JP2000080211A - Aqueous dispersion composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous dispersion composition having a function of developing an adhesive layer having excellent strength, transparency, weather resistance, etc., by making the composition include a resin particle emulsion prepared by subjecting a monomer to emulsion polymerization in the presence of a specific modified polyethylene resin particle under specified conditions, useful as an adhesive composition, etc. SOLUTION: This aqueous dispersion composition comprises a dispersion layer and a continuous layer. The dispersion layer contains a complex resin particle and the continuous layer contains water. The complex particle is obtained by forming (B) an epoxy group side chain-containing copolymer in the presence of (A) a carboxyl group side chain-containing polyolefinbased resin particle. Preferably the main chain skeletons of the components A and B comprise polyolefin-based substances and the component A is constituted of a copolymer composed of 5-40 wt.% repeating unit containing a carboxyl group side chain of the formula etc., based on the weight of the copolymer constituting the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an adhesive layer having excellent strength, transparency, weather resistance, heat resistance, rust resistance, oxidation resistance and the like when applied to an adhesive composition or a coating composition. The present invention relates to an aqueous dispersion composition having a function of developing a coating film, and a method for producing the same.

[0002]

2. Description of the Related Art Japanese Patent Publication No. Sho 63-045705 and Japanese Patent Publication No. Sho 63-045705 (JP-A-57-137339).
No.) discloses an aqueous dispersion composition and a technique relating to a production method thereof.

[0003] The aqueous dispersion composition disclosed in the above publication comprises composite particles obtained by graft-polymerizing a copolymer (A ') with a copolymer (B'), and a homopolymer of the copolymer (b). An aqueous dispersion composition comprising polymer particles, wherein the copolymer (A ') is 5 to 95% by weight and the copolymer (B') is 5% by weight in all copolymers in the aqueous dispersion composition. ~ 9
5% by weight or more of the copolymer (B ′) contained in the composite particles is 5% by weight or more of the total copolymer (b) in the aqueous dispersion composition, and the copolymer (A ′) Is a copolymer comprising ethylene and an α, β-ethylenically unsaturated carboxylic acid and a metal salt thereof, wherein the copolymer (B ′) comprises 5 to 95% by weight of the following component (A):
And (b) a copolymer comprising 5 to 95% by weight of a component,
(A) The glass transition temperature of a single polymer is 70.
Glass transition of styrene derivative, methyl methacrylate, acrylonitrile, vinyl chloride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, or one or more selected from the group consisting of (b) homopolymer having a temperature of ℃ or more An aqueous dispersion composition having a temperature of 50 ° C or lower, which is one or more selected from alkyl methacrylates, vinyl esters, vinyl halides, and conjugated dienes.

The aqueous dispersion composition is prepared by the following method in an aqueous dispersion comprising a copolymer (A ') comprising ethylene and an α, β-ethylenically unsaturated carboxylic acid and a metal salt thereof. The styrene derivative, methyl methacrylate, acrylonitrile, vinyl chloride, acrylic acid, methacrylic acid, fumaric acid, having a glass transition temperature of 70 ° C. or higher when a component (a), a component (b), and a component (a) are homopolymers. One or more selected from itaconic acid, (b) alkyl methacrylates, vinyl esters, vinyl halides, conjugated dienes having a glass transition temperature of 50 ° C. or less when used as a homopolymer. A method for producing an aqueous dispersion composition, characterized in that one or more selected from the group consisting of (a) and (b) are emulsion-polymerized to obtain an aqueous dispersion.

The aqueous dispersion composition is excellent in transparency, adhesion to a substrate, anti-blocking property and heat sealing property, can be widely used as an adhesive, and is industrially very advantageous. It is extremely significant in that such an excellent aqueous dispersion composition can be obtained by the production method disclosed in the publication.

[0006] However, when the aqueous dispersion composition is used as an adhesive composition or a coating composition, the strength of the adhesive layer or coating film mainly depends on the copolymer (A '), that is, the ionomer resin. And the copolymer (B ') having substantially no reactivity hardly contributes, and thus has insufficient strength.

