JP2011246573A - Aqueous emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion not containing a chlorinated polyolefin but giving a coating film excellent in adhesion to polypropylene.SOLUTION: The aqueous emulsion comprises: (A) an olefin copolymer comprising a structural unit derived from ethylene and/or a linear α-olefin and a structural unit derived from a vinyl compound represented by the formula (I): CH=CH-R (I) (wherein R represents a secondary alkyl group, a tertiary alkyl group or an alicyclic hydrocarbon group), or a polymer obtained by graft polymerization of an α,β-unsaturated carboxylic acid anhydride onto the olefin copolymer; (B) an acrylic resin comprising a structural unit derived from an α,β-unsaturated carboxylic acid and a structural unit derived from an α,β-unsaturated carboxylic acid ester; (C) a nonionic emulsifier; and (D) water.

Description

  The present invention relates to an aqueous emulsion and the like.

Polypropylene is used for automobile parts such as bumpers because it is excellent in processability and strength. A paint is usually applied to an automobile part for decoration or the like.
However, since other materials such as paint are difficult to adhere to the surface of polypropylene, chlorinated polyolefin with excellent adhesion to polypropylene is applied to polypropylene to form a cured film of chlorinated polyolefin. After that, it is generally performed to apply a paint (for example, Patent Document 1).

JP 5-7832 A ([Claims])

However, since the chlorinated polyolefin contains chlorine atoms, there is a problem that hydrochloric acid gas or the like is generated when the polypropylene coated with the chlorinated polyolefin is burned, and the disposal of the polypropylene is complicated.
Accordingly, there is a need for an emulsion that does not contain chlorinated polyolefin and that provides a coating film with excellent adhesion to polypropylene.

Under such circumstances, as a result of intensive studies, the inventors have arrived at the inventions shown in [1] to [15] below.
[1] An aqueous emulsion containing the following (A), (B), (C) and (D);
(A) a structural unit derived from ethylene and / or a linear α-olefin, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
An olefin copolymer containing a structural unit derived from a vinyl compound represented by:
A polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the olefin copolymer (B) a structural unit derived from α, β-unsaturated carboxylic acid, and an α, β-unsaturated carboxylic acid [1] Description wherein acrylic resin (C) nonionic emulsifier (D) water [2] (A) MFR (190 ° C., 2.16 kgf) containing 10 to 300 is a structural unit derived from an acid ester. An aqueous emulsion of
[3] The aqueous emulsion according to [1], wherein the MFR (190 ° C., 2.16 kgf) of (A) is 130 to 300;
[4] The aqueous emulsion according to any one of [1] to [3], wherein the vinyl compound represented by the formula (I) is vinylcyclohexane;

[5] The structural unit derived from the α, β-unsaturated carboxylic acid in (B) is derived from at least one α, β-unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid. The aqueous emulsion according to any one of [1] to [4];
[6] At least one α, β-unsaturated carboxylic acid wherein the structural unit derived from the α, β-unsaturated carboxylic acid ester in (B) is selected from the group consisting of alkyl acrylates and alkyl methacrylates. The aqueous emulsion according to any one of [1] to [5], which is a structural unit derived from an ester;
[7] The structural unit derived from the α, β-unsaturated carboxylic acid ester in (B) is obtained from a C 1-10 aliphatic alcohol having a carboxylic acid group and an α, β-unsaturated carboxylic acid. The aqueous emulsion according to any one of [1] to [6], which is a structural unit derived from an α, β-unsaturated carboxylic acid ester;
[8] The structural unit derived from the α, β-unsaturated carboxylic acid ester in (B) is an α obtained from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group and an α, β-unsaturated carboxylic acid. An aqueous emulsion according to any one of [1] to [6], which is a structural unit derived from a β, unsaturated carboxylic acid ester;
[9] (B) is obtained from a structural unit derived from an α, β-unsaturated carboxylic acid, an aliphatic alcohol having 1 to 10 carbon atoms having an amino group, and an α, β-unsaturated carboxylic acid. An acrylic resin containing a structural unit derived from an α, β-unsaturated carboxylic acid ester, wherein the total number of amino groups contained in the resin is less than the total number of carboxylic acid groups contained in the resin [8 ] Aqueous emulsion according to the description;
[10] The aqueous emulsion according to any one of [1] to [9], wherein (B) further contains an ammonium cation;
[11] The aqueous emulsion according to any one of claims 1 to 10, wherein (C) is an acetylene glycol emulsifier or a polyoxyethylene emulsifier.

[12] A cured product obtained by drying the aqueous emulsion according to any one of [1] to [11];
[13] It has an adherent layer made of at least one material selected from the group consisting of woody materials, cellulosic materials, plastic materials, ceramic materials, and metal materials, and a layer made of a cured product as described in [12]. Laminates;

[14] A method for producing an aqueous emulsion comprising a step of melt-kneading the following (A), (B), (C) and (D);
(A) a structural unit derived from ethylene and / or a linear α-olefin, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
An olefin copolymer containing a structural unit derived from a vinyl compound represented by:
A polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the olefin copolymer (B) a structural unit derived from α, β-unsaturated carboxylic acid, and an α, β-unsaturated carboxylic acid Acrylic resin containing a structural unit derived from an acid ester (C) Nonionic emulsifier (D) Water [15] At least one selected from the group consisting of woody materials, cellulosic materials, plastic materials, ceramic materials and metal materials A first step of applying a water-based emulsion according to any one of [1] to [11] to an adherent layer made of a seed material to obtain a coated product having the adherent layer and a layer comprising the aqueous emulsion When,
The manufacturing method of a laminated body which has a 2nd process of drying the coated article obtained at the 1st process, and obtaining the laminated body which consists of the said adhesion layer and the hardened | cured material layer obtained from the said aqueous emulsion.

  The aqueous emulsion of the present invention can give a coating film excellent in adhesiveness with polypropylene.

(A) used in the present invention is a structural unit derived from ethylene and / or a linear α-olefin, and a compound of formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
And an olefin copolymer (hereinafter, referred to as “polymer (Aa)”) including a structural unit derived from a vinyl compound represented by the formula (hereinafter, sometimes referred to as vinyl compound (I)). ) Or
It is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the polymer (Aa) (hereinafter sometimes referred to as “polymer (Ab)”). Hereinafter, the polymer (Aa) and the polymer (Ab) may be collectively referred to as “polymer (A)”.

