JP2011246572A - Aqueous emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion not containing a chlorinated polyolefin and giving a coating film excellent in adhesion to polypropylene.SOLUTION: The aqueous emulsion comprises: (A) an acrylic resin comprising a structural unit derived from an α,β-unsaturated carboxylic acid (1) and a structural unit derived from at least one compound (2) selected from the group consisting of a monomer having a phosphate group and a (meth)acryloyl group and a salt thereof, a monomer having a sulfo group and a (meth)acryloyl group and a salt thereof, a monomer having an epoxy group and a (meth)acryloyl group, a monomer having a group derived from phthalic acid and a (meth)acryloyl group and a salt thereof, a 2-20C aliphatic unsaturated sulfonic acid and a salt thereof, a 6-20C aromatic sulfonic acid and a salt thereof; (B) a thermoplastic polymer different from the component (A); and (C) water.

Description

  The present invention relates to an aqueous emulsion having an acrylic resin as an emulsifier.

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 it is difficult for other materials such as paints to adhere to the surface of polypropylene, after coating the polypropylene with a chlorinated polyolefin excellent in adhesiveness with polypropylene and forming a coating film of chlorinated polyolefin, It is common practice 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 present inventors have reached the inventions described in the following [1] to [15]. That is, the present invention
[1] An aqueous emulsion comprising the following (A), (B) and (C):
(A) a structural unit derived from an α, β-unsaturated carboxylic acid (1);
An acrylic resin <compound group> comprising a structural unit derived from at least one compound (2) selected from the following <compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
C6-C20 aromatic sulfonic acid and its salt (B) thermoplastic polymer (however, different from (A))
(C) Water [2] The aqueous emulsion according to [1], wherein (B) is a thermoplastic polymer containing a structural unit derived from ethylene and / or propylene;
[3] (B) is a structural unit derived from ethylene and / or propylene, 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:
The aqueous emulsion according to the above [1] or [2], which is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the olefin copolymer;
[4] The aqueous emulsion according to [3], wherein the vinyl compound represented by the formula (I) is vinylcyclohexane;
[5] The aqueous emulsion according to any one of [1] to [4], wherein the MFR (190 ° C., 2.16 kgf) of (B) is 10 g / 10 min or more and 300 g / 10 min or less. ;
[6] The structural unit derived from the α, β-unsaturated carboxylic acid (1) in (A) 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 [5], wherein
[7] The structural unit derived from the α, β-unsaturated carboxylic acid ester (2) in (A) is at least one α, β-unsaturated selected from the group consisting of alkyl acrylates and alkyl methacrylates. The aqueous emulsion according to any one of [1] to [6], which is a structural unit derived from a saturated carboxylic acid ester;

[8] A method for producing an aqueous emulsion, comprising a step of melt-kneading the following (A), (B) and (C):
(A) a structural unit derived from an α, β-unsaturated carboxylic acid (1);
An acrylic resin <compound group> comprising a structural unit derived from at least one compound (2) selected from the following <compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
C6-C20 aromatic sulfonic acid and its salt (B) thermoplastic polymer (however, different from (A))
(C) Water [9] A method for forming a coating film comprising a step of coating the aqueous emulsion according to any one of [1] to [7] on a substrate;

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

[11] having a base material made of at least one material selected from the group consisting of a woody material, a cellulosic material, a plastic material, a ceramic material, and a metal material, and a layer made of the cured product according to [10] Laminates;

[12] The aqueous material according to any one of [1] to [7] above, on a base material 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 applying an emulsion to obtain a coated product having the substrate and a layer comprising the aqueous emulsion;
A method for producing a laminate having a second step of drying the coated product obtained in the first step to obtain a laminate comprising the substrate and a cured product layer obtained from the aqueous emulsion;

[13] a structural unit derived from an α, β-unsaturated carboxylic acid (1);
An emulsifier comprising an acrylic resin comprising a structural unit derived from at least one compound (2) selected from the following <compound group>;
<Compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
Aromatic sulfonic acid having 6 to 20 carbon atoms and salt thereof [14] At least one α selected from the group consisting of acrylic acid and methacrylic acid, wherein the structural unit derived from α, β-unsaturated carboxylic acid (1) The emulsifier according to [13] above, which is a structural unit derived from β-unsaturated carboxylic acid;

[15] Use of the aqueous emulsion according to any one of [1] to [7] as a coating film;
About.

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

(A) in the present invention is a structural unit derived from an α, β-unsaturated carboxylic acid (1),
An acrylic resin containing a structural unit derived from “at least one compound (2) selected from the following <compound group>” (hereinafter sometimes referred to as “compound (2)”).
<Compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
Aromatic sulfonic acid having 6 to 20 carbon atoms and salt thereof

Examples of the “α, β-unsaturated carboxylic acid (1)” include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, methyl nadic acid, and highmic. Examples include acids, angelic acid, tetrahydrophthalic acid, sorbic acid, and mesaconic acid.
As the “α, β-unsaturated carboxylic acid (1)”, a plurality of “α, β-unsaturated carboxylic acid (1)” may be used.
As the “α, β-unsaturated carboxylic acid (1)”, acrylic acid and methacrylic acid are preferable. In the present specification, “(meth) acrylic acid” and “acryloyl group” mean “acrylic acid or methacrylic acid”. Or “methacryloyl group”, “(meth) acryloyl group”, “acrylate or methacrylate”, “(meth) acrylate”, and the like.

  Among the “compound (2)”, a monomer having a phosphate group and a (meth) acryloyl group (hereinafter sometimes referred to as “phosphate group-containing monomer”) and a salt thereof include, for example, (mono [poly ( Propylene oxide) (meth) acrylate]) phosphate, (mono [poly (ethylene oxide) (meth) acrylate]) phosphate, (mono [2-methacryloyloxyethyl]) phosphate, (mono [2-acryloyl) Oxyethyl]) A compound in which a phosphate group is bonded to a hydrocarbon having an oxy (meth) acryloyl group at the end, such as a phosphate ester, in the form of a phosphate ester via an oxygen atom. The phosphate group-containing monomer may be in the form of a salt of an organic base such as ethanolamine in the phosphate group. Furthermore, when the organic base is an alcohol amine, it is also preferable that the terminal acrylate is in the form of an ester bond with (meth) acrylic acid. Examples of commercially available phosphate group-containing monomers that can be used in the present invention include 2- (meth) acryloyloxyethyl phosphate ester, 2- (meth) acryloyloxypropyl phosphate ester, 2- (meta) ) Acryloyloxybutyl phosphate ester, poly (meth) acryloyloxyphosphate ester [reaction product of pentaerythritol triacrylate and diphosphorus pentoxide, reaction product of dipentaerythritol pentaacrylate and diphosphorus pentoxide, and the like] Of the mixture. Of these, 2- (meth) acryloyloxyethyl phosphate ester, 2- (meth) acryloyloxypropyl phosphate ester, and 2- (meth) acryloyloxybutyl phosphate ester are preferable.