Therefore, when the aqueous dispersion composition is used as an adhesive composition or a coating composition, the thermoplastic metal ion crosslinking of the ionomer resin present in the adhesive layer or the coating film is caused by covalent bonding at room temperature. Exhibits various physical properties similar to those of thermosetting resins with cross-linking points, but when the temperature rises to 50-70 ° C, molecular movement within the metal ion clusters becomes active, ion cross-linking points are easily dissociated, and the ionomer softens. Therefore, the strength of the adhesive layer or the coating film may be reduced, which may cause a problem.

[Japanese Patent Laid-Open No. 05-286072]
No. 5-286072 has a rust-preventive layer having excellent water resistance and adhesion to metals and the like, and has an adhesive property between a curable resin layer such as a paint formed on the rust-preventive layer and the rust-preventive layer. Also, a laminate having excellent properties is disclosed. This laminate is composed of a metal substrate, a rust-preventive layer mainly composed of a reaction product of an ionomer resin and an epoxy group-containing compound, and a curable resin layer laminated on the metal substrate via the rust-preventive layer. Is done. JP 0
In 5-286072, only "low-molecular-weight compounds such as glycidyl ether and glycidyl ester" are listed as "epoxy group-containing compounds", and there is no disclosure of polymers such as epoxy resins.

[Japanese Patent Application Laid-Open No. 09-302303]
No. 9-302303 comprises an ionomer resin and a modified epoxy resin, and / or a reaction product of both resins,
An aqueous dispersion composition which has good adhesion to a substrate and a coating material and forms a coating film having particularly excellent alkali adhesion resistance, water adhesion resistance and the like is disclosed.

The aqueous dispersion composition comprises (A ") an ionomer resin, (B") a modified epoxy resin, and / or (C ") a reaction product of components A" and B ", The weight composition ratio is: Component (A ″) / {Component (B ″) + Component (C ″)} = 99
/ 1 to 50/50. The component (A ″) is composed of a polymer main chain composed of a hydrocarbon, has a carboxyl group in a side chain,
It is preferable that at least a part of the carboxyl group is a polymer neutralized with a metal ion. The component (B ″) neutralizes a chemical reaction product of an aromatic epoxy resin, a monovalent active hydrogen group-containing compound, and a carboxyl group-containing acrylic resin with a basic compound, for example. It is preferably self-emulsified.

In JP-A-09-302303,
"Epoxy resin" means "The Dictionary of Chemistry", Volume 1, 968
Epoxy resin intermediate (condensation product of epichlorohydrin and polyhydric phenol) having at least two epoxy groups in the molecule, as described in the page (edited by the Editorial Board of the Chemical Dictionary, published by Kyoritsu Shuppan, 1963). Is understood to mean a synthetic resin formed by making the epoxy ring into a high molecular weight by a ring opening reaction. That is, an epoxy resin is an epoxy resin intermediate (a condensate of epichlorohydrin having at least two epoxy groups and a polyhydric phenol) and a curing agent (a polyfunctional compound having a function of opening an epoxy ring or reacting with a hydroxyl group). Compound) which has a three-dimensional cross-linked structure and is formed by the reaction of the compound.

Specific examples of the curing agent include, for example, polyfunctional amines, carboxylic acids, carboxylic anhydrides and the like.

The most typical epoxy resin intermediate is a condensate of epichlorohydrin and bisphenol A (2,2-bis (4'-oxyphenyl) propane) (DGE
BPA, bisphenol A diglycidyl ether). As divalent phenols other than bisphenol A, resole (initial condensate of phenol and formaldehyde) may be used.

As described in "MARUZEN High Polymer Dictionary" (translated by Tatsuta Mita, published by Maruzen, 1994), pp. 118-122, the method for producing an epoxy resin intermediate is represented by the formula (c ') 11).

[0015]

Embedded image As described above, the aqueous dispersion composition disclosed in Japanese Patent Application Laid-Open No. 09-302303 is excellent in adhesiveness because it is an epoxy resin-based one, but the outdoor durability is not always sufficient, and the problem is not solved. There was a case.

[0016]

The problem to be solved by the present invention is to solve the problems of the prior art described above, and when applied to an adhesive composition or a coating composition, the strength, transparency,
Aqueous dispersion composition having a function of expressing an adhesive layer or a coating film excellent in weather resistance, heat resistance, rust resistance, oxidation resistance, and the like, and
It is an object of the present invention to provide a manufacturing method thereof.

