JP2010180397A - Aqueous emulsion of olefinic copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion which does not include chlorine and gives a cured material excellent in adhesiveness and water resistance. <P>SOLUTION: The aqueous emulsion includes an olefinic copolymer having structural units derived from an α-olefin and/or ethylene and/or propylene and structural units derived from a vinyl compound having a substituted group R and represented by formula (I): CH<SB>2</SB>=CHR (wherein R is a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group), an emulsifier, a urea compound, and a cationic polymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous emulsion containing an olefin copolymer, a cured product obtained by drying the emulsion, and a laminate obtained by bonding the cured product.

  Polypropylene is used in a wide range of applications such as automobile parts and building materials because of its excellent processability and strength. However, there is a problem that a coating film such as a paint is difficult to adhere to the polypropylene surface. For this reason, generally, in many cases, a chlorinated polyolefin resin excellent in adhesiveness with polypropylene is applied onto polypropylene, and a paint is applied thereon (Patent Document 1). On the other hand, from the viewpoint of environmental problems, application of a cured film not containing a halogen substance has been proposed, and chlorinated polyolefin containing chlorine is being avoided.

  Therefore, as an alternative to the chlorinated polyolefin, an olefin copolymer containing a structural unit derived from ethylene and a structural unit derived from a vinyl compound having a substituent such as vinylcyclohexane and / or a modified product thereof is included. An aqueous emulsion is proposed (Patent Documents 2 and 3).

  The cured film obtained from the aqueous emulsion has excellent adhesiveness and is used as a primer for coating, a binder for coating, etc., but it is a cloudy opaque film, and when it is mixed with a pigment or the like to obtain a colored cured product It is pointed out that the color is limited, and an aqueous emulsion comprising an olefin copolymer and / or a modified product thereof and ureas as an aqueous emulsion that gives such a cured film in which the opacity is eliminated. An emulsion is described in US Pat. However, the cured product obtained from the aqueous emulsion has excellent transparency and is excellent in moldability, heat resistance, solvent resistance and mechanical properties, but has a problem in water resistance.

JP 05-7832 A JP 2006-124535 A JP 2005-320400 A JP 2008-169380 A

  Under these circumstances, paints, binders, coating agents, adhesives or primers that do not contain chlorine and have excellent adhesion and water resistance are required. Therefore, an object of the present invention is to provide an aqueous emulsion that gives a cured product excellent in water resistance.

Under such circumstances, as a result of intensive studies, the inventors have reached the invention described in any one of [1] to [11] below.
[1] Vinyl compound (I) having a structural unit derived from an α-olefin and / or ethylene and / or propylene and a substituent R:
_{CH 2 = CH-R (I} )
[In formula (I), R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group. ]
An aqueous emulsion having an olefin copolymer, an emulsifier, ureas and a cationic polymer containing a structural unit derived from

[2] The olefin copolymer further contains a structural unit derived from unsaturated carboxylic acids [1]
The aqueous emulsion as described.

〔式（III）中、Ｑは、酸素原子又は硫黄原子を表し、Ｘ¹、Ｘ²、Ｘ³及びＸ^４は互いに独立に、水素原子、炭素数１〜６の直鎖アルキル基、炭素数３〜６の分枝アルキル基、又は、Ｘ¹あるいはＸ²と、Ｘ³あるいはＸ^４とが結合した炭素数１〜６のアルキレン基を表し、但し、アルキル基及びアルキレン基の水素原子は水酸基で置換されていてもよい。〕
で表される化合物である、［１］又は［２］記載の水性エマルジョン。 [3] Urea is represented by the following formula (III):

[In Formula (III), Q represents an oxygen atom or a sulfur atom, and X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a carbon number. A branched alkyl group having 3 to 6 or an alkylene group having 1 to 6 carbon atoms in which X ¹ or X ² and X ³ or X ⁴ are bonded to each other, provided that the hydrogen atom of the alkyl group and the alkylene group is a hydroxyl group May be substituted. ]
The aqueous emulsion according to [1] or [2], which is a compound represented by:

[4] A water-soluble acrylic resin in which the emulsifier contains a structural unit derived from an α, β-unsaturated carboxylic acid, a structural unit derived from a vinyl acrylate ester, and a structural unit derived from a (meth) acrylic acid ester, The aqueous emulsion according to any one of [1] to [3], which is at least one emulsifier selected from the group consisting of a polyoxyethylene polyoxypropylene block copolymer and a polyoxyethylene alkyl ether.

[5] The aqueous emulsion according to any one of [1] to [4], wherein the cationic polymer is a reaction product of a polyamine and epichlorohydrin.

[6] Dispersoid comprising an olefin copolymer and an emulsifier containing a structural unit derived from an α-olefin and / or ethylene and / or propylene, and a structural unit derived from the vinyl compound (I) having a substituent R The water-based emulsion according to any one of [1] to [5], wherein the volume-based median diameter is 0.01 to 1 μm.

[7] The aqueous emulsion according to any one of [1] to [6], wherein the vinyl compound (I) is vinylcyclohexane.

[8] A cured product obtained by drying the aqueous emulsion according to any one of [1] to [7].

[9] Lamination formed by bonding an adherend made of at least one material selected from the group consisting of woody materials, cellulosic materials, plastic materials, ceramic materials, and metal materials, and the cured product described in [8]. body.

[10] The laminate according to [10], wherein the plastic material is polyolefin.

[11] The laminate according to [9] or [10], wherein the plastic material is polypropylene.

  The aqueous emulsion of the present invention does not contain chlorine and gives a cured product having excellent adhesion and water resistance. The formed cured product has transparency, moldability, heat resistance, solvent resistance, mechanical properties, etc. Therefore, it can be suitably used as a paint, binder, coating agent, adhesive or primer.

Hereinafter, the present invention will be described in detail.
The aqueous emulsion of the present invention comprises a specific olefin copolymer, an emulsifier, ureas and a cationic polymer.
The olefin copolymer used in the present invention includes a structural unit derived from an α-olefin and / or ethylene and / or propylene, and the following vinyl compound (I):
_{CH 2 = CH-R (I} )
(In formula (I), R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
And a structural unit derived from.

  Here, the secondary alkyl group is preferably a secondary alkyl group having 3 to 20 carbon atoms, the tertiary alkyl group is preferably a tertiary alkyl group having 4 to 20 carbon atoms, and the alicyclic hydrocarbon group is An alicyclic hydrocarbon group having a 3 to 16 membered ring is preferred. As the substituent R, a C3-C20 alicyclic hydrocarbon group having a 3- to 10-membered ring and a C3-C20 tertiary alkyl group are more preferable.

  Specific examples of the vinyl compound (I) in which the substituent R is a secondary alkyl group include 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1 -Heptene, 3-methyl-1-octene, 3,4-dimethyl-1-pentene, 3,4-dimethyl-1-hexene, 3,4-dimethyl-1-heptene, 3,4-dimethyl-1-octene 3,5-dimethyl-1-hexene, 3,5-dimethyl-1-heptene, 3,5-dimethyl-1-octene, 3,6-dimethyl-1-heptene, 3,6-dimethyl-1-octene 3,7-dimethyl-1-octene, 3,4,4-trimethyl-1-pentene, 3,4,4-trimethyl-1-hexene, 3,4,4-trimethyl-1-heptene, 3,4 , 4-Trimethyl-1-octene And the like.