  R of the vinyl compound (I) is a secondary alkyl group, a tertiary alkyl group or an alicyclic hydrocarbon group. 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 3 to 3. An alicyclic hydrocarbon group having a 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.

As specific examples of the vinyl compound (I), the vinyl compound (I) in which the substituent R is a secondary alkyl group includes 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- Rimechiru-1-octene and the like,
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, 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, etc.
Examples of the vinyl compound (I) in which the substituent R is an alicyclic hydrocarbon group include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, 5-vinyl-2-norbornene, Examples thereof include 1-vinyladamantane and 4-vinyl-1-cyclohexene.

  Preferred vinyl compounds (I) are 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, vinylcyclopentane, Vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, and 5-vinyl-2-norbornene. More preferred vinyl compounds (I) are 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 vinyl compounds (I) are 3,3-dimethyl-1-butene and vinylcyclohexane. The most preferred vinyl compound (I) is vinylcyclohexane.

The content of the structural unit derived from the vinyl compound (I) in the polymer (Aa) is usually based on 100 mol% of the structural unit derived from all monomers constituting the polymer (Aa). It is 5 to 40 mol%, preferably 10 to 30 mol%, particularly preferably 10 to 20 mol%.
It is preferable for the content of the structural unit derived from the monomer of the vinyl compound (I) to be 40 mol% or less since the adhesiveness of the resulting adhesive tends to improve.
The content of the structural unit derived from the monomer of the vinyl compound (I) can be determined using a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

  As a linear alpha olefin used by this invention, a C3-C20 linear alpha olefin containing propylene is mentioned normally. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene , Linear olefins such as 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, and 1-eicocene. Among these, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and propylene is more preferable.

  In the polymer (Aa), the total content of the structural unit derived from ethylene and the structural unit derived from the linear α-olefin is a structure derived from all monomers constituting the polymer (Aa). It is 95-60 mol% normally with respect to 100 mol% of units, Preferably it is 90-70 mol%, More preferably, it is 90-80 mol%.

  As ethylene and / or linear α-olefin, ethylene and propylene are preferable.

(式中、Ｒ’、Ｒ”は、それぞれ独立に、炭素数１〜１８程度の直鎖状、分枝状あるいはシクロのアルキル基、また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、後述するα，β−不飽和カルボン酸、後述するα，β−不飽和カルボン酸エステル、後述するα，β−不飽和カルボン酸無水物などが挙げられる。 The polymer (Aa) may further be copolymerized with a monomer capable of addition polymerization.
Here, the addition-polymerizable monomer is a monomer excluding ethylene, linear α-olefin and vinyl compound (I), and is added with ethylene, linear α-olefin and vinyl compound (I). It is a polymerizable monomer, and the carbon number of the monomer is usually about 3 to 20.
Specific examples of the monomer capable of addition polymerization include cycloolefin, the following general formula (II)

(In the formula, R ′ and R ″ each independently represents a linear, branched or cycloalkyl group having about 1 to 18 carbon atoms, or a halogen atom.)
Vinylidene compounds, diene compounds, vinyl halides, vinyl alkylates, vinyl ethers, acrylonitriles, α, β-unsaturated carboxylic acids described below, α, β-unsaturated carboxylic esters described below, α described below , Β-unsaturated carboxylic acid anhydride and the like.

  Examples of the cycloolefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, and 5-ethyl-2-norbornene. 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopenta Decene, 2-pentacyclohexadecene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxy Carbonyl-2-norbornene 5-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. More preferred cycloolefins are cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricyclo Undecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl 2-norbornene and 5-cyano-2-norbornene, preferably 2-norbornene and 2-tetracyclododecene.

  Examples of the vinylidene compound 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-octene, 2 , 4-dimethyl-1-pentene, 2,4,4-trimethyl-1-pentene, vinylidene chloride and the like. Preferred vinylidene compounds are isobutene, 2,3-dimethyl-1-butene and 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 and the like. Preferred diene compounds are 1,4-pentadiene, 1,5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene. is there.

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

  The content of the structural unit derived from the addition-polymerizable monomer used for the polymer (Aa) is usually in a range where the adhesiveness of the resulting aqueous emulsion is not impaired, and the specific content is Usually about 5 mol% or less, preferably substantially containing structural units derived from addition-polymerizable monomers, with respect to 100 mol% of structural units derived from all monomers constituting the combined (Aa) To the extent that it does not, specifically, the content is 1 mol% or less.

  Examples of the method for producing the polymer (Aa) include a method of producing in the presence of a catalyst using a transition metal compound having a group having an indenyl type anion skeleton or a crosslinked cyclopentadiene type anion skeleton, and the like. Is mentioned. 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 the polymer (Aa), depending on the type of catalyst used and the polymerization conditions, in addition to the copolymer of the present invention, a homopolymer of ethylene or a homopolymer of vinyl compound (I) (vinylcyclohexane, etc.) May be a by-product. 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. As a solvent used for such extraction, 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. (Aa) can be fractionated as a soluble component of both solvents. Of course, if there is no problem depending on the use, the polymer (Aa) may be used in the presence of such a by-product.

The molecular weight distribution (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) of the polymer (Aa) is usually about 1.5 to 10.0, preferably 1.5 to 7. About 0, more preferably about 1.5 to 5.0. It is preferable that the molecular weight distribution of the polymer (Aa) is 1.5 or more and 10.0 or less because the mechanical strength and transparency of the resulting polymer (A) tend to be improved.
Moreover, the weight average molecular weight (Mw) of a polymer (Aa) is about 5,000-1,000,000 normally, and from a viewpoint of mechanical strength, Preferably it is about 10,000-500,000. More preferably, it is about 15,000 to 400,000. The polymer (A-1) preferably has a weight average molecular weight of 5,000 or more because the mechanical strength of the resulting polymer (A) tends to be improved, and is 1,000,000 or less. This is preferable because the fluidity of the resulting polymer (A) tends to be improved.
The molecular weight distribution of the polymer (A-a) can be determined using gel permeation chromatograph (GPC) according to the method specifically described in Examples below.

  The intrinsic viscosity [η] of the polymer (Aa) is usually about 0.25 to 10 dl / g, and preferably about 0.3 to 3 dl / g from the viewpoint of mechanical strength.