[0017]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have an epoxy group side chain under specific conditions in the presence of specific modified polyethylene resin particles. When resin particle emulsions obtained by emulsion polymerization of monomers containing ethylenically unsaturated monomers are applied to adhesive compositions and coating compositions, strength, transparency, weather resistance, heat resistance, rust prevention It has been found that an adhesive layer and a coating film having excellent properties and oxidation resistance are developed, and the present invention has been completed.

The present invention is specified by the following items [1] to [26].

[1] An aqueous dispersion composition comprising a dispersed phase and a continuous phase, wherein the dispersed phase contains composite resin particles, and the continuous phase contains water. An aqueous dispersion composition wherein the composite particles are obtained by forming an epoxy group side chain-containing copolymer (B) in the presence of a polyolefin resin particle (A) having a carboxyl group side chain. .

[2] The main chain skeleton of the copolymer containing a carboxyl side chain constituting the copolymer particles (A) and the main chain of the copolymer containing an epoxy group side chain constituting the copolymer (B) The aqueous dispersion composition according to [1], wherein the chain skeleton is a polyolefin-based one.

[3] The copolymer particles (A) are represented by the general formulas (A-01), (A-02) and (A-02) based on the weight of the copolymer constituting the copolymer particles (A). , (A-
03) a repeating unit having at least one kind of carboxyl group side chain selected from the group consisting of
40% by weight of a copolymer,
The aqueous dispersion composition according to [1] or [2].

[0022]

Embedded image (In the general formula (A-02), R may be the same or different, and represents H or an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. General formula (A-03)
In the formula, M ⁺ represents a monovalent metal ion. [4] The aqueous dispersion composition according to [3], wherein M ⁺ is an alkali metal ion.

[5] The copolymer (B) is represented by the general formula (B-01) or (B-02) based on the weight of the copolymer constituting the copolymer (B). [13] The aqueous dispersion composition according to any one of [1] to [4], which has 0.1 to 80% by weight of a repeating unit having at least one epoxy group side chain selected from the group consisting of: .

[0024]

Embedded image [6] The copolymer particles (A) are represented by the general formulas (A-11), (A-12), and (A) based on the weight of the copolymer constituting the copolymer particles (A). -13) 5 to 40% by weight of a repeating unit having at least one carboxyl group side chain selected from the group consisting of
The aqueous dispersion composition according to [1] or [2], which is composed of a copolymer having the same.

[0025]

Embedded image(General formulas (A-11), (A-12), and (A-1)
In 3), R^A1, R ^A2, And R^A3Is German
May be the same or different, and may be a hydrogen atom or carbon
Represents a hydrocarbon group having 1 to 20 atoms. Formula (A-1)
In 2), R may be the same or different,
H or an alkyl group having 1 to 4 carbon atoms, hydroxyal
Represents a kill group. In the general formula (A-13), M⁺Is
Represents a monovalent metal ion. ) [7] M⁺Is the alkali metal ion described in [6].
The aqueous dispersion composition described above.

[8] The copolymer (B) is composed of the general formulas (B-11), (B-12) and (B-I) based on the weight of the copolymer constituting the copolymer (B). 13) [Chemical 1
Any one of [1], [2], [6] and [7], which has 0.1 to 80% by weight of a repeating unit having at least one epoxy group side chain selected from the group consisting of: 2. The aqueous dispersion composition described in 1. above.

[0027]

Embedded image (General formulas (B-11), (B-12) and (B-13)
In formulas, R ^B11 , R ^B12 and R ^B13 each independently may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. [9] The copolymer (B) has the general formula (B-21) based on the weight of the copolymer constituting the copolymer (B);
(B-22), (B-23), (B-24), (B-2)
5), (B-26) and (B-27) having 20 to 99.9% by weight of at least one repeating unit having no epoxy group side chain selected from the group consisting of [Formula 16]. The aqueous dispersion composition according to any one of [1] to [8].

[0028]

Embedded image (General formulas (B-21), (B-22), (B-23),
(B-24), (B-25), (B-26) and (B-
The symbols in 27) are as follows. R ^B21a ,
R ^B22a , R ^B23a , R ^B24 , R ^B26 or R ^B27 each independently may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^B21b and R
^B22b represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkene group or an aromatic group having 1 to 20 carbon atoms. R ^B23b independently represents a hydrogen atom which may be the same or different, or a hydrocarbon group having 1 to 20 carbon atoms. R ^B25 represents a saturated or unsaturated hydrocarbon group having a side chain having 1 to 10 carbon atoms or having no side chain. [10] Any of [1] to [9], wherein the copolymer particles (A) and the copolymer (B) are in a weight ratio of 1:99 to 95: 5. An aqueous dispersion composition as described.