Specific examples of the vinyl compound (I) in which the substituent R is a tertiary alkyl group include 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, and 3,3-dimethyl-1-hexene. 3,3-dimethyl-1-heptene, 3,3-dimethyl-1-octene, 3,3,4-trimethyl-1-pentene, 3,3,4-trimethyl-1-hexene, 3,3,4 -Trimethyl-1-heptene, 3,3,4-trimethyl-1-octene and the like.
Specific examples of the vinyl compound (I) in which the substituent R is an alicyclic hydrocarbon group include substituents R such as vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and vinylcyclooctane. Vinyl compounds that are cycloalkyl groups; 5-vinyl-2-norbornene, 1-vinyladamantane, 4-vinyl-1-cyclohexene and the like can be mentioned.

  Among the vinyl compounds (I), preferably 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3,4-dimethyl-1-pentene, 3,5-dimethyl. -1-hexene, 3,4,4-trimethyl-1-pentene, 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, 3,3,4-trimethyl-1-pentene, vinyl Cyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, 5-vinyl-2-norbornene, more preferably 3-methyl-1-butene, 3-methyl-1-pentene, 3,4-dimethyl-1 -Pentene, 3,3-dimethyl-1-butene, 3,3,4-trimethyl-1-pentene, vinylcyclohexane, vinylnorbornene, more preferred Is a 3,3-dimethyl-1-butene, vinylcyclohexane. The most preferred vinyl compound (I) is vinylcyclohexane.

The content of the structural unit of the vinyl compound (I) in the olefin copolymer used in the present invention is preferably 5 to 40 with respect to 100 mol% of all the structural units constituting the olefin copolymer. It is mol%, More preferably, it is 10-30 mol%, Most preferably, it is 10-20 mol%.
It is preferable for the content to be 5 to 40 mol% because the adhesiveness of the resulting cured product tends to improve.
The content can be determined using a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

  The α-olefin used in the present invention is usually a linear α-olefin having 4 to 20 carbon atoms, specifically, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-heptene, Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicosene, etc. Linear olefins and the like. Among these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferably used.

  In the olefin copolymer used in the present invention, the total content of the structural unit derived from ethylene, the structural unit derived from propylene, and the structural unit derived from α-olefin constitutes the olefin copolymer. Preferably it is 95-60 mol% with respect to 100 mol% of all the structural units, More preferably, it is 90-70 mol%, Most preferably, it is 90-80 mol%.

  As the α-olefin and / or ethylene and / or propylene, ethylene and / or propylene are suitable.

〔式（ＩＩ）中、Ｒ’、Ｒ”は、それぞれ独立に、炭素数１〜１８程度の直鎖状アルキル基、炭素数３〜１８程度の分枝状アルキル基、炭素数３〜１８程度の環状アルキル基、又はハロゲン原子等を表す。〕
で表されるビニリデン化合物、ジエン化合物、ハロゲン化ビニル、アルキル酸ビニル、ビニルエーテル類、アクリロニトリル類などが挙げられる。 The olefin copolymer used in the present invention is obtained by copolymerizing an α-olefin and / or ethylene and / or propylene and a vinyl compound (I), and is a monomer capable of addition polymerization. May be copolymerized.
Here, the addition-polymerizable monomer is a monomer other than ethylene, propylene, α-olefin and vinyl compound (I), and is added with ethylene, propylene, α-olefin and vinyl compound (I). A polymerizable monomer. The number of carbon atoms of the monomer is usually about 3-20.
Specific examples of the monomer capable of addition polymerization include, for example, cycloolefin, the following formula (II):

[In formula (II), R ′ and R ″ are each independently a linear alkyl group having about 1 to 18 carbon atoms, a branched alkyl group having about 3 to 18 carbon atoms, or about 3 to 18 carbon atoms. Represents a cyclic alkyl group, a halogen atom or the like.]
And vinylidene compounds, diene compounds, vinyl halides, vinyl alkylates, vinyl ethers, acrylonitriles, and the like.

  Examples of the cycloolefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopentadecene 2-pentacyclohexadecene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl 2-norbornene, -Ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyl-2-tetracyclododecene, 8-methyl-8-methoxycarbonyl- 2-tetracyclododecene, 8-cyano-2-tetracyclododecene and the like can be mentioned, preferably cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene 5-methoxycarbonyl-2-norbol Emissions, a 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, more preferably 2-norbornene, 2-tetracyclododecene.

  In the formula (II), examples of the linear alkyl group having about 1 to 18 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group. Examples of the branched alkyl group having about 1 to 18 carbon atoms include i-propyl group, i-amyl group, t-butyl group, 2-ethylhexyl group and the like. Examples of the cyclic alkyl group having about 1 to 18 carbon atoms include a cyclopentyl group, a cyclohexyl group, a dicyclopentahexyl group, and the like.

  Examples of the vinylidene compound (II) include isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1- Octene, 2,3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1-heptene, 2,3-dimethyl-1- Examples include octene, 2,4-dimethyl-1-pentene, 2,4,4-trimethyl-1-pentene, vinylidene chloride, and the like, preferably isobutene, 2,3-dimethyl-1-butene, 2,4,4 -Trimethyl-1-pentene.

  Examples of the diene compound include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, and 2,5-norbornadiene. , Dicyclopentadiene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, etc., preferably 1,4-pentadiene, 1 , 5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene.

Examples of the vinyl halide include vinyl chloride.
Examples of vinyl alkylates include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, and the like.
Examples of acrylonitriles include acrylonitrile and methacrylonitrile.

  The content of the structural unit capable of addition polymerization in the olefin copolymer is usually in a range where the adhesiveness of the resulting modified olefin copolymer is not impaired, and the specific content is the olefin. The structural unit is preferably about 5 mol% or less, more preferably 1 mol% or less, and still more preferably substantially addition-polymerizable structural units with respect to 100 mol% of all the structural units constituting the copolymer. The content is not contained.

  Examples of the method for producing the olefin copolymer used in the present invention include a method of producing in the presence of a catalyst containing a transition metal compound having a group having an indenyl type anion skeleton or a bridged cyclopentadiene type anion skeleton. Etc. Among these, the production method according to the methods described in JP-A No. 2003-82028, JP-A No. 2003-160621 and JP-A No. 2000-128932 is preferable.

  In the production of an olefin copolymer, depending on the type of catalyst used and the polymerization conditions, in addition to the copolymer of the present invention, a homopolymer (polyolefin) or a vinyl compound (I) of ethylene, propylene or α-olefin such as polyethylene, etc. The homopolymer of may be by-produced. In such a case, the copolymer of the present invention can be easily fractionated by performing solvent extraction using a Soxhlet extractor or the like. Solvents that can be used for such extraction include toluene and chloroform. For example, a homopolymer of vinylcyclohexane can be removed as an insoluble component of extraction using toluene, and a polyolefin such as polyethylene can be removed as an insoluble component of extraction using chloroform. Can be fractionated as a soluble component of both solvents. If there is no problem depending on the use, the olefin copolymer may be used in a state where such a by-product exists.