  Among the “compounds (2)”, monomers having a sulfo group and a (meth) acryloyl group and salts thereof include, for example, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid. 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid , P- (meth) acryloyloxymethylbenzenesulfonic acid, etc.], C4-C20 sulfonic acid group-containing (meth) acrylamide [eg, 2- (meth) acryloylaminoethanesulfonic acid, 2- (meth) acryloylaminopropanesulfone Acid, 3- (meth) acryloylaminopro Sulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethyl Benzenesulfonic acid etc.], (meth) acryloyl polyoxyalkylene (C1-6) sulfate [C5-60, for example (meth) acryloyl polyoxyethylene (degree of polymerization 2-50) sulfate etc.], and alkali metals thereof Examples include salts. Among them, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) ) Acrylyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, and alkali metal salts thereof are preferred.

  Among the “compound (2)”, examples of the monomer having an epoxy group and a (meth) acryloyl group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and (meth) acrylic acid 3,4- And epoxy cyclohexyl methyl. Among these, glycidyl (meth) acrylate is preferable.

  Among the “compound (2)”, a monomer having a group derived from phthalic acid and a (meth) acryloyl group and a salt thereof include, for example, 2- (meth) acryloyloxyethylphthalic acid; 2- (meth) acryloyl Oxyethylhexahydrophthalic acid; adduct of pentaerythritol tri (meth) acrylate and acid anhydrides such as phthalic anhydride and hexahydrophthalic anhydride; dipentaerythritol penta (meth) acrylate, phthalic anhydride, hexahydroanhydride And adducts with acid anhydrides such as phthalic acid. Of these, 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate are preferable.

  Among the “compound (2)”, examples of the aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms and a salt thereof include vinyl sulfonic acid and the like.

  Among the “compound (2)”, examples of the aromatic sulfonic acid having 6 to 20 carbon atoms and a salt thereof include sodium 4-vinylbenzenesulfonate.

  The content of “structural unit derived from α, β-unsaturated carboxylic acid (1)” in (A) is, for example, 0.1 to 100 mol% of all structural units constituting (A). 95 mol% etc. can be mentioned, More preferably, 5-80 mol% etc. are mentioned.

  The content of the “structural unit derived from the compound (2)” in (A) is preferably 0.01 to 95 mol% with respect to 100 mol% of all the structural units constituting (A). More preferably, 0.1-80 mol% etc. are mentioned, Especially preferably, 1-40 mol% etc. are mentioned.

  In addition to “a structural unit derived from an α, β-unsaturated carboxylic acid (1)” and “a structural unit derived from a compound (2)”, (A) is optionally substituted with “1-20 carbon atoms”. A structural unit derived from an α, β-unsaturated carboxylic acid ester consisting of an aliphatic alcohol of the above and an α, β-unsaturated carboxylic acid ”,“ a C1-C10 aliphatic alcohol having a hydroxyl group and α, β- A structural unit derived from an α, β-unsaturated carboxylic acid ester comprising an unsaturated carboxylic acid ”, an“ alpha comprising an amino group-containing aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid; , Β-unsaturated carboxylic acid ester-derived structural unit ”,“ α, β-unsaturated consisting of a C1-C10 aliphatic alcohol having a carboxy group (—COOH) and an α, β-unsaturated carboxylic acid. Structural unit derived from saturated carboxylic acid ester "Or the like may also contain.

  As the α, β-unsaturated carboxylic acid in the “structural unit derived from an α, β-unsaturated carboxylic acid ester comprising an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid”, The same thing as said "(alpha), (beta)-unsaturated carboxylic acid (1)" is illustrated, Acrylic acid and methacrylic acid are especially preferable.

  Examples of the aliphatic alcohol in the “α, β-unsaturated carboxylic acid ester comprising an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid” include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol , N-propyl alcohol, n-butyl alcohol, t-butyl alcohol, amyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decanyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, cyclohexyl alcohol and the like.

  Examples of the “α, β-unsaturated carboxylic acid ester composed of an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid” include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, Butyl acrylate, amyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decanyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Examples include butyl, amyl methacrylate, ethyl hexyl methacrylate, nonyl methacrylate, decanyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, and the like.

  As the α, β-unsaturated carboxylic acid in the “α, β-unsaturated carboxylic acid ester comprising a C1-C10 aliphatic alcohol having a hydroxyl group and an α, β-unsaturated carboxylic acid”, the α , Β-unsaturated carboxylic acids are exemplified, and acrylic acid and methacrylic acid are particularly preferable.

  Examples of the “aliphatic alcohol having 1 to 10 carbon atoms” in the “aliphatic alcohol having 1 to 10 carbon atoms having a hydroxyl group” include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, and n-butyl alcohol. , T-butyl alcohol, amyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decanyl alcohol, cyclohexyl alcohol and the like.

  Examples of the “C1-C10 aliphatic alcohol having a hydroxyl group” include 1-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, Examples include 6-hydroxyhexyl acrylate, 1-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and preferably 1- Hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, - hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate.

  As the α, β-unsaturated carboxylic acid in the above “α, β-unsaturated carboxylic acid ester comprising an aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid”, The same thing as an alpha, beta-unsaturated carboxylic acid is illustrated, and acrylic acid and methacrylic acid are especially preferable.

  Examples of the “aliphatic alcohol having 1 to 10 carbon atoms” in the “aliphatic alcohol having 1 to 10 carbon atoms having an amino group” include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, and n-butyl. Examples include alcohol, t-butyl alcohol, amyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decanyl alcohol, cyclohexyl alcohol and the like.

The “C1-C10 aliphatic alcohol having an amino group” means an amino group (—NH ₂ ) or an alkylamino group (—NHR, R is a hydrogen atom of the aliphatic alcohol having 1 to 10 carbon atoms. Represents an alkyl group having 1 to 10 carbon atoms) or a dialkylamino group (-NRR ′, R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and R and R ′ may be the same or different. ) Means a substituted group.
Specifically, amino 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, Alkylamino 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, 2- (N N- diethylamino) ethyl alcohol, 3- (N, N- dimethylamino) propyl alcohol, 3- (N, dialkylamino alcohols such as N- diethylamino) propyl alcohol; and the like are exemplified.

