WO2011010679A1

WO2011010679A1 - Aqueous emulsion

Info

Publication number: WO2011010679A1
Application number: PCT/JP2010/062288
Authority: WO
Inventors: 藤井遥平; 森本順次
Original assignee: 住友化学株式会社
Priority date: 2009-07-21
Filing date: 2010-07-14
Publication date: 2011-01-27
Also published as: TW201107351A; JP2011042781A

Abstract

Provided is an aqueous emulsion comprising components (A), (B), and (C), where: (A) is an acrylic resin containing structural units derived from an α,β-unsaturated carboxylic acid poly(alkylene glycol) ester derived from a poly(alkylene glycol) wherein one of the terminal hydroxyl groups is optionally substituted by an alkoxyl group, and an α,β-unsaturated carboxylic acid ester, and structural units derived from an α,β-unsaturated carboxylic acid ester derived from a C_1-20 aliphatic alcohol and an α,β-unsaturated carboxylic acid; (B) is a copolymer containing structural units derived from ethylene and/or propylene, and structural units derived from a vinyl compound represented by general formula (I) CH₂ = CH-R (I) (where R is a secondary alkyl, tertiary alkyl, or alicyclic hydrocarbon group), or a polymer obtained by graft polymerization of an α,β-unsaturated carboxylic acid anhydride to the copolymer; and (C) is water.　

Description

Water-based emulsion

The present invention relates to an aqueous emulsion.

Polypropylene is used for automobile parts such as bumpers because it has excellent processability and strength. A paint is usually applied to automobile parts for decoration or the like. However, since it is difficult for other materials such as paint to adhere to the surface of polypropylene, generally, a chlorinated polyolefin excellent in adhesiveness with polypropylene is applied to polypropylene, and the paint is applied thereon (for example, JP-A-5-7832).

The present invention
<1> An aqueous emulsion comprising the following component (A), component (B) and component (C);
(A) Poly (alkylene) of α, β-unsaturated carboxylic acid derived from poly (alkylene glycol) in which one hydroxyl group located at the terminal may be substituted with an alkoxy group and α, β-unsaturated carboxylic acid Glycol) ester and a structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. Acrylic resin (B) Structural unit derived from ethylene and / or propylene, and 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.)
Or a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the copolymer (C) water <2> The aqueous emulsion according to <1>, wherein in the component (A), the α, β-unsaturated carboxylic acid is methacrylic acid or acrylic acid;
<3> In the component (A), the poly (alkylene glycol) ester of α, β-unsaturated carboxylic acid is poly (ethylene glycol) methacrylate or poly (ethylene glycol) methyl ether methacrylate <1> or <2> An aqueous emulsion according to claim 1;
<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 aqueous solution according to any one of <1> to <4>, wherein in the component (B), the MFR (190 ° C., 2.16 kgf) of the copolymer is 130 g / 10 min or more and 300 g / 10 min or less. Emulsion;
<6> The content of structural units derived from poly (alkylene glycol) ester of α, β-unsaturated carboxylic acid is 85 with respect to 100 parts by weight of all structural units constituting the acrylic resin in component (A). ~ 95 parts by weight of the aqueous emulsion according to any one of <1> to <5>;
<7> The aqueous emulsion is an aqueous emulsion having the component (A) and the component (B) as a dispersoid and the component (C) as a dispersion medium, and the volume-based median diameter of the dispersoid is 0.01 μm. The aqueous emulsion according to any one of <1> to <6>, which is ~ 3 μm;
<8> Including the following component (A), component (B) and component (C), wherein the component (A) and the component (B) are melt-kneaded and the resulting molten mixture is mixed with water. A method for producing an aqueous emulsion;
(A) Poly (alkylene) of α, β-unsaturated carboxylic acid derived from poly (alkylene glycol) in which one hydroxyl group located at the terminal may be substituted with an alkoxy group and α, β-unsaturated carboxylic acid Glycol) ester and a structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. Acrylic resin (B) Structural unit derived from ethylene and / or propylene, and 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.)
Or a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the copolymer (C) water <9> A cured product obtained by drying the aqueous emulsion according to any one of <1> to <7>;
<10> A laminate having a base material layer made of at least one material selected from the group consisting of a wood material, a cellulose material, a plastic material, a ceramic material, and a metal material, and a layer made of the cured product according to <9>;
<11> The aqueous emulsion according to any one of <1> to <7>, wherein the base material layer is made of at least one material selected from the group consisting of woody materials, cellulose materials, plastic materials, ceramic materials, and metal materials. To obtain a laminate having the base material layer and the aqueous emulsion layer,
A method for producing a laminate comprising: drying the laminate obtained in the step to obtain a laminate having the base material layer and a cured product layer obtained from the aqueous emulsion. .