The molecular weight distribution (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) of the olefin copolymer used in the present invention is preferably about 1.5 to 10.0, more preferably 1. It is about 5 to 7.0, most preferably about 1.5 to 5.0. It is preferable that the molecular weight distribution of the olefin copolymer is 1.5 or more and 10.0 or less because the mechanical strength and transparency of the obtained cured product tend to be improved.
Further, the weight average molecular weight (Mw) of the olefin copolymer is preferably about 5,000 to 1,000,000, more preferably about 10,000 to 500,000, from the viewpoint of mechanical strength. Most preferably, it is about 15,000 to 400,000. It is preferable that the weight average molecular weight of the olefin copolymer is 5,000 or more because the mechanical strength of the resulting cured product tends to be improved, and the weight average molecular weight is 1,000,000 or less. It is preferable because the fluidity of the olefin copolymer tends to be improved.

  The value of the intrinsic viscosity [η] of the olefin copolymer used in the present invention is preferably about 0.25 to 10 dl / g, more preferably 0.3 to 3 dl / g, from the viewpoint of mechanical strength. Degree.

The olefin copolymer used in the present invention preferably further contains a structural unit derived from unsaturated carboxylic acids. Structural units derived from unsaturated carboxylic acids can be obtained by graft polymerization of unsaturated carboxylic acids to the olefin copolymer.
Hereinafter, in the copolymer, a copolymer further containing a structural unit derived from an unsaturated carboxylic acid may be referred to as the present modified product.
The amount of graft polymerization of unsaturated carboxylic acids in the modified product is preferably about 0.01 to 20% by weight, more preferably about 0.05 to 10% by weight, most preferably 100% by weight of the modified product. Is about 0.1 to 5% by weight.
When the graft polymerization amount of unsaturated carboxylic acids is 0.01% by weight or more, it is preferable because the adhesive strength of the resulting cured product tends to be improved, and when the graft polymerization amount is 20% by weight or less, It is preferable because the thermal stability of the obtained cured product tends to be improved.

The unsaturated carboxylic acids used in the present invention include the following:
[Unsaturated carboxylic acid]
Acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, methyl nadic acid, hymic acid, angelic acid, tetrahydrophthalic acid, sorbic acid, mesaconic acid, etc .;
[Unsaturated carboxylic acid anhydride]
Maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, methyl nadic anhydride, hymic anhydride, etc .;
[Unsaturated carboxylic acid ester]
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid-n-butyl, methacrylic acid-n-butyl, acrylic acid-i-butyl, methacrylic acid-i-butyl, glycidyl acrylate, methacrylic acid Glycidyl, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid dimethyl ester, etc .;
[Unsaturated carboxylic acid amide]
Acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutyramide, maleic acid-N, N-dibutylamide, Fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, etc .;
[Unsaturated carboxylic acid imide]
Maleimide, N-butylmaleimide, N-phenylmaleimide, etc .;
[Unsaturated carboxylic acid halide]
Maleic chloride oil, etc .;
[Unsaturated carboxylic acid metal salt]
Sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like.
Moreover, you may use combining said unsaturated carboxylic acid arbitrarily.
As the unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides are preferable, and maleic anhydride is more preferable.

As a method for producing this modified product, for example, a method in which an olefin copolymer is melted and then an unsaturated carboxylic acid is added and graft polymerization is performed, and the olefin copolymer is dissolved in a solvent such as toluene or xylene. After that, a method of adding an unsaturated carboxylic acid and graft polymerization can be mentioned.
After melting the olefin copolymer, the method of adding unsaturated carboxylic acids to graft polymerization is to melt and knead using an extruder to mix the resins or the resin and solid or liquid additives. Therefore, it is preferable because various known methods can be employed. More preferably, all or a part of each component is combined and mixed separately with a Henschel mixer, a ribbon blender, a blender or the like to form a uniform mixture, and then the mixture is melt-kneaded and graft polymerization is performed. For melt kneading, conventionally known kneading means using a Banbury mixer, plast mill, Brabender plastograph, uniaxial or biaxial extruder, etc. can be widely used. Particularly preferably, from the viewpoint that continuous production is possible and productivity is improved, an olefin copolymer, an unsaturated carboxylic acid, and a radical initiator, which are sufficiently premixed in advance using a single or twin screw extruder, are added. It is a method of carrying out graft polymerization by supplying from the supply port of the extruder and kneading. The temperature of the portion where the melt kneading of the extruder is performed (for example, the cylinder temperature in the case of an extruder) is preferably 50 to 300 ° C, more preferably 80 to 270 ° C. When the temperature is 50 ° C. or higher, the amount of graft polymerization tends to be improved, and when the temperature is 300 ° C. or lower, decomposition of the olefin copolymer tends to be suppressed. . The temperature of the portion of the extruder where the melt kneading is performed is preferably set so that the melt kneading is divided into two stages, the first half and the second half, and the temperature in the second half is higher than the first half. The melt kneading time is preferably 0.1 to 30 minutes, more preferably 0.1 to 5 minutes. When the melt-kneading time is 0.1 minutes or more, the amount of graft polymerization tends to be improved, and when the melt-kneading time is 30 minutes or less, decomposition of the olefin copolymer is suppressed. It is preferable because of its tendency.

In order to graft an unsaturated carboxylic acid to an olefin polymer, the graft polymerization is usually carried out in the presence of a radical initiator.
The addition amount of the radical initiator is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the olefin polymer. When the addition amount is 0.01 parts by weight or more, the amount of graft polymerization to the olefin polymer tends to increase and the adhesive strength tends to be improved, and the addition amount is 10 parts by weight or less. When there exists, it is preferable from the tendency for the unreacted radical initiator in the modification | denaturation obtained to be reduced and for adhesive strength to improve. As the radical initiator, an organic peroxide is preferably used, and an organic peroxide having a decomposition temperature of 50 to 210 ° C. at which the half-life is 1 minute is more preferably used. When the decomposition temperature is 50 ° C. or higher, the amount of graft polymerization tends to be improved, and these organic peroxides decompose to generate radicals, and then draw protons from the olefin polymer. It is preferable at the point which has an effect | action.

Examples of organic peroxides having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, and percarbonate compounds. Can be mentioned. Specifically, dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate Bonate, t-butyl peroxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethyl butyl neodecanoate, α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, 1,1 bis (t-butylper Oxy) cyclohexane, 2,2bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxy Acetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-beroxy) valerate, di-t-butylberoxyisophthalate, dic Milperoxide, α-α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t -Butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroper And oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like. If the decomposition temperature at which the half-life is 1 minute is lower than 50 ° C., the graft polymerization amount tends not to be improved, and if the decomposition temperature is higher than 210 ° C., the decomposition of the olefin polymer increases, There is a tendency not to improve.
Among these organic peroxides, dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds, and alkyl perester compounds are preferably used. The amount of component (C) added is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the ethylene vinylcyclohexane copolymer resin (A).

The molecular weight distribution (Mw / Mn) of the modified product is preferably 1.5 to 10, more preferably 1.5 to 7, and most preferably 1.5 to 5. When the molecular weight distribution is 10 or less, the adhesiveness of the obtained cured product tends to be improved, which is preferable.
The molecular weight distribution of the modified product can be measured in the same manner as the molecular weight distribution of the olefin copolymer.
The weight average molecular weight (Mw) of the modified product is usually about 5,000 to 1,000,000, more preferably about 10,000 to 500,000, and most preferably 15,000 to 1,000,000. It is about 400,000. When the weight average molecular weight of the modified product is 5,000 or more, it is preferable because the mechanical strength of the obtained cured product tends to be improved, and when the weight average molecular weight is 1,000,000 or less. It is preferable because the fluidity of the modified product tends to be improved.