Examples of the “α, β-unsaturated carboxylic acid ester comprising 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. Preferably, N, N-dimethylaminoethyl methacrylate is used.
The “α, β-unsaturated carboxylic acid ester comprising an amino group-containing aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid” includes a plurality of different α, β-unsaturated species. Carboxylic acid esters may be used.

  As the α, β-unsaturated carboxylic acid in the “α, β-unsaturated carboxylic acid ester comprising a carboxy group-containing aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid”, The same thing as an alpha, beta-unsaturated carboxylic acid is illustrated, and acrylic acid and methacrylic acid are especially preferable.

“C1-C10 Fatty Acid Having Carboxy Group” in the “α, β-Unsaturated Carboxylic Acid Ester Consisting of C1-C10 Aliphatic Alcohol Having Carboxy Group and α, β-Unsaturated Carboxylic Acid” The “group alcohol” means a group in which a carboxy group is substituted on the hydrogen atom of the “aliphatic alcohol having 1 to 10 carbon atoms”.
Examples of the “α, β-unsaturated carboxylic acid ester comprising a C 1-10 aliphatic alcohol having a carboxy group and an α, β-unsaturated carboxylic acid” include, for example, 2-acryloyloxyethyl succinic acid, Examples include 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl phthalic acid.

The structural unit derived from these α, β-unsaturated carboxylic acid esters contained as necessary in (A) uses structural units derived from different types of α, β-unsaturated carboxylic acid esters. May be.
The content of the “structural unit derived from an α, β-unsaturated carboxylic acid ester consisting of an aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid” in the above (A) is the acrylic Preferably, for example, 5 to 95 mol% can be mentioned with respect to 100 mol% of all the structural units constituting the resin (A), and more preferably 10 to 80 mol% can be mentioned. .
As the content of “a structural unit derived from an α, β-unsaturated carboxylic acid ester comprising a C 1-10 aliphatic alcohol having a hydroxyl group and an α, β-unsaturated carboxylic acid” in the above (A), Preferably, for example, 0 to 80 mol% can be mentioned with respect to 100 mol% of all the structural units constituting the acrylic resin (A), and more preferably, for example, 1 to 50 mol%, etc. Is mentioned.
As the content of “a structural unit derived from an α, β-unsaturated carboxylic acid ester comprising an aliphatic alcohol having 1 to 10 carbon atoms having an amino group and an α, β-unsaturated carboxylic acid” in the above (A) Is preferably, for example, 0 to 80 mol%, more preferably 1 to 50 mol%, for 100 mol% of all the structural units constituting the acrylic resin (A). Etc.
As the content of “a structural unit derived from an α, β-unsaturated carboxylic acid ester comprising a C 1-10 aliphatic alcohol having a carboxy group and an α, β-unsaturated carboxylic acid” in the above (A) May preferably include, for example, 0 to 80 mol%, and more preferably 5 to 40 mol%, for 100 mol% of all the structural units constituting the (A). Can be mentioned.

  In addition, as the (A), the “structural unit derived from the α, β-unsaturated carboxylic acid (1)” is particularly used with respect to 100 mol% of all structural units constituting the acrylic resin of the (A) 5 to 80 mol%, “Structural unit derived from compound (2)” is 1 to 40 mol%, “C 1-10 aliphatic alcohol and α, β-unsaturated carboxylic acid” The content of “a structural unit derived from an α, β-unsaturated carboxylic acid ester consisting of” is 10 to 80 mol%, “a C1-C10 aliphatic alcohol having a hydroxyl group and an α, β-unsaturated carboxylic acid” The content of “structural unit derived from α, β-unsaturated carboxylic acid ester consisting of” is 1 to 50 mol%, “C 1-10 aliphatic alcohol having an amino group and α, β-unsaturated carboxylic acid” Derived from α, β-unsaturated carboxylic acid ester consisting of acid Α, β-unsaturated carboxylic acid ester comprising 1 to 50 mol% of “structural unit” and “alpha-, β-unsaturated carboxylic acid having 1 to 10 carbon-containing aliphatic alcohol having carboxy group” An acrylic resin containing a structural unit having a content of “structural unit derived from” of 5 to 40 mol% (however, the total content of the structural units is 100 mol%) is particularly preferable.

  In the above (A), other than the structural unit derived from the monomer, ethylene, propylene, “linear α-olefin having 4 or more carbon atoms”, “vinyl compound (I)”, and “addition polymerizable” The structural unit derived from the “monomer” may be contained, but the content thereof is usually in a range in which the adhesiveness of the obtained aqueous emulsion is not impaired. About 5 mol% or less with respect to 100 mol% of structural units derived from all monomers constituting the resin, preferably not containing substantially any structural unit derived from a monomer capable of addition polymerization, specifically, For example, the content is 1 mol% or less.

  As a manufacturing method of (A) in this invention, it can manufacture by carrying out addition polymerization of the said monomer mixture, for example. Specifically, for example, 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 usually 70 ° C to 100 ° C, preferably 75 ° C to 95 ° C, particularly preferably. Is a method in which a polymerization initiator such as a radical initiator and the remaining monomer are mixed at 75 ° C. to 85 ° C., and usually stirred for about 1 to 24 hours. In order to control the reaction, the polymerization initiator and the remaining monomers may be dissolved in an organic solvent and then added.

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 peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide Etc. A redox initiator using a thermal polymerization initiator and a reducing agent in combination can also be used as the polymerization initiator.
The amount of the polymerization initiator used is 0.01 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the monomer mixture.

The aqueous emulsion of the present invention preferably has an NH ₃ neutralization degree of, for example, 50 to 300, more preferably 100 to 200. Here, the degree of neutralization of NH ₃ is the ratio of the number of moles of ammonia contained in the aqueous emulsion to the total number of moles of structural units derived from the monomer having an anionic group contained in (A), ie, [(ammonia Number of moles) / (total number of moles of anionic monomer) × 100 (%)]
Means.

  Said (A) can act as an emulsifier for dispersing (B) which is a thermoplastic polymer in (C) which is water, for example, in the aqueous emulsion of the present invention.