The aqueous emulsion of the present invention comprises the following component (A), component (B) and component (C).
(A) Poly (alkylene) of α, β-unsaturated carboxylic acid derived from poly (alkylene glycol) in which one hydroxyl group located at the terminal may be substituted with an alkoxy group and α, β-unsaturated carboxylic acid Glycol) ester-derived structural unit (hereinafter abbreviated as structural unit (a1)), an α, β-unsaturated derivative derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. Acrylic resin containing a structural unit derived from a saturated carboxylic acid ester (hereinafter abbreviated as structural unit (a2))
(B) a structural unit derived from ethylene and / or propylene (hereinafter abbreviated as structural unit (b1)) and 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.)
Or a copolymer containing a structural unit derived from the vinyl compound shown below (hereinafter abbreviated as structural unit (b2)), or α, β-unsaturated carboxylic acid anhydride is grafted to the copolymer. Polymer obtained by polymerizing
(C) Water
First, the component (A) will be described.
The component (A) is an acrylic resin containing the structural unit (a1) and the structural unit (a2).
The structural unit (a1) is an α, β-unsaturated carboxylic acid derived from poly (alkylene glycol) in which one hydroxyl group located at the terminal may be substituted with an alkoxy group and an α, β-unsaturated carboxylic acid. It is a structural unit derived from (polyalkylene glycol) ester.
Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, angelic acid, sorbic acid, mesaconic acid and the like having 3 to 20 carbon atoms. And α, β-unsaturated carboxylic acids. The α, β-unsaturated carboxylic acid is preferably an α, β-unsaturated carboxylic acid having one or two carboxyl groups (—COOH), more preferably acrylic acid or methacrylic acid.
Examples of poly (alkylene glycol) include polymers of alkylene oxides having 1 to 4 carbon atoms such as ethylene oxide and propylene oxide. The number of structural units derived from alkylene oxide in the polymer is usually 2 to 100. Preferably, it is 4-25.
“Poly (alkylene glycol) in which one hydroxyl group located at the end may be substituted with an alkoxy group” means poly (alkylene glycol) in which one hydroxyl group located at the end may be protected with an alkyl group To do. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group. Examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group and an ethyl group. Poly (ethylene glycol) and poly (propylene glycol) are preferred.
Examples of the poly (alkylene glycol) optionally substituted with one hydroxyl group at the terminal include poly (ethylene glycol), methoxy poly (ethylene glycol), ethoxy poly (ethylene glycol), propoxy poly (ethylene glycol), Examples include butoxy poly (ethylene glycol), poly (propylene glycol), methoxy poly (propylene glycol), ethoxy poly (propylene glycol), propoxy poly (propylene glycol), and butoxy poly (propylene glycol). Poly (alkylene glycol) in which one hydroxyl group located at the end is substituted with an alkoxy group is preferred, and poly (alkylene glycol) in which one hydroxyl group located at the end is substituted with an alkoxy group having 1 to 4 carbon atoms is more preferred .
Poly (alkylene glycol) esters of α, β-unsaturated carboxylic acids include poly (ethylene glycol) acrylate, poly (ethylene glycol) methacrylate, poly (ethylene glycol) methyl ether acrylate, poly (ethylene glycol) methyl ether methacrylate, Poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, poly (ethylene glycol) propyl ether acrylate, poly (ethylene glycol) propyl ether methacrylate, poly (ethylene glycol) butyl ether acrylate, poly (ethylene glycol) butyl ether Methacrylate, poly (propylene glycol) acrylate, poly (propylene) Glycol) methacrylate, poly (propylene glycol) methyl ether acrylate, poly (propylene glycol) methyl ether methacrylate, poly (propylene glycol) ethyl ether acrylate, poly (propylene glycol) ethyl ether methacrylate, poly (propylene glycol) propyl ether acrylate, poly (Propylene glycol) propyl ether methacrylate, poly (propylene glycol) butyl ether acrylate and poly (propylene glycol) butyl ether methacrylate may be mentioned, and poly (ethylene glycol) methacrylate and poly (ethylene glycol) methyl ether methacrylate are preferred.
Examples of such poly (alkylene glycol) esters of α, β-unsaturated carboxylic acids include commercially available products such as Blemmer (registered trademark) PME manufactured by NOF Corporation and Kyoeisha Chemical Co., Ltd. functional monomer 130MA (trade name). Can be used as is.
In the acrylic resin of component (A), the content of structural units derived from poly (alkylene glycol) ester of α, β-unsaturated carboxylic acid with respect to 100 parts by weight of all structural units constituting the acrylic resin, From the viewpoint of the dispersibility of the acrylic resin in water, it is usually 80 to 97 parts by weight, and from the viewpoint of adhesion to the substrate of the cured product obtained from the aqueous emulsion of the present invention, it is 85 to 95 parts by weight. Is preferred.
The acrylic resin of the component (A) may have two or more types of structural units (a1).
The structural unit (a2) is a structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. Examples of the α, β-unsaturated carboxylic acid include those described above, and acrylic acid or methacrylic acid is preferable.
Examples of the aliphatic alcohol having 1 to 20 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, 3-methylbutanol, 2,2-dimethylpropanol, 3-methyl-2-butanol, 2 -C1-C20 linear, branched or cyclic aliphatic alcohols such as ethylhexanol, nonanol, decanol, lauryl alcohol, tridecyl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol, etc. A linear, branched or cyclic aliphatic alcohol having a number of 1 to 4 is preferred.
As α, β-unsaturated carboxylic acid ester, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decanyl acrylate, lauryl acrylate, acrylic acid Tridecyl, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, ethyl hexyl methacrylate, nonyl methacrylate, decanyl methacrylate, lauryl methacrylate, Examples include tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate and cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate and methacrylate. Tridecyl formate is preferred.
In the acrylic resin of component (A), the content of the structural unit derived from the α, β-unsaturated carboxylic acid ester is 100% by weight of all the structural units constituting the acrylic resin. From the viewpoint of the adhesiveness to the substrate of the cured product obtained from the aqueous emulsion of the present invention, it is preferably 5 to 15 parts by weight.
The acrylic resin of the component (A) may have two or more types of structural units (a2).
The acrylic resin of component (A) may contain two or more kinds of acrylic resins.
In addition to the structural unit (a1) and the structural unit (a2), the acrylic resin of the component (A) may have another structural unit.
Other structural units include
Α, β-unsaturated carboxylic acid derived from α, β-unsaturated carboxylic acid and aliphatic diol having 1 to 10 carbon atoms having at least one hydroxyl group bonded to primary carbon atom or secondary carbon atom A structural unit derived from an ester (hereinafter abbreviated as structural unit (a3)),
A structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an α, β-unsaturated carboxylic acid and an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent ( Hereinafter, abbreviated as structural unit (a4)), and
A structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an α, β-unsaturated carboxylic acid (hereinafter referred to as structural unit (a5)) Abbreviated).
Examples of the α, β-unsaturated carboxylic acid for deriving the other structural units include those described above, and acrylic acid or methacrylic acid is preferable.
The α, β-unsaturated carboxylic acid ester leading to the structural unit (a3) is an aliphatic diol having 1 to 10 carbon atoms having at least one hydroxyl group bonded to a primary carbon atom or a secondary carbon atom, α, Derived from β-unsaturated carboxylic acid.
The aliphatic diol having 1 to 10 carbon atoms is an aliphatic compound having 1 to 10 carbon atoms and having two hydroxyl groups, and at least one of the hydroxyl groups is a primary carbon atom or Bonded to a secondary carbon atom. A “primary carbon atom” is a carbon atom bonded to only one other carbon atom, and a “secondary carbon atom” is a carbon atom bonded to two other carbon atoms. . Therefore, the aliphatic diol having 1 to 10 carbon atoms has a hydroxyl group bonded to a methylene group or a methine group. An aliphatic diol having 1 to 10 carbon atoms having at least one hydroxyl group bonded to a primary carbon atom is preferable, and an α, ω-alkanediol having 1 to 10 carbon atoms is more preferable. Such α, ω-alkanediol has the following formula:
HO- (CH ₂ ) _y -OH
(Wherein y represents an integer of 1 to 10)
Specific examples include 2-hydroxyethanol, 3-hydroxypropanol, 4-hydroxybutanol, 5-hydroxypentanol and 6-hydroxyhexanol.
Examples of the α, β-unsaturated carboxylic acid ester that leads the structural unit (a3) include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxy. Hexyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate and 6-hydroxyhexyl methacrylate, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate are preferred.
The α, β-unsaturated carboxylic acid ester leading to the structural unit (a4) is an aliphatic alcohol having 1 to 10 carbon atoms having an optionally substituted amino group, an α, β-unsaturated carboxylic acid, Derived from.