  The intrinsic viscosity [η] of the modified product is preferably about 0.25 to 10 dl / g, more preferably about 0.3 to 3 dl / g, from the viewpoint of mechanical strength.

The aqueous emulsion of the present invention comprises an emulsifier in addition to the olefin copolymer or the modified product.
The emulsifiers used in the present invention include the following:
[Anionic emulsifier]
α-olefin sulfonate, alkyl sulfate, alkyl phenyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl phenyl sulfosuccinic acid half ester salt, polyoxyethylene alkyl sulfosuccinic acid metal salt, water-soluble acrylic resin, rosin soap Such;
[Nonionic emulsifier]
Polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene alkyl ether and the like;
[Cationic emulsifier]
Alkyl trimethyl ammonium chloride, polyoxyethylene alkyl amine, etc.
As will be described later, it is preferable that the volume-based median diameter of the dispersoid in the aqueous emulsion of the present invention is 1 μm or less because the adhesiveness of the obtained cured product tends to be improved. Examples of emulsifiers used in emulsions containing such fine particle dispersoids include water-soluble acrylic resins, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene alkyl ethers, and Japanese Patent Application Publication No. 2008-24755. The emulsifier described is mentioned, The water-soluble acrylic resin, The emulsifier described in patent application publication 2008-24755 is used preferably, The emulsifier described in patent application publication 2008-24755 is used more preferably.

Here, the water-soluble acrylic resin is a water-soluble resin containing a structural unit derived from an α, β-unsaturated carboxylic acid, and the resin can be uniformly dissolved in water.
Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, succinic acid, itaconic acid and the like.
Other monomers constituting the water-soluble acrylic resin include the following:
[Α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms]
Acrylic acid, methacrylic acid, maleic acid, maleic anhydride, succinic acid, itaconic acid, etc .;
[C4-C18 (meth) acrylic acid ester]
Methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc .;
[Vinyl halide]
Acrylic acid vinyl esters such as ethylene acrylate and ethylene methacrylate; vinyl chloride, vinyl bromide, etc .;
[Vinylidene halides]
Vinylidene chloride and the like;
[Vinyl compounds]
Vinylphosphonic acid, vinylsulfonic acid and their salts;
[Aromatic vinyl]
Styrene, α-methylstyrene, chlorostyrene, etc .;
[Nitriles]
(Meth) acrylonitrile and the like;
[Acrylamides]
N-methylol acrylamide, N-butoxymethyl acrylamide, etc .;
[Conjugated dienes]
Butadiene, isoprene, etc .;
[Allyl compound]
Allyl sulfonate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, etc.
It is preferable that the water-soluble acrylic resin contains a structural unit derived from each of α, β-unsaturated carboxylic acid, vinyl acrylate, and (meth) acrylate, and moreover, a single amount constituting the resin 10 to 90 mol% of structural units derived from α, β-unsaturated carboxylic acid, 5 to 60 mol% of structural units derived from acrylic acid vinyl ester, with respect to a total of 100 mol% of structural units derived from the body, It is preferable to contain 5-85 mol% of structural units derived from (meth) acrylic acid esters.

  As the emulsifier, a plurality of arbitrary water-soluble acrylic resins may be used, or a water-soluble acrylic resin, a polyoxyethylene polyoxypropylene block copolymer, and a polyoxyethylene polyalkyl ether may be used in combination.

  Dispersoids comprising the copolymer and the emulsifier by dispersing the olefin copolymer or the modified product (hereinafter sometimes referred to collectively as the copolymer) in water together with an emulsifier to form an aqueous emulsion. Can be obtained. The volume-based median diameter of the dispersoid is preferably 0.01 to 5 μm, and more preferably 0.01 to 1 μm, still more preferably 0.05 to 0.5 μm, from the viewpoint of adhesiveness of the resulting cured product. More preferred is an aqueous emulsion having a volume-based median diameter of. The volume-based median diameter is preferably 0.01 μm or more because the dispersoid can be easily produced, and the volume-based median diameter is preferably 5 μm or less because adhesion tends to be improved.

Examples of the method for dispersing the copolymer include: (a) a method in which the copolymer and an emulsifier are kneaded while applying a shear stress, and then dispersed in water; (b) the copolymer is toluene or the like. (C) A method of removing the organic solvent after mixing with an emulsifier while applying shear stress together with an emulsifier, and then removing the organic solvent; (c) This copolymer is organic such as toluene, hexane, heptane, xylene, etc. Examples include a method of dissolving in a solvent, mixing with an emulsifier, emulsifying under high pressure or normal pressure, or applying ultrasonic waves, and then distilling off the solvent.
As a method of dispersing this copolymer, the method of (a) and (b) in which the shear stress is applied to water is used, the volume-based median diameter of the dispersoid is set to 1 μm or less, and as a result, the resulting cured product is obtained. The method (a) is preferable because it tends to improve the adhesiveness of the product, and more preferably the method (a) which does not require removal of the organic solvent.

Here, the shear rate at the time of a shearing stress, usually about 200 to 100,000 sec ^-1, preferably about 1000 to 2500 sec ^-1. When the shear rate is 200 seconds ⁻¹ or more, the adhesiveness of the resulting emulsion tends to be improved, and when the shear rate is 100,000 seconds ⁻¹ or less, industrial production becomes easy. It is preferable because of its tendency.
The shear rate is a numerical value obtained by dividing the peripheral speed [mm / sec] of the outermost periphery of the screw element by the clearance [mm] between the screw and the barrel.

  Examples of the apparatus for applying the shear stress include a multi-screw extruder such as a twin-screw extruder, Labo Plast Mill (Toyo Seiki Seisakusho), Labo Plast Mill Micro (Toyo Seiki Seisakusho), homogenizer, TK Examples include an apparatus in which an aqueous emulsion is placed between a barrel (cylinder) and a stirring blade such as Filmics (Primics Co., Ltd.), and the stirring blade is rotated to apply shear stress.

  As a specific method for producing an emulsion using a multi-screw extruder, the copolymer is supplied from a hopper of a multi-screw extruder having two or more screws in a casing, heated, melt-kneaded, and further extruded. Examples include a method of kneading with at least one liquid supply port provided in the compression zone and / or the metering zone of the machine and then dispersing in water.

  Examples of devices that apply shear stress other than the above devices include, for example, a stirring tank, a chemical stirrer, a vortex mixer, a flow jet mixer, a colloid mill, a static mixer, and a micromixer (the shear stress is applied only by the rotation of the stirring blade. ), An ultrasonic generator, a high-pressure homogenizer, and dispersion (Fujikin Co., Ltd.).

  As a method for producing the aqueous emulsion of the present invention, a method of kneading the copolymer and an emulsifier while applying a shear stress and then dispersing in water is preferable because a desired median diameter described later can be easily obtained. A twin-screw extruder and a multi-screw extruder are preferable because they can process a highly viscous modified product. Among these, a twin screw extruder is preferably used.

The volume-based median diameter of the dispersoid in the aqueous emulsion of the present invention is preferably 0.01 to 5 μm, more preferably 0.01 to 1 μm, particularly preferably from the viewpoint of improving the adhesiveness of the resulting cured product. 0.05 to 0.5 μm.
The volume-based median diameter is preferably 0.01 μm or more because the dispersoid can be easily produced, and the volume-based median diameter is preferably 5 μm or less because adhesion tends to be improved.
Here, the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis.