[11] In the presence of a polyolefin resin particle (A) having a carboxyl group side chain, an ethylenically unsaturated monomer (b-1) having an epoxy group side chain and an epoxy group side chain having No ethylenically unsaturated monomer (b-
A method for producing an aqueous dispersion composition, comprising subjecting an ethylenically unsaturated monomer mixture (b) containing 2) to radical polymerization, wherein the aqueous dispersion composition comprises a dispersed phase and a continuous phase. Wherein the dispersed phase contains composite resin particles, and the continuous phase contains water.

[12] The copolymer particles (A) are represented by the general formula (A-A) based on the weight of all monomers used for copolymerization of the copolymer constituting the copolymer particles (A). 01),
(A-02) and (A-03) an ethylenic composition containing 5 to 40% by weight of an ethylenically unsaturated monomer having at least one carboxyl group side chain selected from the group consisting of A copolymer obtained by radical copolymerization of an unsaturated monomer mixture or neutralization of the copolymer containing (A-1) with ammonia, an amine or a monovalent metal ion. The production method according to [11], which is characterized in that:

[0031]

Embedded image (In the general formula (A-02), R may be the same or different, and represents H or an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. General formula (A-03)
In the formula, M ⁺ represents a monovalent metal ion. [13] The copolymer particles (A) are represented by the general formula (A-21) based on the weight of all monomers used for copolymerization of the copolymer constituting the copolymer particles (A). , (A-2
2) and (A-23) an ethylenically unsaturated monomer containing 5 to 40% by weight of at least one ethylenically unsaturated monomer having a carboxyl group side chain selected from the group consisting of Characterized in that it is obtained by radical copolymerization of a monomer mixture, [1]
1].

[0032]

Embedded image(General formulas (A-21), (A-22), and (A-2
In 3), R^A1, R ^A2, And R^A3Is German
May be the same or different, and may be a hydrogen atom or carbon
Represents a hydrocarbon group having 1 to 20 atoms. General formula (A-2
In 2), R may be the same or different,
H or an alkyl group having 1 to 4 carbon atoms, hydroxyal
Represents a kill group. In the general formula (A-23), M⁺Is
Represents a monovalent metal ion. [14] Ethylenically unsaturated monomer having an epoxy group side chain
(B-1) and ethylene having no epoxy group side chain
Ethylenic unsaturated containing unsaturated unsaturated monomer (b-2)
The monomer mixture (b) is the total weight of the mixture (b).
As a reference, general formulas (B-01) and (B-02)
At least one member selected from the group consisting of
Ethylenically unsaturated monomer having an epoxy group side chain (b-
[1] having 0.1 to 80% by weight of 1)
The production method according to any one of [13] to [13].

[0033]

Embedded image [15] An ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (b-1) having an epoxy group side chain and an ethylenically unsaturated monomer (b-2) having no epoxy group side chain The monomer mixture (b) is selected from the group consisting of the general formulas (B-31), (B-32) and (B-33) based on the total weight of the mixture (b). The method according to any one of [11] to [13], wherein the method further comprises 0.1 to 80% by weight of at least one ethylenically unsaturated monomer (b-1) having an epoxy group side chain.

[0034]

Embedded image (General formulas (B-31), (B-32) and (B-33)
In formulas, R ^B11 , R ^B12 and R ^B13 each independently may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. [16] An ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (b-1) having an epoxy group side chain and an ethylenically unsaturated monomer (b-2) having no epoxy group side chain. The saturated monomer mixture (b) is represented by the general formula (B-41), (B-42) or (B-42) based on the total weight of the mixture (b).
-43), (B-44), (B-45), (B-46)
And 20 to 99.9% by weight of at least one ethylenically unsaturated monomer (b-2) having no epoxy group side chain selected from the group consisting of (R-47) [Formula 21]. The manufacturing method according to any one of [11] to [15].