The value of the melt flow rate (MFR) of the polymer (Aa) is set to 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven) in accordance with JIS K 7210. If it measures below, it is 10-300 normally, Preferably it is 130-300, More preferably, it is 130-220. In particular, from the viewpoint of film forming property, it is preferably 20 to 300, more preferably 20 to 250. More preferably, it is 30-230, More preferably, it is 50-210, Most preferably, it is 60-200.
In addition, MFR of a polymer (Aa) changes the usage-amount of molecular weight modifiers, such as hydrogen, polymerization temperature, etc. in the copolymerization of ethylene and / or a linear alpha olefin, and vinyl compound (I). By doing so, it can be adjusted.

The polymer (Ab) is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the polymer (Aa) thus obtained.
The graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride with respect to 100 parts by weight of the polymer (Ab) is usually 0.01 to 20 with respect to 100% by weight of the resulting polymer (Ab). It is about wt%, preferably about 0.05 to 10 wt%, more preferably about 0.1 to 5 wt%.
When the graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride is 0.01% by weight or more, the adhesive force of the polymer (Ab) tends to be improved, and preferably 20% by weight or less. When it exists, it exists in the tendency for the thermal stability of a polymer (Ab) to improve, and it is preferable.

Examples of the α, β-unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, nadic acid anhydride, methyl nadic anhydride, and hymic anhydride. Further, the above α, β-unsaturated carboxylic acid anhydride may be used in combination.
As the α, β-unsaturated carboxylic acid anhydride, maleic anhydride is preferable.

As a method for producing the polymer (Ab), for example, a method in which the polymer (Aa) is melted and then α, β-unsaturated carboxylic acid anhydride is added to perform graft polymerization, or a polymer ( Examples thereof include a method in which A-a) is dissolved in a solvent such as toluene and xylene, and then α, β-unsaturated carboxylic acid anhydride is added to cause graft polymerization.
After the polymer (Aa) is melted, α, β-unsaturated carboxylic acid anhydride is added and graft polymerization is performed by melt-kneading using an extruder, so that resins or resins and solids are solidified. Alternatively, it is preferable because various known methods for mixing liquid additives can be employed. More preferable examples include a method in which all or some of the components are 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. it can. As the melt-kneading means, conventionally known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed. Preferably, from the viewpoint that continuous production is possible and productivity is improved, an olefin copolymer, an unsaturated carboxylic acid, and a radical initiator that are sufficiently premixed in advance using a single or twin screw extruder are added. This is a method of carrying out kneading by supplying from the supply port of the extruder. The temperature of the portion where the melt kneading of the extruder is carried out (for example, the cylinder temperature in the case of an extruder) is usually 50 to 300 ° C, preferably 80 to 270 ° C. When the temperature is 50 ° C. or higher, the graft amount tends to be improved, and when the temperature is 300 ° C. or lower, the decomposition of the polymer (Aa) 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 usually 0.1 to 30 minutes, preferably 0.1 to 5 minutes. If the melt-kneading time is 0.1 minutes or more, the graft amount tends to be improved, and if the melt-kneading time is 30 minutes or less, the decomposition of the polymer (Aa) tends to be suppressed. To preferred.

In order to graft polymerize the α, β-unsaturated carboxylic acid anhydride to the polymer (Aa), the polymerization is usually carried out in the presence of a radical initiator.
The addition amount of the radical initiator is usually 0.01 to 10 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer (Aa). The amount added is preferably 0.01 parts by weight or more because the amount of grafting to the polymer (Aa) tends to increase and the adhesive strength tends to improve, and the amount added is preferably 10 parts by weight or less. This is preferable because unreacted radical initiator in the modified product is reduced and the adhesive strength tends to be improved.
The radical initiator is usually an organic peroxide, preferably an organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute. When the decomposition temperature is 50 ° C. or higher, the graft amount tends to be improved, and when the decomposition temperature is 210 ° C. or lower, the decomposition of the polymer (Aa) tends to be reduced. Further, these organic peroxides preferably decompose and generate radicals, and then have an action of extracting protons from the polymer (Aa).

  Examples of the organic peroxide 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, percarbonate compounds, and the like. . 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-hexylperoxy Sopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5 dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl Peroxyacetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-beroxy) valerate, di-t-butylberoxyisophthalate , Dicumyl peroxide, 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 And hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, and the like. A decomposition temperature of 50 to 210 ° C. is preferable because the graft amount is improved. Among these organic peroxides, preferred are dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds, and alkyl perester compounds. The addition amount of the organic oxide is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the polymer (Aa).

  The structural unit derived from the α, β-unsaturated carboxylic acid anhydride contained in the polymer (Ab) thus obtained was a ring-opened one even if the acid anhydride group was closed. The ring-closed one and the ring-opened one may be contained.

The molecular weight distribution (Mw / Mn) of the polymer (Ab) is usually 1.5 to 10, preferably 1.5 to 7, and more preferably 1.5 to 5. A molecular weight distribution of 10 or less is preferred because the adhesion of the polymer (A) tends to be improved.
The molecular weight distribution of the polymer (Ab) can be measured in the same manner as the molecular weight distribution of the olefin copolymer.

  The intrinsic viscosity [η] of the polymer (Ab) is usually about 0.25 to 10 dl / g, and preferably about 0.3 to 3 dl / g from the viewpoint of mechanical strength.

The value of the melt flow rate (MFR) of the polymer (Ab) is 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210. If it measures below, it is 10-300 normally, Preferably it is 130-300, More preferably, it is 130-220. In particular, from the viewpoint of dispersibility, it is preferably 20 to 300, more preferably 20 to 250. More preferably, it is 30-230, More preferably, it is 50-210, Most preferably, it is 60-200.
The MFR of the polymer (Ab) is controlled by the reaction temperature at the time of crosslinking in the presence of a radical initiator or graft polymerization with an α, β-unsaturated carboxylic acid anhydride and a radical initiator, It can be carried out depending on conditions such as the type and amount of the radical initiator. In general, when the polymer (Ab) is an ethylene-based polymer, if the amount of the radical initiator is large, the MFR decreases, and when the polymer (A-b) is a polypropylene-based polymer, the radical initiation If the amount of the agent is small, the MFR tends to be small, but the MFR can be controlled by controlling the type of radical initiator and the temperature condition.