〔式（III）中、Ｑは、酸素原子又は硫黄原子を表し、Ｘ¹、Ｘ²、Ｘ³及びＸ^４は互いに独立に、水素原子、炭素数１〜６の直鎖アルキル基、炭素数３〜６の分枝アルキル基、又は、Ｘ¹あるいはＸ²と、Ｘ³あるいはＸ^４とが結合した炭素数１〜６のアルキレン基を表し、但し、アルキル基及びアルキレン基の水素原子は水酸基で置換されていてもよい。〕
で表される尿素類であってよい。
炭素数１〜６の直鎖アルキル基としては、例えば、メチル基、エチル基などが挙げられる。炭素数３〜６の分枝アルキル基としては、例えば、ｉ−イソプロピル基などが挙げられる。炭素数１〜６のアルキレン基としては、例えば、エチレン基、プロピレン基などが挙げられる。 The aqueous emulsion of the present invention contains ureas and a cationic polymer in addition to the copolymer and the emulsifier.
Here, ureas are represented by the formula (III):

[In Formula (III), Q represents an oxygen atom or a sulfur atom, and X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a carbon number. A branched alkyl group having 3 to 6 or an alkylene group having 1 to 6 carbon atoms in which X ¹ or X ² and X ³ or X ⁴ are bonded to each other, provided that the hydrogen atom of the alkyl group and the alkylene group is a hydroxyl group May be substituted. ]
The ureas represented by
Examples of the linear alkyl group having 1 to 6 carbon atoms include a methyl group and an ethyl group. Examples of the branched alkyl group having 3 to 6 carbon atoms include i-isopropyl group. Examples of the alkylene group having 1 to 6 carbon atoms include an ethylene group and a propylene group.

Specific examples of ureas include urea, methylurea, dimethylurea, thiourea, 4,5-dihydroxy-2-imidazolidinone, 1- (2-aminoethyl) -2-imidazolidinone, diethylenetriamine and urea. And a mixture containing 1- (2-aminoethyl) -2-imidazolidinone as a main component obtained by the deammonia reaction.
Different ureas may be used in combination as ureas.
Among ureas, urea is preferable because it is easily available.

  The urea content is preferably 0.1 to 30 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the total copolymer. When the compound is 0.1 part by weight or more, the transparency of the resulting cured product tends to be improved, and when it is 30 parts by weight or less, the adhesive property of the resulting cured product tends to be excellent. This is preferable.

  The cationic polymer used in the present invention means a polymer in which the main polymer is dissociated into cations in an aqueous medium. Typical cationic groups include primary, secondary and tertiary amino groups, and quaternary ammonium salts. Any cationic polymer can be used, and the type thereof is not particularly limited. Examples of the cationic polymer preferably used in the present invention include the following.

a) a polyalkylene polyamide obtained by dehydration condensation of a polyalkylene polyamine and a dibasic carboxylic acid;
b) Polyalkylene polyurea obtained by deammonia condensation of polyalkylene polyamine and urea:
c) polyamide polyurea obtained by deammonia condensation of polyalkylene polyamide and urea; d) polyamino epoxy resin obtained by reacting an amino group-containing compound with epihalohydrin;
e) a reaction product obtained by further reacting any of the polymers a) to d) with an aldehyde;
f) a reaction product obtained by reacting any of the above polymers a) to d) with an alkylating agent;
g) Ring-opening polymer of ethyleneimine;
h) homopolymers of cationic vinyl monomers or copolymers with other copolymerizable monomers;
i) N-vinylamide monomer homopolymer or hydrolyzate of copolymer with other copolymerizable monomer;
j) a Mannich reactant obtained by reacting ammonia, a primary amine or a secondary amine and formaldehyde with a polymer having active hydrogen;
k) a reaction product of a polymer having active hydrogen and a cationizing agent;
l) A reaction product obtained by reacting ammonia or amines with epihalohydrin to a polymer having active hydrogen;
m) chitosan hydrolyzed chitin;
n) A block copolymer obtained by reacting a polymer having active hydrogen with any of the above polymers a) to m) using a crosslinking agent such as an aldehyde, epihalohydrin, polyisocyanate or the like.

Specific examples of the raw material compounds used in producing these various cationic polymers are given below.
The polyalkylene polyamine used in the above a) and b) is a compound in which two primary amino groups and at least one secondary amino group are bonded via alkylene, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine And iminobispropylamine.

  The dibasic carboxylic acid used in the above a) is a compound having two carboxyl groups, an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, isophthalic acid, Illustrative are acids, aromatic dicarboxylic acids such as terephthalic acid, and mixtures thereof.

  Examples of the amino group-containing compound used in d) include ammonia, various amines, polyamine, polyalkylene polyamine, polyalkylene polyamide, polyalkylene polyurea, polyamide polyurea and the like.

  Examples of the epihalohydrin used in the above d), l) and n) include epichlorohydrin, epibromohydrin and the like.

  Examples of the aldehyde used in the above e) and n) include alkyl aldehydes such as formaldehyde, acetaldehyde and propyl aldehyde, and alkyl dialdehydes such as glyoxal, propanedial and butanedial.

As the alkylating agent in f), the following various types can be used.
General formula:
R ¹ -X
[Wherein R ¹ represents a lower alkyl group (for example, about 1 to 6 carbon atoms), a lower alkenyl group (for example, about 2 to 6 carbon atoms), a benzyl group or a phenoxyethyl group, and X represents a halogen atom]
A halogen-containing compound represented by: Examples include methyl chloride, ethyl chloride, propyl chloride, allyl chloride, benzyl chloride, phenoxyethyl chloride, and the bromides and iodides corresponding to these chlorides.

General formula:
(R ² O) ₂ SO _V
[Wherein R ² represents a lower alkyl group (for example, about 1 to 6 carbon atoms), and v represents 1 or 2]
Dialkyl sulfite and dialkyl sulfate represented by Examples thereof include dimethyl sulfite, diethyl sulfite, dimethyl sulfate, diethyl sulfate and the like.

〔式中、Ｒ³ は水素原子、低級アルキル基（例えば炭素数１〜６程度）、ヒドロキシ低級アルキル基（例えば炭素数１〜６程度）またはフェニル基を表す〕
で示されるエチレンオキサイドおよびその誘導体。この例として、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、グリシドールなどが挙げられる。 General formula:

[Wherein R ³ represents a hydrogen atom, a lower alkyl group (for example, about 1 to 6 carbon atoms), a hydroxy lower alkyl group (for example, about 1 to 6 carbon atoms) or a phenyl group]
And ethylene oxide and its derivatives. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidol and the like.

〔式中、Ｘはハロゲン原子を表し、ｗは１、２または３を表す〕
で示されるエピハロヒドリン。この例として、エピクロロヒドリン、エピブロモヒドリンなどが挙げられる。 General formula:

[Wherein X represents a halogen atom and w represents 1, 2 or 3]
Epihalohydrin represented by Examples thereof include epichlorohydrin and epibromohydrin.

General formula:
HOCH ₂ (CH ₂ ) _W X
[Wherein X represents a halogen atom and w represents 1, 2 or 3]
Monohalohydrin represented by Examples thereof include ethylene chlorohydrin and ethylene bromohydrin.