[0035]

Embedded image (General formulas (B-41), (B-42), (B-43),
(B-44), (B-45), (B-46) and (B-44)
The symbols in 47) are as follows. R ^B21a ,
R ^B22a , R ^B23a , R ^B24 , R ^B26 or R ^B27 may each independently be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^B21b and R ^B22b are
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkene group or an aromatic group having 1 to 20 carbon atoms. R ^B23b independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. R ^B25 has a side chain having 1 to 10 carbon atoms,
Alternatively, it represents an ethylenically unsaturated monomer having no side chain. [17] Any of [11] to [16], wherein the copolymer particles (A) and the copolymer (B) are in a weight ratio of 1:99 to 95: 5. Manufacturing method described.

[18] An aqueous dispersion composition obtained by the production method according to any one of [11] to [17].

[19] [1] to [10] and [1]
8] A coating composition comprising the aqueous dispersion composition according to any one of the above.

[20] [1] to [10] and [1]
8] A rust preventive coating composition comprising the aqueous dispersion composition described in any one of the above.

[21] [1] to [10], and
[18] An adhesive composition comprising the aqueous dispersion composition described in any one of the above.

[22] A coated metal having a coating film formed by applying the coating composition according to [19] or [20] to the surface.

[23] A rust-preventive metal coated with the coating composition according to [19] or [20] to form a coating film.

[24] A coated metal sheet on which a coating film is formed by applying the coating composition according to [19] or [20] on at least one surface.

[25] A rust-preventive metal plate on which a coating film is formed by applying the coating composition according to [19] or [20] on at least one surface.

[26] The metal plate according to [24] or [25], wherein the metal plate is a galvanized steel plate.

[0045]

Embodiments of the present invention will be described below.

[Carboxyl Group Side Chain-Containing Copolymer] In the specification of the present application, the “carboxyl group side chain containing copolymer” constituting the copolymer particles (A) refers to a side chain and / or It means a copolymer having a carboxyl group as a pendant group.

Here, the carboxyl group includes not only a carboxyl group but also a metal salt neutralized with ammonia, an amine and a monovalent metal ion.

In a preferred embodiment of the present invention, the main chain skeleton of the carboxyl group side chain-containing copolymer is polyolefinic.

In a further preferred embodiment of the present invention, the main chain skeleton of the carboxyl group side chain-containing copolymer is polyethylene.

[Copolymer particles (A)] In the present invention,
The copolymer particles (A) are composed of a copolymer containing a carboxyl group side chain.

In a preferred embodiment of the present invention, the copolymer particles (A) are represented by the general formulas (A-01) and (A-0) based on the weight of the copolymer constituting the copolymer particles (A).
2) and a copolymer having 5 to 40% by weight of a repeating unit having at least one carboxyl group side chain selected from the group consisting of (A-03) [Formula 22].

[0052]

Embedded image (In the general formula (A-02), R may be the same or different, and represents H or an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. General formula (A-03)
In the formula, M ⁺ represents a monovalent metal ion. In a preferred embodiment of the present invention, R in general formula (A-02) is
All are hydrogen, and M in the general formula (A-03)
⁺ Is an alkali metal ion.

In a preferred embodiment of the present invention, the copolymer particles (A) are represented by the general formulas (A-11) and (A-1) based on the weight of the copolymer constituting the copolymer particles (A).
2) and a copolymer having 5 to 40% by weight of a repeating unit having at least one carboxyl group side chain selected from the group consisting of (A-13) [Formula 23].

[0054]

Embedded image(General formulas (A-11), (A-12), and (A-1)
In 3), R^A1, R ^A2, And R^A3Is German
May be the same or different, and may be a hydrogen atom or a carbon atom.
Represents a hydrocarbon group having 1 to 20 children. General formula (A-12)
In R, R may be the same or different, and H
Or an alkyl group having 1 to 4 carbon atoms, hydroxyalkyl
Represents a group. In the general formula (A-13), M⁺Is monovalent
Represents a metal ion. In a preferred embodiment of the present invention, the compound represented by the general formula (A-12)
R is all hydrogen, and has the general formula (A-13)
M⁺Is an alkali metal ion.