(B) is an acrylic resin containing a structural unit derived from an α, β-unsaturated carboxylic acid and a structural unit derived from an α, β-unsaturated carboxylic acid ester. Hereinafter, an emulsifier (B) and Sometimes written.
Here, as the α, β-unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, methyl nadic acid, highmic acid, Examples include angelic acid, tetrahydrophthalic acid, sorbic acid, and mesaconic acid.
As the α, β-unsaturated carboxylic acid, plural kinds of α, β-unsaturated carboxylic acids may be used.
As the α, β-unsaturated carboxylic acid, acrylic acid and methacrylic acid are particularly preferable.

  The α, β-unsaturated carboxylic acid ester is an ester of α, β-unsaturated carboxylic acid, and is obtained from, for example, an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. α, β-unsaturated carboxylic acid ester, α, β-unsaturated carboxylic acid ester obtained from aliphatic alcohol having 1 to 10 carbon atoms having amino group and α, β-unsaturated carboxylic acid, carbon having hydroxyl group Α, β-unsaturated carboxylic acid ester obtained from aliphatic alcohol of number 1 to 10 and α, β-unsaturated carboxylic acid, C 1-10 aliphatic alcohol having carboxylic acid group and α, β- And α, β-unsaturated carboxylic acid esters obtained from unsaturated carboxylic acids.

  Here, examples of the α, β-unsaturated carboxylic acid constituting the α, β-unsaturated carboxylic acid ester include those similar to the α, β-unsaturated carboxylic acid, and particularly acrylic acid and methacrylic acid. Is preferred.

Examples of the aliphatic alcohol having 1 to 20 carbon atoms include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, t-butyl alcohol, amyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, deca alcohol. Nyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, cyclohexyl alcohol and the like can be mentioned.
Examples of the α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, and acrylic acid. Butyl, amyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decanyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Examples include amyl methacrylate, ethyl hexyl methacrylate, nonyl methacrylate, decanyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, and the like. Two or more α, β-unsaturated carboxylic acid esters obtained from the aliphatic alcohol having 1 to 20 carbon atoms and the α, β-unsaturated carboxylic acid may be used in combination.

Examples of the aliphatic alcohol having 1 to 10 carbon atoms having an amino group include an amino group (—NH ₂ ) and an alkylamino group (—NHR ² and R ² are alkyl having 1 to 10 carbon atoms) on the hydrogen atom of the aliphatic alcohol. Group) or a dialkylamino group (—NR ³ R ⁴ , R ³ and R ⁴ each represent an aliphatic alcohol having 1 to 10 carbon atoms, and R ³ and R ⁴ may be the same or different. ) Means a substituted group. Specifically, aminoalkyl alcohols such as aminomethyl alcohol, aminoethyl alcohol, aminopropyl alcohol; for example, 2- (N-methylamino) ethyl alcohol, 2- (N-ethylamino) ethyl alcohol, 2- (N -Isopropylamino) ethyl alcohol, 3-methylaminopropyl alcohol, 2- (Nn-propylamino) ethyl alcohol, 2- (Nn-butylamino) ethyl alcohol, 2- (N-isobutylamino) ethyl alcohol Alkylaminoalkyl alcohols such as 2- (N-sec-butylamino) ethyl alcohol and 2- (Nt-butylamino) ethyl alcohol; for example, 2- (N, N-dimethylamino) ethyl alcohol, 2- (N-methyl-N-ethylamino) ethyl alcohol And dialkylaminoalkyl alcohols such as 2- (N, N-diethylamino) ethyl alcohol, 3- (N, N-dimethylamino) propyl alcohol and 3- (N, N-diethylamino) propyl alcohol; .
Examples of the α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid include N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N-methyl-N-ethylaminoethyl acrylate, N-methyl-N-ethylaminoethyl methacrylate, etc. N, N-dimethylaminoethyl methacrylate is preferred. Two or more kinds of α, β-unsaturated carboxylic acid esters obtained from the aliphatic alcohol having 1 to 10 carbon atoms having an amino group and the α, β-unsaturated carboxylic acid may be used in combination.

The C1-C10 aliphatic alcohol having a hydroxyl group means a group in which a hydroxyl group is substituted on a hydrogen atom of the aliphatic alcohol. Specific examples include hydroxymethyl alcohol, hydroxyethyl alcohol, hydroxypropyl alcohol, hydroxybutyl alcohol, hydroxypentyl alcohol, hydroxyhexyl alcohol and the like.
Examples of the α, β-unsaturated carboxylic acid ester obtained from a C1-C10 aliphatic alcohol having a hydroxyl group and an α, β-unsaturated carboxylic acid include, for example, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate , Hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxyhexyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, hydroxyhexyl methacrylate, and the like. Two or more α, β-unsaturated carboxylic acid esters obtained from the aliphatic alcohol having 1 to 10 carbon atoms having a hydroxyl group and the α, β-unsaturated carboxylic acid may be used in combination.

As a C1-C10 aliphatic alcohol which has a carboxylic acid group, the carboxylic acid group is substituted by the hydrogen atom of the said aliphatic alcohol. Here, the carboxylic acid group represents an organic group having a carboxy group, and examples thereof include a carboxymethyl group, a 1,2-dicarboxyethyl group, a 2-carboxyphenyl group, and a 2,3-dicarboxyphenyl group. It is done.
Examples of the α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an α, β-unsaturated carboxylic acid include 2-acryloyloxyethyl succinic acid, 2 -Acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, etc. are mentioned. Two or more kinds of α, β-unsaturated carboxylic acid esters obtained from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an α, β-unsaturated carboxylic acid may be used in combination.

The content of the structural unit derived from the α, β-unsaturated carboxylic acid in the emulsifier (B) is usually 5 to 95 mol% with respect to 100 mol% of all the structural units constituting the emulsifier (B). Yes, preferably 5 to 80 mol%.
The content of the structural unit derived from the α, β-unsaturated carboxylic acid ester in the emulsifier (B) is usually 5 to 95 mol% with respect to 100 mol% of all the structural units constituting the emulsifier (B). Preferably, it is 10-80 mol%.

  The emulsifier (B) is an ethylene, linear α-olefin, vinyl compound (I) other than the structural unit derived from α, β-unsaturated carboxylic acid and the structural unit derived from α, β-unsaturated carboxylic acid ester. ) And a structural unit derived from the addition-polymerizable monomer, the content is usually in a range where the adhesiveness of the resulting aqueous emulsion is not impaired, and a specific total The content is about 5 mol% or less, preferably 1 mol% or less, more preferably a single amount capable of addition polymerization, with respect to 100 mol% of structural units derived from all the monomers constituting the emulsifier (B). The content is such that the structural unit derived from the body is not substantially contained.