The amino group which may have a substituent is an amino group; methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, tert-butyl. 2 amino groups such as an amino group having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as amino group; dimethylamino group, methylethylamino group, diethylamino group, dipropylamino group, etc. And an amino group having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; and a cyclic amino group, and two linear and branched chains having 1 to 10 carbon atoms An amino group having a linear or cyclic alkyl group is preferred, and an amino group having two linear, branched or cyclic alkyl groups having 1 to 3 carbon atoms is more preferred.
Examples of the aliphatic alcohol having 1 to 10 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, 3-methylbutanol, 2,2-dimethylpropanol, 3-methyl-2-butanol, 2 -Straight chain, branched chain or cyclic aliphatic alcohols having 1 to 10 carbon atoms such as ethylhexanol, nonanol, decanol, cyclohexanol, etc., straight chain or branched chains having 1 to 4 carbon atoms Or a cyclic aliphatic alcohol is preferable.
Examples of the aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent include N, N-dimethylaminoethanol, N, N-diethylaminoethanol, N-methyl-N-ethylaminoethanol, Examples include N, N-dipropylaminoethanol, N-methyl-N-propylaminoethanol, N-ethyl-N-propylaminoethanol, N, N-dimethylaminopropanol and N, N-dimethylaminobutanol.
The α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent and an α, β-unsaturated carboxylic acid includes N, N -Diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N-methyl-N-ethylaminoethyl acrylate and N-methyl-N-ethylamino Examples thereof include ethyl methacrylate, and N, N-dimethylaminoethyl methacrylate is preferable.
The structural unit (a5) is derived from an α, β-unsaturated carboxylic acid ester derived from a C 1-10 aliphatic alcohol having a carboxylic acid group and an α, β-unsaturated carboxylic acid. Here, “carboxylic acid group” means an organic group having a carboxyl group (—COOH), such as carboxymethyl group, 1,2-dicarboxyethyl group, 2-carboxyphenyl group and 2,3-dicarboxyphenyl. Groups.
Examples of the α, β-unsaturated carboxylic acid ester derived 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- Examples include acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxyethyl phthalic acid.
The acrylic resin of component (A) may have two or more structural units (a3).
The acrylic resin of component (A) may have two or more structural units (a4).
The acrylic resin of component (A) may have two or more structural units (a5).
In the acrylic resin of component (A), the total content of structural units (a3), (a4) and (a5) is usually 0 to 805 mol with respect to 100 mol of all structural units constituting the acrylic resin. And preferably 0 to 50 mol.
In addition to the structural unit, the acrylic resin of component (A) includes a structural unit derived from ethylene, a structural unit derived from propylene, a structural unit derived from a linear α-olefin having 4 or more carbon atoms, which will be described later, May contain a structural unit derived from the vinyl compound represented by the formula (I), a structural unit derived from an addition-polymerizable monomer described later, and the like, the content of which drys the aqueous emulsion of the present invention. It is sufficient that the amount of the cured product obtained is not impaired, and the amount is preferably about 5 mol or less with respect to 100 mol of all the structural units constituting the acrylic resin, and is a structure derived from an addition-polymerizable monomer. The unit is preferably 1 mol or less.
The acrylic resin of component (A) can be produced by addition polymerization of monomers that lead each structural unit. For example, an alcohol solvent such as isopropanol, a solvent such as water, and a monomer are mixed, and the resulting mixture and a polymerization initiator such as a radical initiator are usually mixed at 70 to 100 ° C., preferably 75 to 95 ° C. The resulting mixture is usually stirred for about 1 to 24 hours to carry out the polymerization reaction, the solvent and a part of the monomer are mixed, and the resulting mixture, the polymerization initiator and the remaining monomer are usually added to 70 to 100. There may be mentioned a method in which the polymerization reaction is carried out by mixing at 0 ° C., preferably 75 to 95 ° C., and stirring the resulting mixture usually for about 1 to 24 hours. In order to easily control the polymerization reaction, a solution obtained by dissolving a polymerization initiator and the remaining monomers in an organic solvent may be used. The polymerization initiator can be divided and added to the mixture.
The amount of the polymerization initiator used is usually 0.01 to 3 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of monomers. . By using the polymerization initiator in an amount within this range, the component (A) having a desired weight average molecular weight can be easily produced.
As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate) Azo compounds such as 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxy Oxydicarbonate, dipropyl peroxydicarbonate, tert-butyl peroxyne Organic peroxides such as decanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide . A redox initiator in which a polymerization initiator and a reducing agent are used in combination can also be used as the polymerization initiator.
Component (A) acts as an emulsifier for dispersing component (B) in component (C) in the aqueous emulsion of the present invention.
Subsequently, the component (B) will be described.
Component (B) comprises a structural unit derived from ethylene and / or propylene 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.)
A copolymer (hereinafter abbreviated as polymer (B-1)) containing a structural unit derived from a vinyl compound (hereinafter abbreviated as vinyl compound (I)), or a polymer. (B-1) is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride (hereinafter abbreviated as polymer (B-2)).
In the formula (I), the secondary alkyl group represented by R is preferably a secondary alkyl group having 3 to 20 carbon atoms, and the tertiary alkyl group is preferably a tertiary alkyl group having 4 to 20 carbon atoms. The alicyclic hydrocarbon group is preferably a 3- to 16-membered alicyclic hydrocarbon group. Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group, and a cycloalkyl group is preferable.
R is more preferably a 3- to 10-membered alicyclic hydrocarbon group having 3 to 20 carbon atoms and a tertiary alkyl group having 4 to 20 carbon atoms.
Examples of the vinyl compound (I) include 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3, 4-dimethyl-1-pentene, 3,4-dimethyl-1-hexene, 3,4-dimethyl-1-heptene, 3,4-dimethyl-1-octene, 3,5-dimethyl-1-hexene, 3, 5-dimethyl-1-heptene, 3,5-dimethyl-1-octene, 3,6-dimethyl-1-heptene, 3,6-dimethyl-1-octene, 3,7-dimethyl-1-octene, 3, R of 2,4-trimethyl-1-pentene, 3,4,4-trimethyl-1-hexene, 3,4,4-trimethyl-1-heptene, 3,4,4-trimethyl-1-octene and the like is 2 Vinyl compounds that are secondary alkyl groups I); 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 Vinyl compound (I) wherein R is a tertiary alkyl group; vinyl compound (I) where R is a cycloalkyl group such as vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, etc. ); 1-vinyladamantane, 5-vinyl-2-norbornene and 4-vinyl-1-cyclohexene.
Among them, 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, vinylcyclo Heptane, vinylcyclooctane and 5-vinyl-2-norbornene are preferred, and 3-methyl-1-butene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 3,3-dimethyl-1- More preferred are butene, 3,3,4-trimethyl-1-pentene, vinylcyclohexane and vinylnorbornene, 3,3-dimethyl-1-butene and Particularly preferred Le cyclohexane, vinyl cyclohexane being most preferred.
The content of the structural unit derived from the vinyl compound (I) in the polymer (B-1) is selected from the viewpoint of the adhesiveness of a cured product obtained by drying the aqueous emulsion of the present invention. The amount is usually 5 to 40 mol, preferably 10 to 30 mol, more preferably 10 to 20 mol, per 100 mol of all structural units constituting 1).
The content of the structural unit derived from the vinyl compound (I) in the polymer (B-1) is the same as that of the polymer (B-1). ¹ H-NMR analysis and ¹³ It can be determined by C-NMR analysis.
The polymer (B-1) can further contain a structural unit derived from a linear α-olefin having 4 to 20 carbon atoms. Examples of the linear α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene and 1-eicosene. Of these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.
The total content of structural units derived from ethylene, propylene and a linear α-olefin having 4 to 20 carbon atoms in the polymer (B-1) is all the constituents of the polymer (B-1). The amount is usually 95 to 60 mol, preferably 90 to 70 mol, more preferably 90 to 80 mol, per 100 mol of the structural unit.
The polymer (B-1) may further have a structural unit derived from a monomer capable of addition polymerization.
The addition-polymerizable monomer is a monomer other than ethylene, propylene, a linear α-olefin having 4 to 20 carbon atoms and a vinyl compound (I), and includes ethylene, propylene, and a linear α having 4 to 20 carbon atoms. -A monomer capable of addition polymerization with an olefin and a vinyl compound (I), and the carbon number of the monomer is usually about 3 to 20.
Specific examples of addition-polymerizable monomers include cycloolefins, formula (II)