[Method for Producing Copolymer Particles (A)] In the present invention, the method for producing the copolymer particles (A) is not particularly limited. In a preferred embodiment of the present invention,
The method for producing a copolymer containing a carboxyl group side chain constituting the copolymer particles (A) is a copolymer obtained by copolymerizing an ethylenically unsaturated carboxylic acid such as acrylic acid or methacrylic acid with ethylene, or It can be obtained by a method such as dispersing a copolymer obtained by neutralizing the copolymer with ammosia or metal ions in hot water.

Here, the weight% of the ethylenically unsaturated carboxylic acid based on all monomers to be copolymerized is not particularly limited.

In a preferred embodiment of the present invention, the copolymer particles (A) constitute the copolymer particles (A) in consideration of the amount of the epoxy group side chains in the copolymer (B) composed of the copolymer containing epoxy group side chains. The weight% of the ethylenically unsaturated carboxylic acid based on all monomers to be used for copolymerization of the copolymer containing a carboxyl side chain is preferably in a numerical range of 5 to 40% by weight.

In a preferred embodiment of the present invention, the copolymer particles (A) are based on the weight of all monomers used for copolymerization of the copolymer constituting the copolymer particles (A).
General formulas (A-21), (A-22), and (A-2)
3) 5 to 40% by weight, more preferably 8 to 25% by weight of at least one ethylenically unsaturated monomer having a carboxyl group side chain selected from the group consisting of
It can be obtained by radical copolymerization of the contained ethylenically unsaturated monomer mixture (a).

[0059]

Embedded image(General formulas (A-21), (A-22), and (A-2
In 3), R^A1, R ^A2, And R^A3Is German
May be the same or different, and may be a hydrogen atom or carbon
Represents a hydrocarbon group having 1 to 20 atoms. General formula (A-2
In 2), R may be the same or different,
H or an alkyl group having 1 to 4 carbon atoms, hydroxyal
Represents a kill group. In (A-23), M⁺Is a monovalent
Represents a metal ion. In the invention of the present application, the above-mentioned radical copolymerization is called
The meaning of (A-1) is to modify the copolymer containing (A-1)
-2) or (A-3).

The average particle diameter of the copolymer particles (A) is not particularly limited, but when the aqueous dispersion composition according to the present invention is applied to a coating composition, an adhesive composition or the like,
In consideration of the fact that the film is applied to a thickness of 1 to 3 μm on the surface of the base, the thickness is preferably in the range of 0.01 to 0.5 μm.

The carboxyl group side chain-containing copolymer which can be used in the present invention comprises a polymer main chain mainly composed of hydrocarbon, has a carboxyl group in the side chain, and has at least one carboxyl group. Parts are polymers neutralized with ammonia, amines or metal cations. In the neutralization reaction, the carboxyl group-containing copolymer is reacted with ammonia, amine or metal cation in a molten state or a solution state, or the reaction proceeds effectively by promoting diffusion of the reagent. Many commercial products use sodium as a neutralizing metal. Here, the polymer main chain composed of a hydrocarbon is preferably a polyolefin-based one, and particularly preferably a polyethylene-based one. In other words, the carboxyl group side chain-containing copolymer is preferably an olefin copolymer, and particularly preferably an ethylene copolymer.

As a specific example, for example, a partially neutralized product which is a polymer of an α-olefin and an unsaturated carboxylic acid and in which at least a part of the carboxyl group contained therein is neutralized with ammonia or a metal cation is used. Can be mentioned.

Specific examples of the α-olefin include, for example, ethylene and propylene, and ethylene is particularly preferable.

Preferable examples include a partially neutralized product of a polymer of ethylene and an unsaturated carboxylic acid, wherein at least a part of the carboxyl group contained is neutralized with ammonia or a metal cation. In a preferred example, the ethylene-unsaturated carboxylic acid copolymer constituting the main skeleton is
A random copolymer or a graft copolymer of unsaturated carboxylic acid onto polyethylene may be used, but a random copolymer is preferred in terms of transparency.

Specific examples of the unsaturated carboxylic acid as a monomer used in the production of the ethylene-unsaturated carboxylic acid copolymer include an unsaturated carboxylic acid having 3 to 8 carbon atoms. Specific examples of the unsaturated carboxylic acid having 3 to 8 carbon atoms include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, isocrotonic acid, citraconic acid, allyl succinic acid, mesaconic acid,
Glutaconic acid, nadic acid (endosis-2,2,1-
Hept-2-ene-5,6-dicarboxylic acid), methylnadic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, and the like. Among these, acrylic acid and methacrylic acid are preferred.