〔式中、Ｘはハロゲン原子を表し、ＹおよびＺの一方はハロゲン原子、他方は水酸基を表す〕
で示されるジハロヒドリン。この例として、１，３−ジクロロ−２−プロパノール、２，３−ジクロロ−１−プロパノールなどが挙げられる。 General formula:

[Wherein, X represents a halogen atom, one of Y and Z represents a halogen atom, and the other represents a hydroxyl group]
Dihalohydrin represented by Examples of this include 1,3-dichloro-2-propanol, 2,3-dichloro-1-propanol, and the like.

  Examples of the cationic vinyl monomer used in h) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and these Quaternized products, allylamine, diallylamine, triallylamine, vinylpyrrolidone, diallyldimethylammonium salt and the like are exemplified.

  Examples of the N-vinylamide monomer used in i) include vinylformamide and vinylacetamide.

  Examples of the polymer having active hydrogen used in j), k), l) and n) include starches, polyvinyl alcohol, polyacrylamide, proteins such as casein, and methylcellulose.

  Examples of the cationizing agent used in k) include those represented by the following general formula in addition to ethyleneimine.

〔これらの式中、Ｑは二価の脂肪族基または芳香族基を表し、Ｒ⁴およびＲ⁵はそれぞれ独立に低級アルキル基（例えば炭素数１〜６程度）を表し、Ｒ⁶は水素原子または低級アルキル基（例えば炭素数１〜６程度）を表し、Ａ^-はハロゲン化物イオン、硫酸イオンなどの陰イオンを表し、Ｌはハロゲン原子、スルホン酸エステル基、硫酸エステル基などの脱離基を表す〕 General formula:

[In these formulas, Q represents a divalent aliphatic group or an aromatic group, R ⁴ and R ⁵ each independently represent a lower alkyl group (for example, about 1 to 6 carbon atoms), and R ⁶ represents a hydrogen atom. Or a lower alkyl group (for example, about 1 to 6 carbon atoms), A ⁻ represents an anion such as halide ion or sulfate ion, and L represents a leaving group such as a halogen atom, sulfonate group or sulfate group. Represents)

  In the above formula, examples of the divalent aliphatic group represented by Q include alkylene having about 1 to 10 carbon atoms, and the alkylene may be branched or have a substituent. Also good. Examples of the alkylene substituent include a hydroxyl group, an alkoxy group having about 1 to 6 carbon atoms, an alkanoyloxy group having about 1 to 6 carbon atoms, and a halogen atom. Examples of the divalent aromatic group represented by Q include substituted or unsubstituted phenylene. Examples of the phenylene substituent include those exemplified as the above-mentioned alkylene substituents, and alkyl groups having about 1 to 6 carbon atoms. Groups.

In the above formula, examples of the sulfonic acid ester group represented by L include a methanesulfonic acid residue (CH ₃ SO ₂ O—), an ethanesulfonic acid residue (C ₂ H ₅ SO ₂ O—), and benzenesulfonic acid. Examples thereof include ester groups of alkyl or aryl sulfonic acids such as residues (C ₆ H ₅ SO ₂ O—), toluenesulfonic acid residues (CH ₃ C ₆ H ₄ SO ₂ O—), and sulfate groups. In addition to sulfate residues (HOSO ₂ O—), for example, methyl sulfate residues (CH ₃ OSO ₂ O—), ethyl sulfate residues (C ₂ H ₅ OSO ₂ O—), phenyl sulfate residues (C ₆ the ester groups of alkyl or aryl sulfates, such as H ₅ OSO ₂ O-) and the like.

  The various cationic polymers exemplified above can be obtained, for example, according to the method described in JP-A-6-166994.

  The amount of the cationic polymer used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight with respect to 100 parts by weight as a total of the olefin copolymer or the modified product. When the amount of the cationic polymer used is 0.1 parts by weight or more, it is preferable because the water resistance of the resulting cured product tends to be improved, and when the amount used is 30 parts by weight or less, it is obtained. It is preferable because the adhesiveness of the cured product tends to be excellent.

  As a method for producing the aqueous emulsion of the present invention, for example, ureas are mixed with the copolymer, and then an emulsifier is kneaded while applying a shear stress, and then dispersed in water. Mixing method: Urea is mixed with water together with emulsifier, kneaded with this copolymer while applying shear stress, then dispersed in water, and then cationic polymer is mixed; emulsifier and main copolymer A method in which a polymer is kneaded while applying a shear stress, and then dispersed in water to obtain an aqueous emulsion, and then ureas and a cationic polymer are mixed; the emulsifier, the copolymer and the cationic polymer are subjected to a shear stress. Examples thereof include a method of kneading while acting and dispersing in water to obtain an aqueous emulsion and then mixing ureas.

Examples of the aqueous emulsion of the present invention include aqueous emulsions such as polyurethane aqueous emulsions and ethylene-vinyl acetate copolymer aqueous emulsions, thermosetting resins such as urea resins, melamine resins, and phenol resins, clays, kaolin, talc, carbonic acid. Fillers such as calcium, preservatives, rust preventives, antifoaming agents, foaming agents, polyacrylic acid, polyether, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, starch and other thickeners, viscosity modifiers, flame retardants, oxidation A pigment such as titanium, a high-boiling solvent such as dimethyl succinate or dimethyl adipate, a dibasic acid, or a plasticizer may be blended.
In particular, when the aqueous emulsion of the present invention is applied to an adherend having a low interfacial tension such as polypropylene or polyester, silicon such as polyether-modified polydimethylsiloxane is used as necessary from the viewpoint of increasing wettability. It is preferable to add a system additive or an acetylene glycol surfactant.
It is recommended to use the filler to improve the flame retardancy and the coating property at the time of adhesion. The amount used is usually 1 to 500 parts by weight with respect to 100 parts by weight of the solid content of the emulsion. The degree is preferably about 5 to 200 parts by weight.

  Examples of the adherend bonded to the adhesive layer derived from the aqueous emulsion of the present invention include wood-based materials such as wood, plywood, MDF (medium specific gravity fiber board), particle board, fiber board; wallpaper, wrapping paper Paper-based materials such as: Cellulose-based materials such as cotton, linen, and rayon; Polyethylene (polyolefins mainly composed of structural units derived from ethylene, the same shall apply hereinafter), Polypropylene (polyolefins composed mainly of structural units derived from propylene) ), Polyolefins such as polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, and other plastic materials; glass, ceramics, etc. Ceramic material; iron, stainless steel Scan, copper, a metal material such as aluminum and the like.

  Such an adherend may be a composite material composed of a plurality of materials. Further, it may be a kneaded molded product of an inorganic filler such as talc, silica, activated carbon or the like or carbon fiber and a plastic material.

When one of the adherends is an adherend having water absorbency such as a wood-based material, a paper-based material, and a cellulose-based material, the aqueous emulsion of the present invention is used as it is as an adhesive, Can be pasted. In other words, after applying an aqueous emulsion to a water-absorbent adherend, if another adherend (which may be water-absorbing or non-water-absorbing) is laminated on the layer derived from the aqueous emulsion, the moisture contained in the aqueous emulsion Is absorbed by the water-absorbent adherend, and the layer derived from the aqueous emulsion becomes an adhesive layer, whereby a laminate having a water-absorbent adherend / adhesive layer / adherent body can be obtained.
When both of the adherends are non-water-absorbing, after applying the aqueous emulsion of the present invention to one adherend on one side and drying to form an adhesive layer derived from the aqueous emulsion, the other adherend The adherends may be bonded together and heated to be bonded.