Examples of (B) in the present invention include thermoplastic polymers containing ethylene, thermoplastic polymers containing propylene, ester waxes, carnauba waxes, Fischer-Trops waxes, microcrystalline waxes, paraffin waxes and oxides thereof. And amide compounds such as low molecular weight polyamide and fatty acid amide.
(B) is preferably a thermoplastic polymer containing ethylene and / or propylene. Examples of the thermoplastic polymer containing ethylene and / or propylene include polyethylene such as low density polyethylene, polyethylene wax, ethylene / vinyl acetate copolymer, ethylene / propylene / vinyl acetate copolymer, and ethylene / acrylic acid copolymer. Copolymer, ethylene / propylene / acrylic acid copolymer, ethylene / acrylic ester copolymer, ethylene / propylene / acrylic ester copolymer, ethylene / acrylic acid copolymer, ethylene / propylene / methacrylic acid copolymer, ethylene / propylene copolymer Methacrylic ester copolymer, ethylene / propylene / methacrylic ester copolymer, polypropylene, ethylene / propylene copolymer, ethylene / hexene copolymer, propylene / hexene copolymer, ethylene / propylene / hexene copolymer, ethylene Len butene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer and their maleic acid-modified products, and the like.

Preferred thermoplastic polymers containing ethylene and / or propylene include, for example, structural units derived from ethylene and / or propylene, and the formula (I)
_{CH 2 = CH-R (I} )
(In the formula, R of the vinyl compound (I) represents a secondary alkyl group, a tertiary alkyl group, or an alicyclic hydrocarbon group.)
And an olefin copolymer (hereinafter referred to as “polymer (B-1)”) containing a structural unit derived from a vinyl compound represented by the formula (hereinafter sometimes referred to as “vinyl compound (I)”). Or a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the polymer (B-1) (hereinafter referred to as “polymer (B-2)”). And the like.

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 more preferable. Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group, and a cycloalkyl group is preferable.
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 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- Such as 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- Examples include 1-heptene and 3,3,4-trimethyl-1-octene.
As the vinyl compound (I) in which the substituent R is an alicyclic hydrocarbon group, the substituent R such as vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and vinylcyclooctane is a cycloalkyl group. And vinyl compounds such as 5-vinyl-2-norbornene, 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 (B-1) is preferably based on 100 mol% of the structural unit derived from all the monomers constituting the polymer (B-1). Is from 5 to 40 mol%, more preferably from 10 to 30 mol%, still more preferably from 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.

  The polymer (B-1) may further contain a structural unit derived from a linear α-olefin having 4 to 20 carbon atoms. Specifically, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 Examples include linear olefins such as -pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, and 1-eicocene. Of these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  In the polymer (B-1), as the total content of structural units derived from ethylene, propylene and a linear α-olefin having 4 to 20 carbon atoms, all monomers constituting the polymer (B-1) The amount is preferably 95 to 60 mol%, more preferably 90 to 70 mol%, still more preferably 90 to 80 mol% with respect to 100 mol% of the structural unit derived from the above.

(式中、Ｒ’、Ｒ”は、それぞれ独立に、炭素数１〜１８程度の直鎖状、分枝状あるいは環状のアルキル基、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、アルカン酸ビニル、ビニルエーテル類、アクリロニトリル類、前記アクリル樹脂におけるα，β−不飽和カルボン酸、前記アクリル樹脂におけるα，β−不飽和カルボン酸エステル、後記α，β−不飽和カルボン酸無水物などが挙げられる。 The polymer (B-1) may further be copolymerized with a monomer capable of addition polymerization.
Here, the addition-polymerizable monomer is a monomer other than ethylene, propylene, a linear α-olefin having 4 to 20 carbon atoms, and the vinyl compound (I), and ethylene, propylene, having 4 to 20 carbon atoms. The monomer is capable of addition polymerization with the linear α-olefin and the vinyl compound (I), and the number of carbon atoms of the monomer is preferably 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 cyclic alkyl group having about 1 to 18 carbon atoms, or a halogen atom.)
Vinylidene compounds, diene compounds, vinyl halides, vinyl alkanoates, vinyl ethers, acrylonitriles, α, β-unsaturated carboxylic acid in the acrylic resin, α, β-unsaturated carboxylic acid ester in the acrylic resin And α, β-unsaturated carboxylic acid anhydrides described later.

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.
Preferred cycloolefins are cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricyclounone. Decene, 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, more 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 alkanoates 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 (B-1) is usually a range in which the adhesiveness of the resulting aqueous emulsion is not impaired, and the specific content is , About 5 mol% or less with respect to 100 mol% of structural units derived from all monomers constituting the polymer (B-1), preferably substantially free of structural units derived from addition-polymerizable monomers The degree, specifically, for example, the content is 1 mol% or less.

  As a method for producing the polymer (B-1), for example, a method produced in the presence of a catalyst comprising a transition metal compound having a group having an indenyl type anion skeleton or a crosslinked 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 method of the polymer (B-1), depending on the type of the catalyst used and the polymerization conditions, in addition to the copolymer of the present invention, an ethylene homopolymer, a propylene homopolymer, or a vinylcyclohexane homopolymer may be used. 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 polyolefins such as polyethylene and polypropylene can be removed as an insoluble component of extraction using chloroform, The copolymer can be fractionated as a soluble component of both solvents. Of course, the olefin copolymer may be used in the presence of such a by-product if there is no problem depending on the application.

The molecular weight distribution (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) of the polymer (B-1) is preferably about 1.5 to 10, more preferably about 1.5 to 7. More preferably, it is about 1.5-5. When the molecular weight distribution of the olefin copolymer is 1.5 or more and 10 or less, it is preferable because the mechanical strength and transparency of the resulting modified olefin copolymer are likely to be improved.
From the viewpoint of mechanical strength, the weight average molecular weight (Mw) of the polymer (B-1) is preferably about 5,000 to 1,000,000, more preferably 10,000 to 500,000. About 15,000 to 400,000. The weight average molecular weight of the olefin copolymer is preferably 5,000 or more, since the mechanical strength of the resulting polymer (B-1) tends to be improved, and preferably 1,000,000 or less. It is preferable because the fluidity of the polymer (B-1) tends to be improved.
The molecular weight distribution of the polymer (B-1) can be determined using gel permeation chromatograph (GPC) in accordance with the method specifically described in Examples below.

  The polymer (B-1) was measured under the conditions of 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210 from the viewpoint of dispersibility. The value of the melt flow rate (MFR) is preferably 130 to 300 g / 10 minutes, more preferably 130 to 220 g / 10 minutes.