(In the formula, R ′ and R ″ each independently represent a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a halogen atom.)
An olefin, a diene compound, a vinyl halide, a vinyl aliphatic carboxylate, a vinyl ether compound, a cyanovinyl compound, the α, β-unsaturated carboxylic acid, the α, β-unsaturated carboxylic acid ester, and α, β described below. -Unsaturated carboxylic acid anhydrides.
Cycloolefins include cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5 -Butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl- 2-norbornene, 5-d Xoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyl-2-tetracyclododecene, 8-methyl-8-methoxycarbonyl-2 -Tetracyclododecene and 8-cyano-2-tetracyclododecene. Among them, cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2- Norbornene and 5-cyano-2-norbornene are preferred, and 2-norbornene and 2-tetracyclododecene are more preferred.
Examples of the olefin represented by the formula (II) include isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, and 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 and vinylidene chloride, isobutene, 2,3-dimethyl-1-butene and 2,4,4-trimethyl -1-pentene is preferred.
Examples of the diene compound include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, 2,5-norbornadiene, and diene. And cyclopentadiene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 4-vinyl-1-cyclohexene and 5-ethylidene-2-norbornene, and include 1,4-pentadiene, 1,5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinyl-1-cyclohexene and 5-ethylidene-2-norbornene are preferred.
Aliphatic vinyl carboxylates include vinyl acetate, vinyl propionate and vinyl butyrate, and vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether. Examples of the vinyl halide include vinyl chloride, and examples of the cyanovinyl compound include acrylonitrile and methacrylonitrile.
The content of the structural unit derived from the addition-polymerizable monomer in the polymer (B-1) may be an amount that does not impair the adhesion of the cured product obtained by drying the aqueous emulsion of the present invention. 5 mol or less is preferable with respect to 100 mol of all the structural units constituting the combination (B-1), and 1 mol or less is more preferable.
The polymer (B-1) can be produced, for example, by polymerizing a corresponding monomer using a transition metal compound having a group having an indenyl anion skeleton or a crosslinked cyclopentadienyl anion skeleton as a catalyst. . Of these, the methods described in JP-A No. 2003-82028, JP-A No. 2003-160621 and JP-A No. 2000-128932 are preferable.
In the production of the polymer (B-1), depending on the type of catalyst used and the polymerization conditions, in addition to the polymer (B-1), an ethylene homopolymer, a propylene homopolymer and / or a vinyl compound (I) ) Homopolymer may be formed. In such a case, the polymer (B-1) can be easily taken out by performing solvent extraction using a Soxhlet extractor or the like. When toluene is used as the solvent, the homopolymer of the vinyl compound (I) can be removed as an insoluble component. When chloroform is used as the solvent, olefin homopolymers such as ethylene homopolymer and propylene homopolymer can be removed as insoluble components. The polymer (B-1) can be separated as a soluble component in these solvents. When there is no problem in the use, the polymer (B-1) containing the by-product as described above may be used.
The molecular weight distribution (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) of the polymer (B-1) indicates the mechanical strength and transparency of the cured product obtained by drying the aqueous emulsion of the present invention. From the viewpoint, it is usually about 1.5 to 10.0, preferably about 1.5 to 7.0, and more preferably about 1.5 to 5.0.
The weight average molecular weight (Mw) of the polymer (B-1) is usually 5 from the viewpoint of the mechanical strength of the cured product obtained by drying the aqueous emulsion of the present invention and the fluidity of the polymer (B-1). It is about 1,000 to 1,000,000, preferably about 10,000 to 500,000, and more preferably about 15,000 to 400,000.
The molecular weight distribution of the polymer (B-1) can be determined by gel permeation chromatography (GPC).
The melt flow rate (MFR) of the polymer (B-1) measured under the conditions of 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven) in accordance with JIS K 7210. ) Is usually 130 to 300 g / 10 min, preferably 130 to 220 g / 10 min, from the viewpoint of dispersibility of the polymer (B-1) in the aqueous emulsion of the present invention.
The polymer (B-2) is a polymer obtained by graft polymerizing an α, β-unsaturated carboxylic acid anhydride to the polymer (B-1).
The graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride is usually about 0.01 to 20 parts by weight, preferably about 0.05 to 10 parts by weight with respect to 100 parts by weight of the polymer (B-2). More preferably, it is about 0.1 to 5 parts by weight.
The aqueous emulsion of the present invention containing the polymer (B-2) in which the graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride is 0.01 parts by weight or more tends to improve the adhesion. The aqueous emulsion of the present invention containing a polymer (B-2) having a graft polymerization amount of α, β-unsaturated carboxylic acid anhydride of 20 parts by weight or less tends to hardly cause coloring.
Examples of the α, β-unsaturated carboxylic acid anhydride include α, β-unsaturated carboxylic acid anhydrides having 4 to 20 carbon atoms such as maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. preferable. Two or more α, β-unsaturated carboxylic acid anhydrides may be used in combination.
For example, the polymer (B-2) is graft-polymerized by adding an α, β-unsaturated carboxylic acid anhydride to the melt polymer (B-1) obtained by melting the polymer (B-1). The polymer (B-1) is dissolved in a solvent such as toluene and xylene, and α, β-unsaturated carboxylic acid anhydride is added to the resulting solution to perform graft polymerization. it can.
Graft polymerization is usually performed in the presence of a radical initiator.
When the amount of the radical initiator used is small, the amount of graft polymerization of the α, β-unsaturated carboxylic acid anhydride is reduced, and the adhesiveness of the cured product obtained by drying the aqueous emulsion of the present invention is improved. Since the amount of the unreacted radical initiator contained in the polymer (B-2) tends to increase if the amount is too much, the amount of the polymer (B-1) is 100 parts by weight. The amount is usually 0.01 to 10 parts by weight, preferably 0.01 to 1 part by weight.
As the radical initiator, an organic peroxide is usually used, and an organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute is preferable. When an organic peroxide having a decomposition temperature of 50 ° C. or higher is used, the amount of graft polymerization of α, β-unsaturated carboxylic acid anhydride tends to be improved, and an organic peroxide having a decomposition temperature of 210 ° C. or lower is preferred. When an oxide is used, decomposition of the polymer (B-1) in graft polymerization tends to be reduced. An organic peroxide having a function of extracting protons from the polymer (B-1) after generating radicals by decomposition is preferred.
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. Dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds and alkyl perester compounds are preferred. Specifically, dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate Bonate, tert-butyl peroxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, tert-butyl peroxyneo Decanoate, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 1,1-bis (tert-butylperoxy) ) Clododecane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di (benzoylper) Oxy) hexane, tert-butyl peroxyacetate, 2,2-bis (tert-butylperoxy) butene, tert-butyl peroxybenzoate, butyl 4,4-bis (tert-butylperoxy) valerate, di-tert -Butylberoxyisophthalate, dicumyl peroxide, α-α'-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane 1,3-bis (tert-butyl -Oxyisopropyl) benzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide and 2,5-dimethyl-2,5-di (tert-butylperoxy) -3-hexyne Is mentioned.
The addition amount of the organic peroxide is usually 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymer (B-1).