The monomer used for producing the ethylene-unsaturated carboxylic acid copolymer may contain a third monomer component in addition to ethylene and the unsaturated carboxylic acid. Examples of the third monomer component include unsaturated carboxylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate and isobutyl (meth) acrylate, and vinyl esters such as vinyl acetate. .

In the ethylene-unsaturated carboxylic acid copolymer, the content of the repeating unit derived from ethylene is generally preferably from 95 to 60% by weight, and preferably from 92 to 60% by weight.
75% by weight is more preferred.

When the content of the repeating unit derived from ethylene is 95% by weight or less, the emulsifiability is good, and when it is 60% by weight or more, it is preferable that the coating film does not deteriorate in corrosion resistance and solvent resistance.

The content of the repeating unit derived from the unsaturated carboxylic acid is preferably 5 to 40% by weight, and 8 to 2% by weight.
5% by weight is more preferred.

When the ethylene-unsaturated carboxylic acid copolymer contains a third repeating unit which is an unsaturated monomer other than ethylene and unsaturated carboxylic acid, the amount of the third repeating unit is 40% by weight or less. Is preferred from the viewpoint of solvent resistance.

Specific examples of the metal cation neutralizing at least a part of the carboxyl group in the side chain of the ethylene-unsaturated carboxylic acid copolymer include, for example, a monovalent metal such as sodium or potassium. Cations are mentioned.

Ammonia, for all carboxyl groups in the side chain of the ethylene-unsaturated carboxylic acid copolymer,
The ratio of the carboxyl groups neutralized with the amine or metal cation, that is, the degree of neutralization is excellent in the adhesion of the coating film, in that an aqueous dispersion having good stability can be obtained.
Usually, it is about 20 to 100%, preferably 30 to 100%.
80%.

[Preferred Method for Producing Carboxyl Group Side Chain-Containing Copolymer Particles (A)] The method for producing the copolymer particles (A) used in the present invention is not particularly limited. As a specific example of the method for producing the copolymer used in the present invention, for example, it is obtained by copolymerizing ethylene, an unsaturated carboxylic acid, and, if necessary, the third component by a high-pressure radical polymerization method. Further, a production method of neutralizing a carboxyl group of the obtained copolymer with the compound having a metal cation, graft copolymerizing an unsaturated carboxylic acid to polyethylene, and converting the carboxyl group of the obtained copolymer to the metal A production method of neutralizing with a compound having a cation can be exemplified.

In these production methods, the required components may be supplied to an extruder and melted and kneaded for the reaction, or the reaction may be performed in an appropriate solution.

The aqueous dispersion of the carboxyl group-containing copolymer particles (A) can be easily prepared. For example, it can be prepared by a method in which the copolymer having a solid content of 1 to 60% by weight with respect to water is mixed, heated and melted at a temperature of 100 to 270 ° C., cooled, and dispersed.

The method for producing the aqueous dispersion containing the polyolefin copolymer particles used in the present invention is as follows.
There is no particular limitation.

Specific examples of the method for producing an aqueous dispersion containing the polyolefin-based copolymer particles used in the present invention include, for example, JP-B-42-000275, JP-B-42-023085, and JP-B-45-245. No. 029909,
It is disclosed in the claims and examples of JP-A-51-062890. Among these, from the viewpoint of the uniformity of the resin particles in the aqueous dispersion and the production advantage on an industrial scale, polyolefin copolymers disclosed in JP-A-51-062890 and the like are used. A method of dispersing in water at 120 ° C. or higher is preferred.

In the present invention, specific examples of commercially available copolymer particles (A) that can be preferably used as the copolymer particles (A) include Toho Chemical Industry Co., Ltd.
Hitec S-8512, S-3121, S-31
27, S-7024, Chemipearl S manufactured by Mitsui Chemicals, Inc.
-100, S-111, S-120, S-650 and the like, and these commercially available products can be used alone or in combination of two or more.

[Epoxy Group Side Chain-Containing Copolymer] In the present invention, the copolymer (B) is composed of an epoxy group side chain containing copolymer. In the specification of the present application, "epoxy group side chain-containing copolymer" constituting copolymer particles (B)
The term means a copolymer having an epoxy group on a side chain and / or a pendant group. Here, the epoxy group is
It includes not only epoxy groups but also glycidyl groups. In a preferred embodiment of the present invention, the main chain skeleton of the epoxy group-containing copolymer is polyolefinic.