The polymer (B-2) is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the polymer (B-1) thus obtained.
The graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride with respect to 100 parts by weight of the polymer (B-2) is preferably 0.01 to 100% by weight with respect to 100% by weight of the resulting polymer (B-2). About 20% by weight, more preferably about 0.05 to 10% by weight, and still more preferably about 0.1 to 5% by weight.
When the graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride is 0.01% by weight or more, the adhesive strength of the resulting aqueous emulsion tends to be improved, and when it is 20% by weight or less, It is preferable because coloring of the resulting aqueous emulsion tends to be reduced.

  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 anhydrides may be used in combination. As the α, β-unsaturated carboxylic acid anhydride, maleic anhydride is preferable.

Examples of the method for producing the polymer (B-2) include a method in which the polymer (B-1) is melted, and then α, β-unsaturated carboxylic acid anhydride is added and graft polymerization is performed. Examples include a method in which a polymer is dissolved in a solvent such as toluene or xylene, and then α, β-unsaturated carboxylic acid anhydride is added to cause graft polymerization.
After melting the polymer (B-1), 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 solid. 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. Particularly preferable is an olefin copolymer, unsaturated carboxylic acid, radical initiator, which is sufficiently premixed in advance using a single-screw or twin-screw extruder from the viewpoint that continuous production is possible and productivity is improved. A method is recommended in which kneading is carried out by feeding from the feed port of the extruder. 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 grafting tends to be improved, and when the temperature is 300 ° C. or lower, decomposition of the polymer (B-1) 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, particularly 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 (B-1) tends to be suppressed. To preferred.

In order to graft polymerize the α, β-unsaturated carboxylic acid anhydride to the polymer (B-1), the 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 polymer (B-1). The amount added is preferably 0.01 parts by weight or more because the amount of grafting to the polymer (B-1) tends to increase and the adhesive strength tends to improve, and the amount added is 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 (B-1) tends to be reduced. In addition, these organic peroxides preferably have an action of extracting protons from the polymer (B-1) after being decomposed to generate radicals.

  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, and percarbonate compounds. . 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. When the decomposition temperature is lower than 50 ° C., the graft amount is not improved. Further, the amount of grafting does not improve even when the decomposition temperature is higher than 210 ° C. Of these organic peroxides, preferred are dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds, and alkyl perester compounds. The amount of the organic peroxide 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 polymer (B-1).

  The structural unit derived from the α, β-unsaturated carboxylic acid anhydride contained in the polymer (B-2) thus obtained is a ring-opened one even if the acid anhydride group remains closed. In addition, both a closed ring and a ring-opened ring may be contained.

Examples of the molecular weight distribution (Mw / Mn) of the polymer (B-2) in the aqueous emulsion of the present invention include 1.5 to 10 and the like. Preferably 1.5-7 grade | etc., More preferably, 1.5-5 grade | etc., Is mentioned.
The molecular weight distribution of the polymer (B-2) can be measured in the same manner as the molecular weight distribution of the polymer (B-1).

  The polymer (B-2) was measured under conditions of 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210 from the viewpoint of dispersibility. The value of the melt flow rate (MFR) is preferably 130 g / 10 min or more and 300 g / 10 min or less, and particularly preferably 130 g / 10 min or more and 200 g / 10 min or less.

As the method for producing the aqueous emulsion of the present invention, for example, (A), (B) and (C) which is water are melt-kneaded; for example, obtained by a heating step and a heating step of heating (B). A method of mixing (A) with heated (B); for example, a step of heating and kneading (B) and (A), and a kneaded product obtained in the step dispersed in (C) For example, a dissolution step in which (B) is dissolved in an organic solvent such as toluene, a mixing step in which the dissolution product obtained in the dissolution step is mixed in (A), and a mixture obtained in the mixing step And a method including a removing step of removing the organic solvent from.
Moreover, the emulsion manufacturing method by chemical emulsification methods, such as self-emulsification other than the above mechanical emulsification methods, is also illustrated.
In particular, (A), (B) and (C) are melt-kneaded, and (B) is heated, and (B) obtained in the heating step is mixed with (A). A method having a mixing step is preferred.

  Examples of the apparatus used in the step of melting and kneading (A) and (B) and, if necessary, (C) include, for example, a twin screw extruder, Labo Plast Mill (Toyo Seiki Seisakusho Co., Ltd.), Labo Plast Mill Micro ( Toyo Seiki Seisakusho Co., Ltd.) and other multi-screw extruders, homogenizers, TK film mixes (Primics Co., Ltd.) and other equipment with barrels (cylinders) such as stirring tanks, chemical stirrers, vortex mixers, flow jet mixers, colloids Equipment that does not have a barrel (cylinder) such as a mill, an ultrasonic generator, a high-pressure homogenizer, dispersion (Fujikin Co., Ltd.), a static mixer, or 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 part of the screw element by the clearance [mm] between the screw and the barrel.

As a method of melt kneading (A), (B) and (C), for example, (B) is continuously supplied from a hopper or supply port of a twin-screw extruder, heated and melt-kneaded, and further this (A) is pressurized and supplied from at least one supply port provided in the compression zone, metering zone or degassing zone of the extruder, and (B) is kneaded with a screw, followed by compression of the extruder. Examples thereof include a method of continuously producing an aqueous emulsion from a die by supplying (C) from at least one supply port provided in the zone.
As a method including a heating step of heating (B) and a mixing step of mixing (A) with the heated thermoplastic polymer (B) obtained in the heating step, for example, after heating a cylinder of a kneader Then, (B) is introduced into the cylinder and a heating process is performed to melt while rotating, then (A) is introduced and a mixing process is performed to rotate, and then the resulting mixture is placed in warm water. A method of adding and dispersing to obtain an aqueous emulsion is exemplified.

A method using a multi-screw extruder is suitable as the method including the heating step of heating (B) and the mixing step of mixing (A) with the heated (B) obtained in the heating step.
Specifically, first, a heating step in which (B) 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 (C) while kneading with (A) supplied from at least one liquid supply port provided in the measurement zone. .

