispersion (E2) of the present invention has an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder for pigment printing) because of its water resistance, solvent resistance and mechanical strength. Composition, binder composition for non-woven fabric, sizing agent composition for reinforcing fibers, binder composition for antibacterial agent and raw material composition for synthetic leather, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition and prevention) Stainable coating compositions, etc.), aqueous paper treatment compositions, aqueous ink compositions, and the like, and are particularly suitable as aqueous coating compositions, aqueous adhesive compositions, and aqueous fiber processing compositions.

Claims (7)

A polyolefin resin (P3) obtained by reacting the polyamine (A) represented by the general formula (1) with a polyolefin resin (P2) having a carboxylic anhydride group, and an aqueous medium (M). Polyolefin resin aqueous dispersion.

[Wherein, R ¹ and R ² each independently represents an alkylene group having 2 to 10 carbon atoms, a represents an integer of 1 to 5, and X represents a monovalent polyoxy having an oxyethylene group as an essential constituent unit. An alkylene (C2-C12 alkylene) group is shown. ] The aqueous resin dispersion according to claim 1, wherein, in the general formula (1), X is represented by the following general formula (2).

[AO is an oxyalkylene group having 3 to 12 carbon atoms, and when there are a plurality of AOs, they may be the same or different, b represents an integer of 5 to 200, c represents an integer of 0 to 195, When 5 ≦ b + c ≦ 200 is satisfied and c is 1 or more, the bonding form of b oxyethylene groups and c oxyalkylene groups (AO) may be random, block, or a mixture thereof. ]   The polyolefin resin aqueous dispersion according to claim 2, wherein b in the general formula (2) is 40 to 200, and c is 0.   In general formula (1), a is 1, The polyolefin resin aqueous dispersion of any one of Claims 1-3.   The polyolefin resin aqueous dispersion according to any one of claims 1 to 4, wherein a weight ratio of oxyethylene groups in the polyamine (A) based on the weight of the polyolefin resin (P3) is 10 to 50 wt%. . A polyolefin resin (P4) obtained by reacting the polyolefin resin (P3) according to any one of claims 1 to 5 with a compound (B) having reactivity with an amino group and an aqueous medium ( A polyolefin resin aqueous dispersion comprising M). The polyolefin resin aqueous dispersion according to claim 6, wherein the compound (B) is at least one compound selected from the group consisting of an epoxy compound, an aziridine compound, an oxazoline compound, an isocyanate compound, a blocked isocyanate compound, and a melamine compound.