As the structural unit derived from the α, β-unsaturated carboxylic acid ester in the emulsifier (B), structural units derived from different kinds of α, β-unsaturated carboxylic acid esters may be used.
Among structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acid esters obtained from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid The content of the derived structural unit is usually 5 to 95 mol%, preferably 10 to 80 mol%, based on 100 mol% of all the structural units constituting the emulsifier (B).
Among the structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated obtained from an α, β-unsaturated carboxylic acid and an aliphatic alcohol having 1 to 10 carbon atoms having an amino group Content of the structural unit derived from carboxylic acid ester is 1-80 mol% normally with respect to 100 mol% of all the structural units which comprise an emulsifier (B), Preferably, it is 1-50 mol%. is there.
Among structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated compounds obtained from α, β-unsaturated carboxylic acids and C 1-10 aliphatic alcohols having carboxylic acid groups Content of the structural unit derived from saturated carboxylic acid ester is 0.1-80 mol% normally with respect to 100 mol% of all the structural units which comprise an emulsifier (B), Preferably, it is 5-40 Mol%.
Among structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acids obtained from α, β-unsaturated carboxylic acids and C1-C10 aliphatic alcohols having a hydroxyl group A structural unit derived from an acid ester may be contained, and the content thereof is usually 0 to 50 mol% with respect to 100 mol% of all the structural units constituting the emulsifier (B), preferably It is 0-30 mol%, More preferably, it is 1 mol% or less, More preferably, it is not containing substantially.

  As the emulsifier (B), the content of structural units derived from α, β-unsaturated carboxylic acid is 5 to 80 mol% and the number of carbon atoms with respect to 100 mol% of all structural units constituting the emulsifier (B). The content of structural units derived from an α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol of 1-20 and an α, β-unsaturated carboxylic acid is 10 to 80 mol%, and the number of carbons having an amino group The content of structural units derived from an α, β-unsaturated carboxylic acid ester obtained from 1 to 10 aliphatic alcohols and an α, β-unsaturated carboxylic acid is 1 to 50 mol%, and a carboxylic acid group The content of the structural unit derived from the α, β-unsaturated carboxylic acid ester obtained from the aliphatic alcohol having 1 to 10 carbon atoms and the α, β-unsaturated carboxylic acid is 5 to 30 mol% (however, the above Total content of structural units is 100 It is preferable to contain a structural unit of

  As a method for producing the emulsifier (B), for example, a mixture of monomers (such as a monomer having a structural unit derived from an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid ester) is subjected to addition polymerization. The method of manufacturing by doing is mentioned. Specifically, alcohol such as isopropyl alcohol or water is used as a solvent, and a part or all of the monomer is mixed in the solvent, and the radical is usually at 0 to 50 ° C., preferably 0 to 30 ° C. The initiator and the remaining monomer are mixed, and usually stirred for about 1 to 24 hours. In order to control the reaction, a radical initiator may be added after dissolving in an organic solvent.

  Here, examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbohydrate). Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2- Azo compounds such as methyl propionate) and 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene Hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, tert Organic peroxides such as butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxidation such as potassium persulfate, ammonium persulfate, hydrogen peroxide Thing etc. are mentioned. A redox initiator using a thermal polymerization initiator and a reducing agent in combination can also be used as the polymerization initiator.

  (C) is a nonionic emulsifier, and may hereinafter be referred to as an emulsifier (C). As the nonionic emulsifier, sorbitan aliphatic ester, glycerin aliphatic ester and the like can be used, but acetylene glycol emulsifier or polyoxyethylene emulsifier is preferably used. As these nonionic emulsifiers, usually commercially available ones can be used.

  Examples of the acetylene glycol emulsifier include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol. And ethylene oxide adducts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and polyalkylene oxide. These are commercially available as “Surfinol®”.

  Examples of the polyoxyethylene emulsifier include polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer, polyoxyethylene alkyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene Examples thereof include ethylene sorbitan aliphatic ester, polyoxyethylene sorbitol aliphatic ester, polyoxyethylene aliphatic ester, polyoxyethylene-polyoxypropylene block polymer of ethylenediamine, and polyoxyethylene hydrogenated castor oil. Of these, polyoxyethylene-polyoxypropylene block polymers and polyoxyethylene alkyl ethers are preferred.

  Examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, and polyoxyethylene octyldodecyl ether. Among these, polyoxyethylene lauryl ether is preferable.

  Examples of the polyoxyethylene sorbitan aliphatic ester include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate. And polyoxyethylene sorbitan trioleate.

  Examples of the polyoxyethylene sorbitol aliphatic ester include polyoxyethylene sorbitol tetraoleate.

  Examples of the polyoxyethylene aliphatic ester include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol dilaurate, and polyethylene glycol monooleate.

  The emulsifier (C) preferably has an average molecular weight of 1000 to 20000.

The aqueous emulsion of the present invention contains the above (A), (B), (C) and (D).
The amount of (B) used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of (A).
The amount of (C) used is preferably 0.001 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of (A). When the amount of (C) used is 0.001 part by weight or more, the temporal stability of the aqueous emulsion tends to be improved, and when it is 10 parts by weight or less, workability during spray coating tends to be improved. is there.
The amount of (D) used is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight with respect to (A) 100 parts by weight.

As a method for producing the aqueous emulsion, (A), (B), (C) and (D) are melt-kneaded; (A) is heated, and the heated (A) obtained in the heating step is used. (B) and (C) are mixed with each other; (A), (B) and (C) are heated and kneaded, and the kneaded product obtained in the above step is (D). A step of dissolving; a dissolving step of dissolving (A) in an organic solvent such as toluene; a mixing step of mixing the solution obtained in the dissolving step with (B) and (C); and the mixing A step of removing the organic solvent from the mixture obtained in the step; a step of melt kneading (A), (B) and (D); and a kneaded product obtained in the step (C) A step of mixing (B) with (A), and the above step And the like; the method comprising the step of mixing the kneaded mixture (C) that is.
Moreover, the emulsion manufacturing method by chemical emulsification methods, such as self-emulsification other than the above mechanical emulsification methods, is also illustrated.
A method comprising a step of melt kneading (A), (B) and (D) and a step of mixing (C) with the kneaded product obtained in the above step is suitable.