In the aqueous emulsion of the present invention, the dispersoid containing (A) and (B) is dispersed in (C) which is a dispersion medium.
The lower limit of the volume-based median diameter of the dispersoid is, for example, preferably 0.01 μm or more, and more preferably 0.1 μm or more. Further, the upper limit of the volume-based median diameter of the dispersoid is, for example, 3 μm or less, preferably 2 μm or less, more preferably 1 μm or less.
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 and stationary stability tend to be improved. Here, the standing stability is a property that the aqueous emulsion is uniform even after standing for 3 days, that is, a layer rich in (B) and / or (C ) Means a property that is difficult to form a rich layer.
Here, the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis.

Content of (A) in the aqueous emulsion of this invention is 1-30 weight part with respect to 100 weight part of (B), Preferably it is 2-10 weight part.
The content of (B) in the aqueous emulsion of the present invention is, for example, 10 to 70 parts by weight, preferably 30 to 60 parts by weight, and more preferably 40 to 60 parts by weight with respect to 100 parts by weight of the aqueous emulsion.
The content of (C) in the aqueous emulsion of the present invention is, for example, 10 to 90 parts by weight, preferably 30 to 70 parts by weight, and more preferably 40 to 60 parts by weight with respect to 100 parts by weight of the aqueous emulsion.

  Examples of the aqueous emulsion of the present invention include pigments, surfactants, neutralizers, stabilizers, thickeners, antifoaming agents, surface conditioners, leveling agents, pigment dispersants, ultraviolet absorbers, antioxidants, An inorganic filler such as silica, a conductive carbon, a conductive filler, a conductive filler such as metal powder, an organic modifier, a plasticizer, and the like can be blended as necessary.

  Examples of the thickener include associative nonionic urethane thickener, alkali swelling thickener, bentonite which is an inorganic intercalation compound, and the like.

  Examples of the pigment include inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, and bitumen, and organic pigments such as azo pigments, anthracene pigments, perylene pigments, quinacridone pigments, indigo pigments, and phthalocyanine pigments. Color pigments such as talc, body pigments such as precipitated barium sulfate; conductive pigments such as whiskers coated with conductive carbon and antimony-doped tin oxide; metals or alloys such as aluminum, copper, zinc, nickel, tin, and aluminum oxide Examples thereof include non-colored or colored metallic luster materials.

  Examples of the pigment dispersant include an aqueous acrylic resin; a styrene-maleic acid copolymer; an acetylenic diol derivative; a water-soluble carboxymethyl cellulose acetate butyrate. By using these pigment dispersants, a stable pigment paste can be prepared. Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.

In the aqueous emulsion of the present invention thus obtained, the dispersoid containing (A) and (B) tends to be uniformly dispersed in the dispersion medium (C), and there are few foreign matters such as aggregates of the dispersoid. Tend. The cured product obtained by drying moisture from the emulsion of the present invention tends to give a smooth surface, and the foreign matter means a component that is not smooth on a smooth surface.
As a result, as will be described later, the aqueous emulsion of the present invention tends to be excellent in workability when applied to a substrate as a paint, and the resulting cured product tends to be excellent in appearance.

In the present invention, a film-like product of the cured product is referred to as a coating film. A coating film (coating film) of the aqueous emulsion can be formed on the substrate by coating the aqueous emulsion of the present invention on the substrate and then drying.
The coating film can be used, for example, for paints, primers, base materials, adhesives and the like.

  The drying is performed, for example, at 30 ° C. to 180 ° C., preferably 60 ° C. to 150 ° C. for about 1 minute to 12 hours, preferably about 10 minutes to 6 hours. At this time, drying may be performed under ventilation or under reduced pressure.

The “base material” in the present invention means an article having an arbitrary shape intended to be coated with the aqueous emulsion of the present invention, such as an adherend and an adherent layer.
Examples of the base material in the present invention include wood-based materials such as wood, plywood, MDF, particle board, and fiber board; paper-based materials such as wallpaper and wrapping paper: cellulosic materials such as cotton cloth, linen, and rayon; polyethylene ( Polyolefins whose main component is a structural unit derived from ethylene (hereinafter the same), polypropylene (polyolefins whose main component is a structural unit derived from propylene, the same applies hereinafter), polyolefins such as polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer Plastic materials such as coalescence (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane; ceramic materials such as glass and ceramics; metal materials such as iron, stainless steel, copper, and aluminum All It is.

  Such a substrate 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 foamed polyurethane 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.

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

  The hardened | cured material derived from the aqueous emulsion of this invention has the outstanding adhesiveness with respect to the base materials of polyolefins, such as a polypropylene conventionally considered difficult adhesiveness.

When one of the substrates is a water-absorbing substrate such as a wood-based material, a paper-based material, or a cellulosic material, the aqueous emulsion of the present invention can be applied as it is and bonded to another substrate. . That is, after coating an aqueous emulsion on a water-absorbing substrate, if another substrate (which may be water-absorbing or non-water-absorbing) is laminated on the layer derived from the aqueous emulsion, the water content in the aqueous emulsion is A cured product that is absorbed by the water-absorbing substrate and is derived from the aqueous emulsion becomes an adhesive layer, and a laminate having the water-absorbing substrate / cured material / substrate derived from the aqueous emulsion of the present invention can be obtained.
When the substrate is non-water-absorbing, such as polyolefin, after coating an aqueous emulsion on one side of the substrate and heating to form a coating film derived from the aqueous emulsion of the present invention, the other group What is necessary is just to bond a material and to heat and to make it adhere | attach further.
As a heating temperature at the time of forming the coating film derived from the aqueous emulsion and a coating film derived from the other base material and the aqueous emulsion, for example, 60 to 200 ° C. and the like are exemplified. be able to. In the aqueous emulsion of the present invention, the heating temperature after bonding the other base material and the coating film derived from the aqueous emulsion is not less than 90 ° C. but also 60 ° C. or more and less than 90 ° C., preferably 65 to 65 ° C. Excellent adhesion between the coating film derived from the aqueous emulsion obtained at a low temperature of 80 ° C. and the substrate.

  A liquid material may be further applied as a paint to the coating film derived from the aqueous emulsion of the present invention. The coating material is a material exemplified as a material for the base material such as polyurethane, and a liquid material is preferable because it is excellent in adhesiveness with a coating film derived from the aqueous emulsion of the present invention.

  Therefore, the present invention also provides a base material containing at least one material selected from the group consisting of woody materials, cellulosic materials, plastic materials, ceramic materials and metal materials, and a cured product derived from the aqueous emulsion of the present invention. And a laminate comprising:

  Furthermore, the present invention applies the aqueous emulsion of the present invention to a substrate containing at least one material selected from the group consisting of woody materials, cellulosic materials, plastic materials, ceramic materials and metal materials, A first step of obtaining a coated product comprising a base material and a layer containing the aqueous emulsion, and drying the coated product obtained in the first step to cure derived from the base material and the aqueous emulsion of the present invention. The manufacturing method of a laminated body including the 2nd process of obtaining the laminated body containing a thing is provided.