The adhesive layer derived from the aqueous emulsion of the present invention can have excellent adhesiveness with an adherend of polyolefin such as polypropylene, which has been conventionally considered to be difficult to adhere.
At the same time, the adhesive layer may have excellent adhesion to the polyurethane adherend.
As described above, in order to bond the adherend of polyolefin and the adherend of polyurethane, it has been conventionally known that a chlorine-based polyolefin is used as an adhesive layer, but the adhesion derived from the aqueous emulsion of the present invention. The layer does not contain chlorine, and only the adhesive layer can have excellent adhesion to both the polyolefin adherend and the polyurethane adherend. A laminate in which the polyurethane adherend is foamed polyurethane is suitable for automobile interior and exterior.

  Here, the polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by a reaction of alcohol (—OH) and isocyanate (—NCO). The foamed polyurethane as shown in the examples may be a polyurethane foamed by a volatile solvent such as carbon dioxide or freon resulting from the reaction of isocyanate with water used as a crosslinking agent. Semi-rigid polyurethane can be used for automobile interiors.

  As the adherend, polypropylene, polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), polyethylene terephthalate, polyvinyl chloride, (meth) acrylic resin, glass, aluminum, polyurethane and the like are preferable. More preferred are vinyl chloride, glass, aluminum and polyurethane.

A cured product having improved water resistance can be obtained from the aqueous emulsion of the present invention.
The cured product is excellent in transparency, adhesiveness, moldability, heat resistance, solvent resistance and mechanical properties.
The cured product can be obtained by drying the aqueous emulsion of the present invention at 80 ° C. for 20 minutes.
In addition, the aqueous emulsion of the present invention can be used for paints, binders, coating agents, adhesives or primers. In particular, when the aqueous emulsion of the present invention is applied onto polypropylene, which has been conventionally referred to as a difficult-to-adhere material, it does not contain chlorine, and has transparency, adhesiveness, moldability, heat resistance, solvent resistance and mechanical properties. An excellent paint or primer can be obtained.

Hereinafter, the present invention will be described in more detail based on examples, but it is needless to say that the present invention is not limited to these examples.
In the examples, parts and% mean weight basis unless otherwise specified.
The solid content was measured by a measuring method according to JIS K-6828.
The viscosity is a value measured with a Brookfield viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C.
The median diameter is a value on a volume basis measured by a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd.).
The intrinsic viscosity [η] was measured at 135 ° C. using tetralin as a solvent using an Ubbelohde viscometer.

The molecular weight of the olefin copolymer and the modified product of the olefin copolymer is calibrated with polystyrene (molecular weight 688 to 400,000) standard substance using gel permeation chromatograph (GPC), It calculated | required on the following conditions. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (hereinafter referred to as Mw) and the number average molecular weight (hereinafter referred to as Mn).
Model Waters 150-C
Column shodex packed column A-80M
Measurement temperature 140 ℃
Measurement solvent Orthodichlorobenzene measurement concentration 1mg / ml

The content of vinylcyclohexane units in the olefin copolymer was determined by the following ¹³ C-NMR apparatus.
¹³ C-NMR apparatus: DRX600 manufactured by BRUKER
Measurement solvent: orthodichlorobenzene: orthodichlorobenzene-d4 =
4: 1 (volume ratio) liquid mixture Measurement temperature: 135 ° C

The graft polymerization amount of maleic anhydride was quantified by the following procedure: 1.0 g of sample was dissolved in 20 ml of xylene, and the sample solution was dropped into 300 ml of methanol while stirring to recover the sample, and then recovered. After vacuum drying the sample (80 ° C., 8 hours), a film having a thickness of 100 μm was prepared by hot pressing, the infrared absorption spectrum of the obtained film was measured, and the maleic acid graft was determined from the absorption near 1780 cm ^−1. The amount of polymerization was quantified.

<Production Example 1 of Olefin Copolymer>
386 parts of vinylcyclohexane (hereinafter sometimes referred to as VCH) and 3640 parts of toluene were charged into a SUS reactor substituted with argon. After raising the temperature to 50 ° C., ethylene was charged from atmospheric pressure to 0.6 MPa. 10 parts of a toluene solution of triisobutylaluminum (hereinafter sometimes referred to as TIBA) [TIBA concentration 20% manufactured by Tosoh Akzo Co., Ltd.] was charged, followed by diethylsilyl (tetramethylcyclopentadienyl) (3- tert-butyl-5-methyl-2-phenoxy) titanium dichloride 0.001 part dissolved in dehydrated toluene 87 parts and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.03 part dissolved in dehydrated toluene 122 parts Was added and stirred for 2 hours. The obtained reaction solution was poured into about 10,000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 300 parts of an ethylene / vinylcyclohexane copolymer was obtained. [Η] of the copolymer is 0.48 dl / g, Mn is 27,000, molecular weight distribution (Mw / Mn) is 2.0, melting point (Tm) is 62 ° C., glass The transition point (Tg) was −28 ° C., and the content of structural units derived from VCH in the copolymer was 12.2 mol%.

<Example 2 of Production of Olefin Copolymer>
441 parts of vinylcyclohexane and 947 parts of a dehydrated hexane mixture (2-methylpentane, 3-methylpentane, normal hexane, methylcyclopentane, cyclohexane) were charged into a SUS reactor substituted with argon. After charging 350 parts of propylene, the temperature was raised to 60 ° C. 3 parts of hexane solution of triisobutylaluminum (TIBA) [manufactured by Tosoh Finechem Co., Ltd., TIBA concentration 10 wt%] was charged, and then dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl). 2-phenoxy) titanium dichloride 0.0010 parts dissolved in dehydrated hexane 3.4 parts, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 0.0064 parts, dehydrated hexane 3.8 parts, And the mixture was stirred for 2 hours. After 5 parts of ethanol was added to the resulting reaction mixture to stop the polymerization, the pressure was released to remove propylene, the resulting reaction liquid was poured into about 5000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 140 parts of a propylene / vinylcyclohexane copolymer was obtained. [Η] of the copolymer is 0.65 dl / g, molecular weight distribution (Mw / Mn) is 1.9, melting point (Tm) is not observed, glass transition point (Tg) is −1.2 ° C., The content of VCH units in the copolymer was 4.7 mol%.

<Example of production of modified product of unsaturated copolymer of olefin copolymer>
To 100 parts of the ethylene / vinylcyclohexane copolymer obtained in the section <Preparation Example 1 of Olefin Copolymer>, 0.4 part of maleic anhydride and 1,3-bis (t-butylperoxyisopropyl) benzene 0.04 part was added and sufficiently premixed, then supplied from the supply port of the twin screw extruder and melt kneaded to obtain a maleic anhydride modified product (this modified product) of an ethylene / vinylcyclohexane copolymer. . The temperature of the melt kneading part of the extruder is divided into two stages, the first half and the second half, and the first half is 180 ° C. and the second half is 260 ° C. and the temperature is increased to 260 ° C. I got a thing. The amount of maleic acid graft polymerization of the obtained modified olefin copolymer was 0.2%.