  (A), (B) and (C) and, if necessary, as an apparatus used in the step of melt kneading (D), for example, a twin-screw extruder, Labo Plast Mill (Toyo Seiki Seisakusho Co., Ltd.), Lab Multi-screw extruders such as Plast Mill Micro (Toyo Seiki Seisakusho), homogenizer, T. Equipment with a barrel (cylinder) such as K Fillmix (registered trademark of Primix Co., Ltd.), for example, stirring tank, chemical stirrer, vortex mixer, flow jet mixer, colloid mill, ultrasonic generator, high-pressure homogenizer, Disperse-kun (stock) Examples of such devices include a company that does not have a barrel (cylinder) such as Fujikin's registered trademark), a static mixer, and a micromixer.

As a shear rate of the apparatus which has a barrel, it is about 200-100000 second- ¹ normally, Preferably it is about 1000-2500 second- ¹ . When the shear rate is 200 seconds ⁻¹ or more, the adhesiveness of the resulting emulsion tends to improve, and when it is 100,000 seconds ⁻¹ or less, production tends to be easy industrially. preferable.
Here, the shear rate is a numerical value obtained by dividing the peripheral speed [mm / sec] of the outermost peripheral portion of the screw element by the clearance [mm] between the screw and the barrel.

As a method of melt kneading (A), (B), (C) and (D), for example, (A) is continuously supplied from the hopper or supply port of a twin screw extruder, and this is heated and melt kneaded. Further, (B) and (C) are supplied under pressure from at least one supply port provided in the compression zone, metering zone or degassing zone of this extruder, and (A) is kneaded with a screw, Subsequently, a method of continuously producing an aqueous emulsion from a die by supplying (D) from at least one supply port provided in the compression zone of the extruder may be mentioned.
As a method including a heating step of heating (A) and a mixing step of mixing (B) with the heated (A) obtained in the heating step, for example, after heating a cylinder of a kneader, the cylinder (A) is charged into the inside, and a heating step for melting while rotating is performed. Next, (B) is added and a mixing step for rotating is performed. Subsequently, the obtained mixture is charged into warm water, For example, a method of obtaining an aqueous emulsion by dispersing it may be mentioned.
A method using a multi-screw extruder is suitable as the method including the heating step of heating (A) and the mixing step of mixing (B) with the heated (A) obtained in the heating step.
Specifically, first, a heating step in which (A) is supplied from a hopper of a multi-screw extruder having two or more screws in a casing, and heated and melt-kneaded, then, a compression zone of the extruder or / And a method for producing the aqueous emulsion of the present invention through a mixing step of dispersing in (D) while kneading with (B) supplied from at least one liquid supply port provided in the measurement zone. .

The aqueous emulsion of the present invention is preferably one in which the dispersoid containing (A), (B) and (C) is dispersed in (D) which is a dispersion medium.
The volume-based median diameter of the dispersoid is usually 0.01 to 3 μm, preferably 0.5 to 2.5 μm, more preferably 0.5 to 1.5 μm.
When the volume-based median diameter is 0.01 μm or more, it is preferable from the viewpoint of easy production, and when it is 3 μm or less, adhesiveness 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.

  Examples of the 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, calcium carbonate. Such as fillers; antiseptics; rust preventives; antifoaming agents; foaming agents; thickeners such as polyacrylic acid, polyether, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, starch; viscosity modifiers; flame retardants; titanium oxide Pigments such as dibasic acids such as dimethyl succinate and dimethyl adipate; plasticizers and the like may be blended.

  The aqueous emulsion of the present invention is applied to the adherent layer and then dried to give a cured product. Such a cured product can usually be used for paints, primers, base materials, adhesives and the like. In the present invention, a film-like product of the cured product is sometimes referred to as a coating film.

  For example, wood, plywood, medium density fiberboard (MDF), particleboard, fiberboard, and other woody materials; wallpaper, wrapping paper, and other paper-based materials: cellulose, cotton, linen, rayon, etc. Materials: Polyethylene (polyolefin having a structural unit derived from ethylene as a main component, the same shall apply hereinafter), polypropylene (polyolefin having a structural unit derived from propylene as a main component, the same shall apply hereinafter), polystyrene (mainly a structural unit derived from styrene) Polyolefins such as polyolefin as a component, the same applies hereinafter), plastic materials such as polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), (meth) acrylic polyester, polyether, polyvinyl chloride, polyurethane, urethane foam; Glass, ceramic Ceramic materials; iron, stainless steel, copper, a metal material such as aluminum and the like.

  Such an adhesion layer may be a composite material composed of a plurality of materials. Further, an inorganic filler such as talc, silica and activated carbon, a kneaded molded product of carbon fiber and a plastic material may be used.

  Here, the polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO). The urethane foam is a polyurethane foamed by a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water used as a crosslinking agent. Semi-rigid polyurethane is used for automobile interiors, and hard polyurethane is used for paints.

The adherent layer is preferably at least one material selected from the group consisting of wood-based materials, cellulosic materials, plastic materials, ceramic materials, and metal materials. Among these materials, polypropylene, polystyrene, polycarbonate, acrylonitrile / butadiene / styrene are preferable. A polymer (ABS resin), polyethylene terephthalate, polyvinyl chloride, (meth) acrylic resin, glass, aluminum, polyurethane and the like are preferable, and polypropylene, polyvinyl chloride, glass, aluminum and polyurethane are more preferable.
The cured product derived from the aqueous emulsion of the present invention has excellent adhesion to an adherent layer of polyolefin such as polypropylene, which has been conventionally considered to be difficult to adhere.

When one of the adhering layers is a water-absorbing adhering layer such as a wood-based material, a paper-based material, or a cellulosic material, the aqueous emulsion of the present invention is applied as it is and bonded to the other adhering layer. be able to. That is, after an aqueous emulsion is applied to a water-absorbing layer, another layer (which may be water-absorbing or non-water-absorbing) is laminated on the layer derived from the aqueous emulsion. Moisture is absorbed by the water-absorbing adherent layer, and the layer derived from the aqueous emulsion becomes an adhesive layer, and a laminate having a water-absorbing adherent layer / cured product layer / adhesive layer can be obtained.
When both of the adherend layers are non-water-absorbing, after applying the aqueous emulsion of the present invention to one adherend on one side and drying to form a cured product layer derived from the aqueous emulsion, the other The adhering layer may be bonded and heated for adhesion.