The polymer (B) can be melt kneaded using an extruder, and various polymers or various known methods for mixing polymers and solid or liquid additives can be used. A method of graft polymerization by adding an α, β-unsaturated carboxylic acid anhydride to the molten polymer (B-1) obtained by melting -1). It is more preferable to combine all or some of the components for graft polymerization and separately mix them with a Henschel mixer, ribbon blender, blender or the like to obtain a uniform mixture, and then melt and knead the mixture. As the melt-kneading means, known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed. From the viewpoint that the polymer (B-2) can be continuously produced and the productivity is improved, the polymer (B-1), the α, β-unsaturated carboxylic acid anhydride and the radical initiator are sufficiently sufficient in advance. A method is preferred in which the mixture obtained by mixing is fed from the feed port of a single-screw or twin-screw extruder and kneaded. The temperature of the portion where the melt kneading of the extruder is performed (for example, the cylinder temperature of the 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 (B-1) tends to be suppressed. The melt kneading is preferably performed in two stages, and the temperature of the second stage melt kneading is preferably higher than the temperature of the first stage melt kneading. 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, decomposition of the polymer (B-1) tends to be suppressed.
The structural unit derived from the α, β-unsaturated carboxylic acid anhydride in the polymer (B-2) may be a structural unit in which the acid anhydride structure is retained, or the acid anhydride structure is ring-opened. It may be a structural unit derived from an α, β-unsaturated carboxylic acid, derived from an α, β-unsaturated carboxylic acid in which the acid anhydride structure is held and the structural unit in which the acid anhydride structure is retained. It may be a structural unit including both of the structural units.
The molecular weight distribution (Mw / Mn) of the polymer (B-2) is usually 1.5 to 10, preferably 1.5 to 7, and more preferably 1.5 to 5. The molecular weight distribution of the polymer (B-2) can be measured by the same method as the molecular weight distribution of the polymer (B-1).
The melt flow rate (MFR) of the polymer (B-2) measured under the conditions of 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven) in accordance with JIS K 7210. ) Is usually 130 g / 10 min to 300 g / 10 min, preferably 130 g / 10 min to 200 g / 10 min.
The aqueous emulsion of the present invention contains water as the component (C) in addition to the component (A) and the component (B), the component (A) and the component (B) are dispersoids, and the component (C) is dispersed. It is an emulsion used as a medium.
The volume-based median diameter of the dispersoid is usually 0.01 μm or more and 3 μm or less, preferably 2.5 μm or less, more preferably 2 μm or less.
When the volume-based median diameter is 0.01 μm or more, production of an aqueous emulsion is easy, and when it is 3 μm or less, the stationary stability of the aqueous emulsion and the adhesiveness of a cured product obtained by drying the aqueous emulsion are obtained. There is a tendency to improve. “Standing stability” refers to the property that the aqueous emulsion is homogeneous when the aqueous emulsion is stored for 3 days without stirring, ie, the layer rich in component (B) and / or component (C) in the aqueous emulsion. This means that a layer rich in is difficult to form. “Volume-based median diameter” means a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis.
The content of the component (A) in the aqueous emulsion of the present invention is usually 1 to 30 parts by weight, preferably 2 to 10 parts by weight with respect to 100 parts by weight of the component (B).
The total content of component (A) and component (B) in the aqueous emulsion of the present invention is usually 10 to 90 parts by weight, preferably 30 to 70 parts by weight, more preferably 100 parts by weight of the aqueous emulsion. 40 to 60 parts by weight.
The content of (C) in the aqueous emulsion of the present invention is usually 90 to 10 parts by weight, preferably 70 to 30 parts by weight, more preferably 60 to 40 parts by weight with respect to 100 parts by weight of the aqueous emulsion.
The aqueous emulsion of the present invention is a method in which component (A) and component (B) are melt-kneaded, and the resulting molten mixture and water are mixed; the step of mixing component (A) with heated component (B) A method comprising: heating and kneading component (A) and component (B), and dispersing the obtained kneaded mixture in component (C); and dissolving component (B) in an organic solvent such as toluene, The method of mixing the obtained solution and component (A) and including the process of removing the said organic solvent from the obtained mixture is mentioned.
A chemical emulsification method such as self-emulsification can also be used.
Among them, a method comprising melting and kneading the component (A) and the component (B), mixing the obtained molten mixture and water, and a method including the step of mixing the component (A) with the heated component (B) are preferable. It is.
As an apparatus used for the process of melt kneading component (A) and component (B), a twin screw extruder, Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), Labo Plast Mill Micro (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Multi-screw extruder, homogenizer, T. et al. K-Filmics (Primics Co., Ltd.) and other equipment with barrels (cylinders), stirring tanks, chemical stirrers, vortex mixers, flow jet mixers, colloid mills, ultrasonic generators, high-pressure homogenizers, Dispersion (registered by Fujikin Co., Ltd.) Trademarks), static mixers, micro mixers, and other devices that do not have a barrel (cylinder).
The shear rate of equipment with a barrel is typically 200-100,000 seconds ^-1 Degree, preferably 1,000 to 2,500 seconds ^-1 Degree. Shear rate is 200 seconds ^-1 When it is above, the adhesiveness of the cured product obtained by drying the aqueous emulsion tends to be improved, and 100,000 seconds. ^-1 When it is below, it tends to be easy to industrially produce an aqueous emulsion. “Shear rate” means a 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 component (A) and component (B), component (B) is continuously supplied from the hopper or supply port of a twin-screw extruder, and component (B) is heated and melt-kneaded. The component (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 the component (A) and the component (B) are kneaded with a screw. Subsequently, a method of continuously producing an aqueous emulsion from a die by supplying component (C) from at least one supply port provided in the compression zone of the extruder can be mentioned.
As a method including the step of mixing the component (A) with the heated component (B), after heating the cylinder of the kneader, the component (B) is put into the cylinder and rotated while rotating the component (B). Next, the component (A) and the component (B) are mixed while the component (A) and the component (B) are mixed while rotating, and the resulting mixture is poured into warm water. There is a method in which (B) is dispersed in component (C) to obtain an aqueous emulsion.
A method using a multi-screw extruder is suitable for the method including the step of mixing the component (A) with the heated component (B). Specifically, first, component (B) is supplied from a hopper of a multi-screw extruder having two or more screws in the casing, and component (B) is heated and melt-kneaded, and then the extruder The component (A) is supplied from at least one liquid supply port provided in the compression zone or / and the metering zone, and the component (A) and the component (B) are kneaded and dispersed in the component (C). Is mentioned.
The emulsion of the present invention is an aqueous polyurethane emulsion, other aqueous emulsion such as ethylene-vinyl acetate copolymer aqueous emulsion, thermosetting resin such as urea resin, melamine resin, phenol resin, clay, kaolin, talc, calcium carbonate, etc. Fillers, antiseptics, rust inhibitors, antifoaming agents, foaming agents, polyacrylic acid, polyether, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, starch and other thickeners, viscosity modifiers, flame retardants, titanium oxide, etc. Pigments, high-boiling solvents such as dimethyl succinate and dimethyl adipate, plasticizers and the like.
By drying the aqueous emulsion of the present invention, a cured product having excellent adhesion to a substrate such as a wood material, a cellulose material, a plastic material, a ceramic material, or a metal material can be obtained. The drying temperature is usually 30 to 180 ° C, preferably 60 to 150 ° C. The drying time is usually about 1 minute to 12 hours, preferably about 10 minutes to 6 hours. Drying may be performed under ventilation or under reduced pressure. The cured product obtained by drying the aqueous emulsion of the present invention has excellent adhesion to polyolefins (for example, polypropylene and the like) to which other materials such as paints are difficult to adhere.
By applying the aqueous emulsion of the present invention on a substrate, a laminate in which the aqueous emulsion layer is laminated on the substrate is obtained, and by drying the laminate, the substrate layer and the cured product are obtained. It is possible to form a laminate having a layer made of Such a layer formed of a cured product can be used as a paint, a primer, a base material, an adhesive, or the like.