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.
[Solid content]
The solid content was measured by a measuring method according to JIS K-6828.

[Molecular weight and molecular weight distribution]
The molecular weight of the thermoplastic polymer (B) was determined under the following conditions after calibrating with a polystyrene (molecular weight 688 to 400,000) standard substance using a gel permeation chromatograph (GPC). 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

[NH ₃ neutralization degree]
The degree of neutralization of NH ₃ of the acrylic resin (A) is determined based on the number of moles of acrylic acid (AA) ([AA]), the number of moles of methacrylic acid (MAA), and 2-methacryloyloxyethyl. Ratio of the number of moles of ammonia used ([NH ₃ ]) to the total number of moles of succinic acid (HO-MS) ([HO-MS]),
([NH ₃ ] / ([AA] + [MAA] + [HO-MS])) × 100 (%)
Represents.

[Content of vinylcyclohexane unit]
The content of the vinylcyclohexane unit in (B) 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

[Graft amount]
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 grafted maleic acid was quantified from the absorption near 1780 cm ⁻¹ .

<Production example of (A)>
As the monomer (A), the monomers listed in Table 1 were used.

(Reference production example: Production example of acrylic resin)
"AA" 7.5 parts (10.9 mole ratio), "MAA" 22.5 parts (27.4 mole ratio), "HEA" 29.5 parts (26.6 mole ratio), "EA" 29. 5 parts (30.8 molar ratio) and 11.0 parts (4.4 molar ratio) of “SLMA” 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 mixture of 100 parts of ion-exchanged water, 150 parts of isopropyl alcohol (hereinafter sometimes referred to as IPA) and 100 parts of the monomer mixture was charged into the reactor and stirred at 80 ° C. under nitrogen substitution. While gradually adding about 0.9 part of 2,2′-azobisisobutyronitrile as a polymerization initiator to the obtained reaction solution, the mixture was stirred at the same temperature and under nitrogen substitution for 3 hours. Subsequently, the temperature of the resulting reaction solution was raised to a boiling point to distill off the IPA. After distilling off, the internal temperature was lowered to 50 ° C., and then 28 parts (46 molar ratio) of 28% aqueous ammonia solution was mixed. Then, water was added and it adjusted so that components (solid content) other than water and ammonia might be 50%, and the viscous acrylic resin was obtained (yield 90%).

<Production Examples 1 to 5 of (A): Production of acrylic resins (A-1) to (A-5)>
Except for changing the type and amount of monomer to be used, the amount of solids, and the amount of ammonia water to those shown in Tables 2 and 3, it was carried out in accordance with Reference Production Example, and acrylic resin (A) A-1) to (A-5) were obtained.

<Production Example 1 of (B) 1: Production Example of Polymer (B-1a)>
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 while being pressurized at 0.6 MPa. 10 parts of a toluene solution of triisobutylaluminum (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 87 parts dehydrated toluene and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.03 part dissolved in 122 parts dehydrated toluene were added and stirred for 2 hours. did. The resulting 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 a polymer (B-1a) which was an ethylene / VCH copolymer was obtained. [Η] of the polymer (B-1a) 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 ) Was −28 ° C., and the content of structural units derived from VCH in the polymer (B-1a) was 13 mol%.

<Production Example 2 of (B): Production Example of Polymer (B-2a)>
To 100 parts of the obtained polymer (B-1a), 0.4 part of maleic anhydride and 0.04 part of 1,3-bis (t-butylperoxyisopropyl) benzene were added and thoroughly premixed. The polymer (B-2a) obtained by graft polymerization of maleic anhydride to an ethylene / VCH copolymer was obtained by supplying from a supply port of a shaft extruder and performing melt kneading. 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 the polymer (B-2a) was 0.2%. The MFR of the polymer (B-2a) was 180 g / 10 min (190 ° C., load: 2.16 kgf).

<Production Example 3 of (B): Production Example of Polymer (B-1b)>
By changing the ethylene in <Production Example 1 of (B)> to propylene, a polymer (B-1b) that is a propylene / VCH copolymer can be obtained.

<Production Example 4 of (B): Production Example of Polymer (B-2b)>
<Polymer (B-1a) produced by graft polymerization of maleic anhydride to propylene / VCH copolymer by changing polymer (B-1a) to polymer (B-1b) in <Production Example 2 of (B)> B-2b) can be obtained.

<Production of aqueous emulsion>
(Reference Example 1)
After setting the cylinder temperature of a co-rotating meshing twin screw extruder (manufactured by Nippon Steel Works Co., Ltd .: TEX30φ, L / D = 30) to 110 ° C., the polymer (B ) 110 parts of (B-2a) was continuously supplied at a screw rotational speed of 350 rpm, and (B-2a) was heated.
From the supply port provided in the vent part of the extruder, 10 parts (solid content) of the acrylic resin obtained in the reference production example, which is an emulsifier, is continuously supplied while being pressurized with a gear pump, and the acrylic resin and (B-2a ) Were continuously extruded to obtain a milky white aqueous emulsion. The obtained aqueous emulsion had a particle size of 0.6 μm (volume basis).
(Examples 1-5)
In Reference Example, the aqueous emulsion of the present invention was obtained in the same manner as in Reference Example except that (A-1) to (A-5) were used as emulsifiers in place of the acrylic resin obtained in Reference Production Example.

<Example of pigment paste production>
In a 200 mL container made of SUS for sand grinder, Acryset ARL-460 (pigment dispersant (aqueous acrylic resin), solid content 50.8%, manufactured by Nippon Shokubai Co., Ltd.) 53.4 g, Surfynol 104 (antifoaming agent (acetylene diol) Derivative), solid content 50.0%, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.2 g and ion-exchanged water 85.1 g were stirred and stirred at 300 rpm for 10 minutes to obtain a blend.
Subsequently, carbon black: MA-100 (Mitsubishi Resin Co., Ltd.) 15.1 g, talc: NK-64 (Fuji Talc Co., Ltd.) 30.1 g and titanium oxide: Typaque R820 (Ishihara Sangyo Co., Ltd.) ) 15.1 g and the mixture was stirred at 600 rpm for 30 minutes to obtain a blend.
Furthermore, 200 g of glass beads (1.0 mmφ) were added to the obtained composition, and after stirring for 8 hours at 2000 rpm in the range of 25-30 ° C. with a 6-cylinder sand grinder (manufactured by Igarashi Machinery Co., Ltd.), A pigment paste having a solid content of 45.5% was obtained by filtering through a 200-mesh filter cloth.