  The cured product of the present invention may be further coated with a liquid material as a paint. As the coating material, a material exemplified as the material of the adherent layer such as polyurethane, and a liquid material is preferable because of excellent adhesion to the cured product.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples mean weight basis unless otherwise specified.
Moreover, the solid content in an emulsifier and an aqueous emulsion was measured by the measuring method according to JIS K-6828.

(1) The molecular weight of the olefin copolymer and the polymer (A) is calibrated with polystyrene (molecular weight 688 to 400,000) standard substance using gel permeation chromatograph (GPC), and then Obtained under 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

(2) 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
Measuring solvent: orthodichlorobenzene and orthodichlorobenzene-d4
4: 1 (volume ratio) liquid mixture Measurement temperature: 135 ° C
Measurement method: Powergate Decoupling method Pulse angle: 45 degrees Measurement standard: Tetramethylsilane

Vinylcyclohexane unit content in ethylene-vinylcyclohexane copolymer The vinylcyclohexane unit content in the ethylene-vinylcyclohexane copolymer was calculated from the following formula.
<Calculation formula>
Vinylcyclohexane unit content (mol%) = 100 × A / (B-2A)
A: Integrated integrated value of 45 ppm to 40 ppm signal B: Integrated integrated value of 35 ppm to 25 ppm signal

Vinylcyclohexane unit content in propylene-vinylcyclohexane copolymer The vinylcyclohexane unit content in propylene-vinylcyclohexane copolymer was calculated from the following formula.
<Calculation formula>
Vinylcyclohexane unit content (mol%) = 100 × A / (A + B + C)
A: 1/6 of the integrated signal integration value of 28 ppm to 27 ppm
B: Signal integration integration value of 22 ppm to 19.5 ppm C: Signal integration integration value of 18 ppm to 14 ppm

(3) Intrinsic viscosity ([η], unit: dl / g)
An Ubbelohde viscometer was used and measured at 135 ° C. using tetralin as a solvent.

(4) Glass transition point (Tg) (unit: ° C), melting point (Tm) (unit: ° C)
A differential scanning calorimetry curve is measured using a differential scanning calorimeter (SSC-5200, manufactured by Seiko Denshi Kogyo Co., Ltd.) under the following conditions, and the glass transition point and melting point are determined from the differential scanning calorimetry curve at the second temperature increase. It was.
<Measurement conditions>
Temperature rise (first time): The temperature was raised from 20 ° C. to 200 ° C. at 10 ° C./min, and then held at 200 ° C. for 10 minutes.
Temperature decrease: Immediately after the first temperature increase operation, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of 10 ° C./min, and then held at −100 ° C. for 10 minutes.
Temperature increase (second time): Immediately after the temperature decrease operation, the temperature was increased from −100 ° C. to 200 ° C. at 10 ° C./min.

  The grafted amount of maleic anhydride is obtained by dissolving 1.0 g of a sample in 20 ml of xylene, dropping the sample solution into 300 ml of methanol while stirring to reprecipitate the sample, and then vacuum drying the collected sample. A film having a thickness of 100 μm was prepared by hot pressing (80 ° C., 8 hours), the infrared absorption spectrum of the obtained film was measured, and the amount of maleic acid graft was quantified from the absorption near 1780 cm −1.

Production Example 1: Olefin Copolymer 386 parts of vinylcyclohexane (hereinafter sometimes referred to as VCH) and 3640 parts of toluene were charged into a reactor made of SUS substituted with argon. After raising the temperature to 50 ° C., 0.01 MPa of hydrogen and 0.6 MPa of ethylene were charged. 10 parts of a toluene solution of triisobutylaluminum (TIBA) [manufactured by Tosoh Finechem Co., Ltd., TIBA concentration 20 wt%] was charged, followed by diethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl) 2-phenoxy) titanium dichloride 0.0006 parts dissolved in dehydrated toluene 87 parts, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 0.03 parts and dehydrated toluene 122 parts And stirred for 2 hours. After 10 parts of ethanol was added to the resulting reaction mixture to stop the polymerization, the pressure was released to remove ethylene, the resulting mixture 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 olefin copolymer was obtained. [Η] of the copolymer is 0.48 dl / g, Mn is 15,600, molecular weight distribution (Mw / Mn) is 2.0, melting point (Tm) is 57 ° C., glass transition point (Tg) is − At 28 ° C., the content of VCH units in the copolymer was 13 mol%.

Production Example 2: Polymer (A-1)
To 100 parts of the olefin copolymer obtained in Production Example 1, 0.4 parts of maleic anhydride and 0.04 parts of 1,3-bis (t-butylperoxyisopropyl) benzene were added and thoroughly mixed. It was supplied from the supply port of the twin screw extruder and melt kneaded to obtain (A-1) which is one type of the polymer (A). The temperature of the part of the extruder where the melt kneading was performed was divided into two stages, the first half and the latter half, and the melt kneading was performed at a temperature setting of 180 ° C in the first half and 260 ° C in the second half. The maleic acid graft amount of (A-1) was 0.2%. Moreover, MFR of (A-1) was 180 g / 10min (190 degreeC, load: 2.16kgf).

Production Example 3: Emulsifier (B-1)>
As the monomer for the emulsifier (B), the monomers listed in Table 1 were used.

"AA" 14.5 parts (27.6 molar ratio), "HO-MS" 22.5 parts (13.4 molar ratio), "DMA" 38 parts (33.2 molar ratio), "MMA" 15 parts (20.6 molar ratio) and 10 parts of “SLMA” (5.2 molar ratio) were mixed at 10 to 30 ° C. to obtain 100 parts of a monomer mixture. Here, the molar ratio represents the number of moles when the total number of moles of the monomers is 100.
A 1 L reactor equipped with a cooler, a nitrogen introducing tube, a stirrer, a dropping funnel and a heating jacket was charged with 150 parts of isopropyl alcohol (hereinafter sometimes referred to as IPA) and 100 parts of ion-exchanged water while stirring. The internal temperature was adjusted to 80 ° C. After the reaction vessel was purged with nitrogen, 20 parts of the monomer mixture was added all at once. Further, 2 parts of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and stirred at the same temperature. Next, it stirred at the same temperature, dripping 80 parts of this monomer liquid mixture over 4 hours. Every 1 hour after the start of dropping of the monomer mixture, 0.15 parts of the polymerization initiator was added in four portions, and the mixture was further stirred for 3 hours at the same temperature. Subsequently, the temperature of the resulting reaction solution was raised to a boiling point to distill off IPA. After distilling off, the internal temperature was lowered to 50 ° C., and then 29 parts (49 mole ratio) of 28% aqueous ammonia solution was mixed. Thereafter, a viscous emulsifier (B) was obtained (yield 90%, hereinafter referred to as (B-1)).