The base material should just be a thing which can apply | coat the aqueous emulsion of this invention, The shape is also arbitrary.
Base materials include wood materials such as wood, plywood, MDF, particleboard, fiberboard; paper materials such as wallpaper and wrapping paper: cellulose materials such as cotton, linen, rayon; polyethylene (mainly structural units derived from ethylene) Polyolefin as component, the same applies hereinafter), polypropylene (polyolefin mainly composed of structural units derived from propylene, the same applies hereinafter), polyolefin such as polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), (meta ) Acrylic resin Polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane and other plastic materials; glass, ceramics and other ceramic materials; and metal materials such as iron, stainless steel, copper and aluminum.
Such a substrate may be a composite material composed of a plurality of materials. Further, an inorganic filler such as talc, silica, activated carbon, or a kneaded molded product of carbon fiber and a plastic material may be used.
Here, polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by a reaction between an alcohol (compound having —OH) and an isocyanate (compound having —NCO). The foamed polyurethane is a polyurethane foamed with a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water as a crosslinking agent. Semi-rigid polyurethane is usually used for automobile interior members, and hard polyurethane is usually used for paints.
Among them, polypropylene, polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), polyethylene terephthalate, polyvinyl chloride, (meth) acrylic resin, glass, aluminum and polyurethane are preferable, and polypropylene, More preferred are polyvinyl chloride, glass, aluminum and polyurethane.
The cured product obtained from the emulsion of the present invention can be used as an adhesive layer for bonding two kinds of substrates. When one of the substrates is a water-absorbing substrate such as a woody material, a paper-based material, or a cellulose material, when the aqueous emulsion of the present invention is applied onto the water-absorbing substrate, components contained in the aqueous emulsion ( C) is absorbed by the water-absorbing substrate, and an adhesive layer containing the component (A) and the component (B) is formed on the water-absorbing substrate. Therefore, a laminated body in which the water-absorbing base material, the adhesive layer, and the other base material are laminated in this order is obtained by pasting the other base material on the adhesive layer.
When one of the substrates is a non-water-absorbing substrate such as polyolefin, the aqueous emulsion of the present invention is applied on the non-water-absorbing substrate and then heated to cure on the non-water-absorbing substrate. After the product is formed, the other substrate is bonded onto the cured product and further heated to obtain a laminate. The heating temperature is usually 60 to 200 ° C. The aqueous emulsion of the present invention gives a cured product having excellent adhesiveness even when the heating temperature is 60 to 90 ° C, and further, cured product having excellent adhesiveness even when the heating temperature is a low temperature of 65 to 80 ° C. give.
A liquid material may be further applied as a paint to the cured product of the present invention. Examples of the coating material include materials for the base material such as polyurethane. When the material is a liquid material, the adhesiveness to the cured product is excellent.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[Solid content]
The solid content was measured by a method according to JIS K-6828.
[Molecular weight and molecular weight distribution]
The molecular weight of component (B) was measured by gel permeation chromatography (GPC). Calibration was performed with polystyrene (molecular weight 688 to 400,000) standard substance, and the measurement was performed under the following conditions.
Device: Waters 150-C
Column: shodex packed column A-80M
Measurement temperature: 140 ° C
Measurement solvent: Orthodichlorobenzene Measurement concentration: 1 mg / ml
[Content of structural unit derived from vinylcyclohexane]
The content of the structural unit derived from vinylcyclohexane in the component (B) is calculated based on the result obtained by measuring the ¹³ C-NMR spectrum of the component (B) under the following conditions and the following formula (X). did.
Device: DRX600 manufactured by BRUKER
Measurement solvent: Orthodichlorobenzene and orthodichlorobenzene-d4 4: 1 (volume ratio) mixed solution Measurement temperature: 135 ° C.
Measuring method: Powergate Decoupling method Pulse angle: 45 degrees Measurement standard: Content of structural unit derived from tetramethylsilanevinylcyclohexane (mol%)
= 100 × A / (B-2A) (X)
(In the formula (X), A represents an integrated integrated value of a signal of 45 ppm to 40 ppm, and B represents an integrated integrated value of a signal of 35 ppm to 25 ppm.)
[Graft amount]
The amount of maleic anhydride grafted in component (B) was determined as follows.
(I) A sample solution is prepared by dissolving 1.0 g of a sample in 20 ml of xylene.
(Ii) The prepared solution is dropped into 300 ml of methanol while stirring.
(Iii) The precipitate deposited in methanol is collected and dried at 80 ° C. for 8 hours.
(Iv) Using the dried solid, a film having a thickness of 100 μm is prepared by hot pressing.
(V) The infrared absorption spectrum of the produced film was measured, and the amount of maleic acid graft was quantified based on the absorption peak near 1780 cm ⁻¹ .
[Melt flow rate]
The melt flow rate (MFR) of the polymer 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.
[Glass transition temperature and melting point]
The glass transition temperature ([Tg], unit: ° C) and melting point ([Tm], unit: ° C) of the component (B) are as follows using a differential scanning calorimeter (SSC-5200 manufactured by Seiko Denshi Kogyo Co., Ltd.). The differential scanning calorimetry curve was measured by using the differential scanning calorimetry curve obtained in step (c).
<Measurement conditions>
(A) The sample is heated from 20 ° C. to 200 ° C. at a rate of 10 ° C./min, and then held at 200 ° C. for 10 minutes.
(B) The sample obtained in (a) is cooled from 200 ° C. to −100 ° C. at 10 ° C./min, and then held at −100 ° C. for 10 minutes.
(C) The sample obtained in (b) is heated from −100 ° C. to 200 ° C. at 10 ° C./min.
[Intrinsic viscosity]
The intrinsic viscosity ([η], unit: dl / g) of component (B) was measured at 135 ° C. using tetralin as a solvent using an Ubbelohde viscometer.
The following monomer was used for manufacture of a component (A).
130MA (trade name) manufactured by Kyoeisha Chemical Co., Ltd .: poly (ethylene glycol) methyl ether methacrylate (including an average of 9 structural units derived from ethylene oxide per molecule, hereinafter abbreviated as 130MA)
NOF Corporation's Blemmer (registered trademark) PME1000 (product name): poly (ethylene glycol) methyl ether methacrylate (including a structural unit derived from an average of 23 ethylene oxide per molecule, hereinafter abbreviated as PME). )
Lauryl methacrylate (hereinafter abbreviated as SLMA) manufactured by Mitsubishi Rayon Co., Ltd.
In the following examples, “parts” and “%” mean weight basis unless otherwise specified.
<Production Example 1 of Component (A)>
90 parts of 130MA (82.6 mole ratio) and 10 parts of SLMA (17.4 mole ratio) were mixed at 10 to 30 ° C. to prepare 100 parts of a monomer mixture. Here, the “molar ratio” represents the number of moles of each monomer when the total number of moles of the monomer is 100.
To the reactor, 150 parts of isopropanol and 20 parts of the monomer mixture prepared above were added. After replacing the gas in the reaction vessel with nitrogen, 0.19 part of 2,2′-azobisisobutyronitrile was gradually added as a polymerization initiator while heating the mixture in the reactor. The resulting mixture was stirred at 80 ° C. for 3 hours. The resulting reaction mixture was heated to a boiling point to distill off isopropanol. After adjusting the internal temperature of the obtained concentrate to 50 degreeC, water was added, solid content was adjusted to 50%, and the viscous component containing an acrylic resin was obtained. Yield 90%. The obtained component is referred to as (A-1). The results are shown in Table 1.
<Production Example 2 of Component (A)>
Except having changed the kind and usage-amount of the monomer to be used into the thing of Table 1, it carried out similarly to the manufacture example 1 of the said component (A), and obtained the viscous component containing an acrylic resin. The obtained component is referred to as (A-2). The results are shown in Table 1.