<Manufacture of coating film and laminate>
(Reference Example 2)
While stirring 20.0 g of the pigment paste obtained in <Pigment Paste Production Example> with a three-one motor, there was added the aqueous emulsion obtained in Reference Example 1 (3.9 g in terms of solid content) and 20% urea water in an amount of 0. A mixture with 68 g was added dropwise over 5 minutes, and after the addition, the mixture was further stirred for 5 minutes to prepare a blend.
A coating is applied to a polypropylene substrate so that the film thickness is about 10 μm after drying, and the resulting coated product is heat-treated at 120 ° C. for 30 minutes. The resulting laminate was obtained.
(Examples 6 to 10)
In Reference Example 2, the coating film of the present invention, the coating film and polypropylene were used in the same manner as in Reference Example 2, except that the aqueous emulsion obtained in Examples 1 to 5 was used instead of the aqueous emulsion obtained in Reference Example 1. A laminate comprising a substrate was obtained.

<Adhesion test example>
A cut of 1 mm width 100 squares was made on the surface of the coating film obtained in each of Examples 6 to 10 and Reference Example 2, and the number of squares where the coating film remained was counted by cellophane tape peeling. Adhesiveness was evaluated by both coating film remaining after cellophane tape peeling 3 times. A larger number (closer to 100) means better adhesion. The results are shown in Table 4.

(Example 6)
An aqueous emulsion can be obtained by carrying out in the same manner as in Example 3, except that the polymer (B-2a) in (B) in Example 3 is changed to the polymer (B-1a).

(Example 7)
An aqueous emulsion can be obtained by carrying out in the same manner as in Example 3, except that the polymer (B-2a) in (B) in Example 3 is changed to the polymer (B-1b).

(Example 8)
An aqueous emulsion can be obtained by carrying out in the same manner as in Example 3, except that the polymer (B-2a) in (B) in Example 3 is changed to the polymer (B-2b).

Example 9
An aqueous emulsion can be obtained by carrying out in the same manner as in Example 4 except that the polymer (B-2a) of (B) in Example 4 is changed to the polymer (B-1a).

(Example 10)
An aqueous emulsion can be obtained by carrying out in the same manner as in Example 4 except that the polymer (B-2a) in (B) in Example 4 is changed to the polymer (B-1b).

(Example 11)
An aqueous emulsion can be obtained by carrying out in the same manner as in Example 4 except that the polymer (B-2a) in (B) in Example 4 is changed to the polymer (B-2b).

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

Claims (15)

An aqueous emulsion comprising the following (A), (B) and (C).
(A) a structural unit derived from an α, β-unsaturated carboxylic acid (1);
An acrylic resin <compound group> comprising a structural unit derived from at least one compound (2) selected from the following <compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
C6-C20 aromatic sulfonic acid and its salt (B) thermoplastic polymer (however, different from (A))
(C) Water   The aqueous emulsion according to claim 1, wherein (B) is a thermoplastic polymer containing a structural unit derived from ethylene and / or propylene. (B) is a structural unit derived from ethylene and / or propylene, 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:
The aqueous emulsion according to claim 1 or 2, which is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the olefin copolymer.   The aqueous emulsion according to claim 3, wherein the vinyl compound represented by the formula (I) is vinylcyclohexane.   MFR (190 degreeC, 2.16kgf) of (B) is 10 g / 10min or more and 300 g / 10min or less, The aqueous emulsion in any one of Claims 1-4 characterized by the above-mentioned.   The structural unit derived from the α, β-unsaturated carboxylic acid (1) in (A) 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 claims 1 to 5.   The structural unit derived from the α, β-unsaturated carboxylic acid ester (2) in (A) is at least one α, β-unsaturated carboxylic acid selected from the group consisting of alkyl acrylates and alkyl methacrylates. The aqueous emulsion according to any one of claims 1 to 6, which is a structural unit derived from an ester. The manufacturing method of the water-based emulsion characterized by including the process of melt-kneading the following (A), (B) and (C).
(A) a structural unit derived from an α, β-unsaturated carboxylic acid (1);
An acrylic resin <compound group> comprising a structural unit derived from at least one compound (2) selected from the following <compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
C6-C20 aromatic sulfonic acid and its salt (B) thermoplastic polymer (however, different from (A))
(C) Water   A method for forming a coating film, comprising a step of coating the aqueous emulsion according to any one of claims 1 to 7 on a substrate.   Hardened | cured material formed by drying the aqueous emulsion in any one of Claims 1-7.   The laminated body which has a base material consisting of at least 1 sort (s) of material chosen from the group which consists of a wood type material, a cellulosic material, a plastic material, a ceramic material, and a metal material, and the layer which consists of hardened | cured material of Claim 10. Applying the aqueous emulsion according to any one of claims 1 to 7 to a base material made of at least one material selected from the group consisting of a woody material, a cellulosic material, a plastic material, a ceramic material and a metal material, A first step of obtaining a coated product having the substrate and a layer comprising the aqueous emulsion;
The manufacturing method of the laminated body which has the 2nd process of drying the coating material obtained at the 1st process, and obtaining the laminated body which consists of the said base material and the hardened | cured material layer obtained from the said aqueous emulsion. a structural unit derived from an α, β-unsaturated carboxylic acid (1);
An acrylic resin <compound group> comprising a structural unit derived from at least one compound (2) selected from the following <compound group>
A monomer having a phosphate group and a (meth) acryloyl group and a salt thereof;
A monomer having a sulfo group and a (meth) acryloyl group and a salt thereof;
A monomer having an epoxy group and a (meth) acryloyl group,
A monomer having a group derived from phthalic acid and a (meth) acryloyl group, and a salt thereof;
C2-C20 aliphatic unsaturated sulfonic acid and its salt, and
Aromatic sulfonic acid having 6 to 20 carbon atoms and salt thereof   The structural unit derived from α, β-unsaturated carboxylic acid (1) 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. 14. Emulsifier according to claim 13 characterized in that   Use of the aqueous emulsion according to any one of claims 1 to 7 as a coating film.