Reference Example: Aqueous emulsion not containing emulsifier (C) After setting the cylinder temperature of the same direction rotating meshing twin screw extruder (manufactured by Nippon Steel Works, Ltd .: TEX30φ, L / D = 30) to 110 ° C From the hopper of the extruder, 110 parts of the polymer (A) (A-1) was continuously supplied at a screw rotation speed of 350 rpm, and (A-1) was heated.
10 parts (solid content) of (B-1), which is an emulsifier (B), are continuously supplied from a supply port provided in the vent part of the extruder while being pressurized with a gear pump, and (A-1) and (B -1) was mixed while continuously extruded to obtain a milky white aqueous emulsion.

Examples 1 to 10: Aqueous emulsion of the present invention The total amount of the aqueous emulsion obtained in the Reference Example and 1 part of each of the emulsifiers (C) described in Tables 2 and 3 were mixed, and the aqueous emulsion of the present invention was mixed. Obtained.

  The adhesiveness evaluation and the temporal stability evaluation of the aqueous emulsions obtained in Reference Examples and Examples 1 to 10 were carried out as follows, and the results are shown in Tables 2 and 3.

<Adhesion evaluation>
After washing a polypropylene plate (thickness 3 mm: hereinafter referred to as PP plate) with IPA, the aqueous emulsion was applied using a bar coater so that the thickness of the coating film after drying was 10 μm. This was dried with a hot air dryer at 80 ° C. for 5 minutes, and further heated and dried in an oven at 90 ° C. for 30 minutes to obtain a coating film. Based on JIS-K5400 (cross-cut peeling tape method test), the obtained coating film was cut into a grid-like cut with a gap interval of 1 mm, and then a cellophane tape was affixed on the coating film. Next, one to two minutes after the cellophane tape was applied, one end of the tape was held and peeled off at a right angle to evaluate adhesion. The evaluation criteria were as follows.
A: There was no peeling at a glance at the intersection of the cuts and the square.
○: The area of peeling is less than 40% of the square area.
X: The area of peeling is 40% or more of the square area.

<Stability evaluation over time>
30 g of the obtained aqueous emulsion was put into a 100 ml polypropylene container, covered, and stored in a gear oven at 50 ° C. for 6 days, then the cover was opened and the skin was observed. The evaluation criteria were as follows.
X: There is skin on the emulsion surface.
○: There is no skinning on the emulsion surface.

  The aqueous emulsion of the present invention can give a coating film excellent in adhesiveness with polypropylene. Furthermore, it is excellent in stability over time.

Claims (15)

An aqueous emulsion containing the following (A), (B), (C) and (D).
(A) a structural unit derived from ethylene and / or a linear α-olefin, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
An olefin copolymer containing a structural unit derived from a vinyl compound represented by:
A polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the olefin copolymer (B) a structural unit derived from α, β-unsaturated carboxylic acid, and an α, β-unsaturated carboxylic acid Acrylic resin (C) nonionic emulsifier (D) water containing a structural unit derived from an acid ester   The aqueous emulsion according to claim 1, wherein MFR (190 ° C, 2.16 kgf) of (A) is 10 to 300.   The aqueous emulsion according to claim 1, wherein MFR (190 ° C, 2.16 kgf) of (A) is 130 to 300.   The aqueous emulsion according to any one of claims 1 to 3, wherein the vinyl compound represented by the formula (I) is vinylcyclohexane.   The structural unit derived from α, β-unsaturated carboxylic acid in (B) is a structural unit derived from at least one α, β-unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid. Item 5. The aqueous emulsion according to any one of Items 1 to 4.   The structural unit derived from the α, β-unsaturated carboxylic acid ester in (B) is derived from at least one α, β-unsaturated carboxylic acid ester selected from the group consisting of alkyl acrylates and alkyl methacrylates. The aqueous emulsion according to claim 1, which is a structural unit.   The structural unit derived from the α, β-unsaturated carboxylic acid ester in (B) is an α, β obtained from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an α, β-unsaturated carboxylic acid. The aqueous emulsion according to claim 1, which is a structural unit derived from an unsaturated carboxylic acid ester.   The structural unit derived from the α, β-unsaturated carboxylic acid ester in (B) is an α, β-obtained from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group and an α, β-unsaturated carboxylic acid. The aqueous emulsion according to any one of claims 1 to 6, which is a structural unit derived from an unsaturated carboxylic acid ester.   (B) is a structural unit derived from an α, β-unsaturated carboxylic acid, and an α, β obtained from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group and an α, β-unsaturated carboxylic acid. The acrylic resin containing a structural unit derived from an unsaturated carboxylic acid ester, wherein the total number of amino groups contained in the resin is less than the total number of carboxylic acid groups contained in the resin. Aqueous emulsion.   The aqueous emulsion according to claim 1, wherein (B) further contains an ammonium cation.   The aqueous emulsion according to any one of claims 1 to 10, wherein (C) is an acetylene glycol emulsifier or a polyoxyethylene emulsifier.   Hardened | cured material formed by drying the aqueous emulsion in any one of Claims 1-11.   A laminate comprising an adherent layer 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 a layer made of a cured product according to claim 12. The manufacturing method of the aqueous emulsion including the process of melt-kneading the following (A), (B), (C) and (D).
(A) a structural unit derived from ethylene and / or a linear α-olefin, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
An olefin copolymer containing a structural unit derived from a vinyl compound represented by:
A polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the olefin copolymer (B) a structural unit derived from α, β-unsaturated carboxylic acid, and an α, β-unsaturated carboxylic acid Acrylic resin (C) nonionic emulsifier (D) water containing a structural unit derived from an acid ester The aqueous emulsion according to any one of claims 1 to 11 is applied to an adherent layer 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. A first step of obtaining a coated product having the adherent layer and the aqueous emulsion layer;
The manufacturing method of a laminated body which has a 2nd process of drying the coated article obtained at the 1st process, and obtaining the laminated body which consists of the said adhesion layer and the hardened | cured material layer obtained from the said aqueous emulsion.