<Production Example 1 of Component (B)>
After replacing the gas inside the stainless steel reactor with argon gas, 386 parts of vinylcyclohexane and 3,640 parts of toluene were added. After heating up the obtained mixture to 50 degreeC, it charged in the reactor, pressurizing ethylene at 0.6 Mpa. Furthermore, 10 parts of a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo Co., Ltd., concentration 20%) was added, and then diethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl- 2-phenoxy) obtained by dissolving 0.001 part of titanium dichloride in 87 parts of dehydrated toluene and 0.03 part of dimethylanilinium tetrakis (pentafluorophenyl) borate in 122 parts of dehydrated toluene. The resulting solution was charged into the reactor. The resulting mixture was stirred for 2 hours. The obtained reaction mixture was poured into about 10,000 parts of acetone, and the precipitated white solid was removed by filtration. The solid thus taken out was washed with acetone and then dried under reduced pressure to obtain 300 parts of an ethylene / vinylcyclohexane copolymer. Mn of the obtained copolymer is 15,600, Mw / Mn is 2.0, [η] is 0.48 dl / g, Tm is 57 ° C., and Tg is −28 ° C. Yes, the content of structural units derived from vinylcyclohexane was 13 mol%. The obtained copolymer is referred to as (B-1a).
<Production Example 2 of Component (B)>
To 100 parts of (B-1a), 0.4 part of maleic anhydride and 0.04 part of 1,3-bis (tert-butylperoxyisopropyl) benzene are added, and the resulting mixture is sufficiently stirred and preliminarily prepared. Mixing was performed. The obtained mixture was supplied from a supply port of a twin screw extruder and melt kneaded. The melt kneading is performed in two stages, the first half and the latter half, and the temperature of the first half of the portion where the melt kneading of the extruder is set to 180 ° C. and the temperature of the second half is set to 260 ° C. went. As a result, a polymer obtained by graft polymerization of maleic anhydride to an ethylene / vinylcyclohexane copolymer was obtained. The resulting polymer had a maleic acid graft amount of 0.2% and an MFR of 180 g / 10 min (190 ° C., load: 2.16 kgf). The obtained polymer is referred to as (B-2a).
<Production Example 3 of Component (B)>
<Producing Example 1 of Component (B)> In the same manner as <Manufacturing Example 1 of Component (B)> except that propylene is used instead of ethylene, a propylene / vinylcyclohexane copolymer is obtained. Can do. This copolymer is referred to as (B-1b).
<Production Example 4 of Component (B)>
In <Production Example 2 of Component (B)>, in the same manner as in <Production Example 2 of Component (B)> except that (B-1b) is used instead of (B-1a), propylene. A polymer obtained by graft polymerization of maleic anhydride to a vinylcyclohexane copolymer can be obtained. This polymer is referred to as (B-2b).
Example 1
After setting the cylinder temperature of the table type kneader PBV-0.3 (purchased from Irie Shokai) to 97 ° C, put 110 parts of (B-2a) into the cylinder and rotate it forward at 10 revolutions per minute. However, (B-2a) was melted over 10 minutes. Thereafter, (A-1) in an amount of 10 parts in solid content was added, and the cover glass was sometimes opened at 60 revolutions per minute, followed by kneading and emulsification for 4 minutes. Next, 110 parts of warm water at 90 ° C. was added to obtain an aqueous emulsion.
The volume-based median diameter of the dispersoid in the obtained aqueous emulsion was 1.8 μm. The volume-based median diameter was measured with a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd.).
The adhesiveness of the cured product obtained from the aqueous emulsion was evaluated by the following test method (cross cut tape method). The results are shown in Table 2.
<Adhesion test method>
After washing the surface of the 3 mm thick polypropylene plate with isopropanol, the aqueous emulsion was applied onto the polypropylene plate using a bar coater so that the cured product obtained by drying had a thickness of 10 μm. The obtained coating film was dried at 80 ° C. for 5 minutes with a hot air dryer, and further heated and dried in an oven at 90 ° C. for 30 minutes to obtain a cured product.
In accordance with JIS-K5400 (cross-cut peeling tape method test), each cured product was cut with a grid-like cut with a gap interval of 1 mm, and then a cellophane tape was affixed thereon. After 1 to 2 minutes, the tape was held at one end and peeled off at a right angle, and the adhesion was evaluated based on the following evaluation criteria.
A: No peeling of the cured product is observed.
◯: Peeling of the cured product is observed, and the peeling area is less than 40% of the square area.
X: Peeling of the cured product is observed, and the peeling area is 40% or more of the square area.
Example 2
In Example 1, except having replaced (A-1) with (A-2), it implemented similarly to Example 1 and obtained the aqueous emulsion.
Table 2 shows the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the evaluation results of the adhesiveness of the cured product obtained from the aqueous emulsion.