<Mixed product, emulsifier and water>
After setting the cell of Labo Plast Mill Micro manufactured by Toyo Seiki to 95 ° C, 3.12 g of the modified product obtained in <Production example of modified product of unsaturated copolymer of olefin copolymer with unsaturated carboxylic acid> is enclosed in the cell. And stirred for 3 minutes at 300 rpm. The maximum shear rate at this time was 1173 sec- ¹ . Thereafter, 0.46 g of oxyethyleneoxypropylene block copolymer (weight average molecular weight 15500: Pluronic F108: manufactured by Asahi Denka Co., Ltd.) is added as an emulsifier together with 0.21 g of water, and the temperature in the cell is kept at 95 ° C. Further, the mixture was kneaded at 300 rpm for 3 minutes (shear speed 1173 sec- ¹ ). After kneading, the contents were taken out and stirred and dispersed in a container containing warm water of about 70 ° C. to obtain an emulsion having a volume-based median diameter of the dispersoid of 0.43 μm.

<Mixing of olefin copolymer, emulsifier and water>
After setting the cylinder temperature of the table type kneader PBV-0.3 type manufactured by Irie Shokai Co., Ltd. to 97 ° C., 110 parts of the copolymer obtained in <Olefin-based copolymer production example 2> was placed in the cylinder. The resin was melted for 10 minutes while rotating forward at 10 revolutions per minute. After melting, oxyethylene oxypropylene block copolymer (weight average molecular weight 15500: Pluronic F108: manufactured by Asahi Denka Co., Ltd.) as an emulsifier is added in an amount of 11 parts as a solid content, and the cover glass is occasionally opened at 60 rpm to remove. The mixture was kneaded and emulsified for 4 minutes while foaming. Subsequently, 110 parts of warm water of 90 ° C. was added and dispersed to obtain an aqueous emulsion having a volume-based median diameter of 1.5 μm.

<Production of aqueous cationic polymer solution>
A four-necked flask equipped with a thermometer, a reflux condenser and a stirring rod was charged with 176.5 g of water and 73.1 g (1.0 mol) of butylamine, and 191.6 g (1.1 mol) of ethylene glycol diglycidyl ether. ) Was added dropwise, followed by reaction at 50 to 60 ° C. for 2 hours. Thereafter, the pH was adjusted to 9.0 with sulfuric acid and water to a concentration of 40% to obtain an aqueous solution of a cationic polymer having a viscosity of 55 cps.

Example 1
100 parts by weight (40% solids) of the emulsion obtained in the section <mixing of the present modified product, emulsifier and water> and 1.68 parts by weight of the aqueous solution obtained in <Manufacture of an aqueous cationic polymer solution> (40% solids) %) And 1.58 parts by weight of urea were stirred for 30 minutes at a rotation speed of 500 rpm, and mixed thoroughly to obtain an aqueous emulsion of the present invention.

(Example 2)
100 parts by weight (solid content 40%) of the emulsion obtained in the section <Mixed product, emulsifier and water> and 1.00 parts by weight of the aqueous solution obtained in <Preparation of aqueous cationic polymer solution> (solid content 40 %) And 0.95 parts by weight of urea at 500 rpm for 30 minutes and thoroughly mixed to obtain an aqueous emulsion of the present invention.

(Example 3)
100 parts by weight of the emulsion (solid content 40%) obtained in the section <Mixed modified product, emulsifier and water> and 2.52 parts by weight of the aqueous solution obtained in <Production of cationic polymer aqueous solution> (solid content 40 %) And 2.36 parts by weight of urea were stirred at a rotation speed of 500 rpm for 30 minutes to completely mix them to obtain an aqueous emulsion of the present invention.

Example 4
<Emulsion copolymer, emulsifier and water mixture> 100 parts by weight of the emulsion obtained in the section (solid content 49.6%) and <Preparation of cationic polymer aqueous solution> 3.13 parts by weight (Solid content 40%) and 2.92 parts by weight of urea were stirred at a rotation speed of 500 rpm for 30 minutes and mixed thoroughly to obtain an aqueous emulsion of the present invention.

(Comparative Example 1)
Water was added to the emulsion obtained in the section <Mixed modified product, emulsifier and water> (adjustment of solid content 40%) and stirred at 500 rpm for 30 minutes to obtain an aqueous emulsion.

(Comparative Example 2)
<100 parts by weight of emulsion (solid content 40%) and 1.58 parts by weight of urea obtained in section <Mixing of modified product, emulsifier and water> and 1.58 parts by weight of urea are stirred at 500 rpm for 30 minutes to completely dissolve urea. An aqueous emulsion was obtained.

(Comparative Example 3)
100 parts by weight (40% solids) of the emulsion obtained in the section <mixing of the present modified product, emulsifier and water> and 1.68 parts by weight of the aqueous solution obtained in <Manufacture of an aqueous cationic polymer solution> (40% solids) %) Was stirred for 30 minutes at a rotation speed of 500 rpm and mixed thoroughly to obtain an aqueous emulsion.

<Water resistance evaluation>
The aqueous emulsions obtained in the Examples and Comparative Examples were applied to a 75 μm thick polyethylene terephthalate film with a bar coater so that the film thickness after drying was 10 μm, and then cured by drying at 80 ° C. for 35 minutes with a hot air dryer. I got a thing. One drop of pure water was dropped on the obtained cured product, the surface of the cured product was rubbed with a finger together with water, and the time until the surface was peeled was measured.

  According to the present invention, it is possible to obtain a cured product that is excellent in adhesiveness, does not contain chlorine, and has excellent water resistance.

Claims (11)

Vinyl compound (I) having a structural unit and a substituent R derived from α-olefin and / or ethylene and / or propylene:
_{CH 2 = CH-R (I} )
[In formula (I), R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group. ]
An aqueous emulsion having an olefin copolymer, an emulsifier, ureas and a cationic polymer containing a structural unit derived from   The aqueous emulsion according to claim 1, wherein the olefin copolymer further comprises a structural unit derived from unsaturated carboxylic acids. Ureas have the following formula (III):

[In Formula (III), Q represents an oxygen atom or a sulfur atom, and X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a carbon number. A branched alkyl group having 3 to 6 or an alkylene group having 1 to 6 carbon atoms in which X ¹ or X ² and X ³ or X ⁴ are bonded to each other, provided that the hydrogen atom of the alkyl group and the alkylene group is a hydroxyl group May be substituted. ]
The aqueous emulsion of Claim 1 or 2 which is a compound represented by these.   Water-soluble acrylic resin, polyoxyethylene, wherein the emulsifier contains a structural unit derived from an α, β-unsaturated carboxylic acid, a structural unit derived from a vinyl acrylate ester, and a structural unit derived from a (meth) acrylic acid ester The aqueous emulsion according to any one of claims 1 to 3, which is at least one emulsifier selected from the group consisting of a polyoxypropylene block copolymer and a polyoxyethylene alkyl ether.   The aqueous emulsion according to any one of claims 1 to 4, wherein the cationic polymer is a reaction product of a polyamine and epichlorohydrin.   Dispersoid volume standard comprising an olefin copolymer and an emulsifier comprising a structural unit derived from an α-olefin and / or ethylene and / or propylene and a structural unit derived from a vinyl compound (I) having a substituent R The aqueous emulsion according to any one of claims 1 to 5, wherein the median diameter is 0.01 to 1 µm.   The aqueous emulsion according to any one of claims 1 to 6, wherein the vinyl compound (I) is vinylcyclohexane.   Hardened | cured material formed by drying the aqueous emulsion in any one of Claims 1-7.   A laminate formed by laminating an adherend made of at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material, and the cured product according to claim 8.   The laminate according to claim 9, wherein the plastic material is polyolefin.   The laminate according to claim 9 or 10, wherein the plastic material is polypropylene.