Example 3
In Example 1, an aqueous emulsion can be obtained by carrying out similarly to Example 1 except using (B-1a) instead of (B-2a).
Example 4
In Example 2, an aqueous emulsion can be obtained by carrying out similarly to Example 2 except using (B-1b) instead of (B-2a).
Example 5
In Example 1, it replaces with (B-2a), and except using (B-2b), by implementing similarly to Example 1, an aqueous emulsion can be obtained.

The aqueous emulsion of the present invention can give a cured product having excellent adhesion to a substrate to which other materials such as paint such as polypropylene are difficult to adhere.

Claims

An aqueous emulsion comprising the following component (A), component (B) and component (C).
(A) Poly (alkylene) of α, β-unsaturated carboxylic acid derived from poly (alkylene glycol) in which one hydroxyl group located at the terminal may be substituted with an alkoxy group and α, β-unsaturated carboxylic acid Glycol) ester and a structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. Acrylic resin (B) Structural unit derived from ethylene and / or propylene, and 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.)
Or a copolymer (C) water obtained by graft-polymerizing an α, β-unsaturated carboxylic acid anhydride to the copolymer.
The aqueous emulsion according to claim 1, wherein in the component (A), the α, β-unsaturated carboxylic acid is methacrylic acid or acrylic acid.
The aqueous emulsion according to claim 1 or 2, wherein in the component (A), the poly (alkylene glycol) ester of α, β-unsaturated carboxylic acid is poly (ethylene glycol) methacrylate or poly (ethylene glycol) methyl ether methacrylate. .
The aqueous emulsion according to any one of claims 1 to 3, wherein the vinyl compound represented by the formula (1) is vinylcyclohexane.
The aqueous emulsion according to any one of claims 1 to 4, wherein in the component (B), the MFR (190 ° C, 2.16 kgf) of the copolymer is 130 g / 10 min or more and 300 g / 10 min or less.
The content of structural units derived from poly (alkylene glycol) esters of α, β-unsaturated carboxylic acid is 85 to 95 weights with respect to 100 weight parts of all structural units constituting the acrylic resin as component (A). The aqueous emulsion according to any one of claims 1 to 5, which is a part.
The aqueous emulsion is an aqueous emulsion having the component (A) and the component (B) as a dispersoid and the component (C) as a dispersion medium, and the volume-based median diameter of the dispersoid is 0.01 μm to 3 μm. The aqueous emulsion according to any one of claims 1 to 6.
An aqueous emulsion comprising the following component (A), component (B) and component (C), wherein the component (A) and the component (B) are melt-kneaded and the resulting molten mixture and water are mixed. Production method.
(A) Poly (alkylene) of α, β-unsaturated carboxylic acid derived from poly (alkylene glycol) in which one hydroxyl group located at the terminal may be substituted with an alkoxy group and α, β-unsaturated carboxylic acid Glycol) ester and a structural unit derived from an α, β-unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. Acrylic resin (B) Structural unit derived from ethylene and / or propylene, and 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.)
Or a copolymer (C) water obtained by graft-polymerizing an α, β-unsaturated carboxylic acid anhydride to the copolymer.
A cured product obtained by drying the aqueous emulsion according to any one of claims 1 to 7.
A laminate having a base material layer made of at least one material selected from the group consisting of a wood material, a cellulose material, a plastic material, a ceramic material, and a metal material, and a layer made of the cured product according to claim 9.
The aqueous emulsion according to any one of claims 1 to 7 is applied to a base material 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, Obtaining a laminate having a base material layer and the aqueous emulsion layer;
A method for producing a laminate comprising: drying the laminate obtained in the step to obtain a laminate having the base material layer and a cured product layer obtained from the aqueous emulsion.