In a further preferred embodiment of the present invention, the main chain skeleton of the epoxy group side chain-containing copolymer is a polyethylene type.

[Repeating Unit Having Epoxy Group Side Chain]
In a preferred embodiment of the present invention, the copolymer (B) is represented by the general formulas (B-01) and (B-02) based on the weight of the copolymer constituting the copolymer (B). Chemical 2
5] is 0.1 to 80% by weight of a repeating unit having at least one epoxy group side chain selected from the group consisting of:

[0082]

Embedded image In a preferred embodiment of the present invention, the copolymer (B) has the general formulas (B-11), (B-12) and (B) based on the weight of the copolymer constituting the copolymer (B). -1
3) 0.1 to 8 repeating units having at least one epoxy group side chain selected from the group consisting of
0% by weight.

[0083]

Embedded image (General formulas (B-11), (B-12) and (B-1
In ^{3), R B11, R B} 12 and R ^B13 are each independently, may be separate in the same, represent a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. As described above, the repeating unit having an epoxy group side chain is preferably from 0.1 to 80% by weight, more preferably from 1 to 50% by weight, based on the weight of the copolymer constituting the copolymer (B). Is more preferable, and 2.5 to 30% by weight is further preferable. When this value is less than 0.1% by weight, it cannot be generally said that the epoxy group is substantially introduced into the copolymer particles (B), and it is difficult to obtain a sufficient effect. Also,
When the amount exceeds 80% by weight, aggregates increase during polymerization, or the stability of the resin particles in the aqueous dispersion composition (for example, dispersibility capable of maintaining uniform dispersion, characteristics as an emulsion for a certain period of time can be maintained) Storage stability).

[Significance of Epoxy Group Side Chain of Copolymer (B)] In the present invention, it is characteristic that an epoxy group side chain is introduced into the copolymer (B). In the present invention, by introducing an epoxy group side chain into the copolymer (B),
When the aqueous dispersion composition according to the present invention is applied to an adhesive composition, it is particularly noteworthy that the adhesion between the adhesive layer and the surface of the adherend (for example, a metal surface) is significantly improved. You.

In the present invention, when the aqueous dispersion composition according to the present invention is applied to a coating composition by introducing an epoxy group side chain into the copolymer (B), the coating film and the base ( For example, the adhesion to metal surfaces etc.) is significantly improved,
It is particularly noteworthy that when a top coat is further formed on this coat with a top coat, the adhesion between this coat and the top coat is significantly improved.

Although the mechanism of such an improvement effect is not always clear, the polarity of the epoxy group and the co-polymerization in the process of forming the adhesive layer and the coating film by forming the aqueous dispersion composition according to the present invention into a film. An epoxy group side chain of the combination (B);
The carboxyl group of the copolymer particles (A) reacts to form crosslinks and contributes to enhancing the microscopic compatibility of the copolymer particles (A) and the copolymer (B). It is considered to be.

That is, in the process of applying the aqueous dispersion composition according to the present invention to a base such as a metal surface and forming a film to form an adhesive layer or a coating film, the composite resin particles are used in the process of forming a film. Crosslinks are formed by the reaction between the epoxy group side chains of the copolymer (B) and the carboxyl groups of the copolymer particles (A) between and within the particles, whereby the copolymer particles (A)
And the copolymer (B) are microscopically compatible with each other to form a film, thereby toughening the adhesive layer and the coating film. By these actions, physical properties (strength), rust resistance, top coat adhesion and It is considered to improve the solvent resistance.

[Repeating Unit Having No Epoxy Group Side Chain] In a preferred embodiment of the present invention, the copolymer (B)
Are represented by the general formulas (B-21), (B-22), and (B-) based on the weight of the copolymer constituting the copolymer (B).
23) a repeating unit having no epoxy group side chain selected from the group consisting of (B-24), (B-25), (B-26) and (B-27) From 20 to 99.9% by weight.

[0089]

Embedded image (General formulas (B-21), (B-22), (B-23),
The symbols in (B-24) and (B-25), (B-26) and (B-27) are as follows. R
^{B21a, R B22a, R B23a,} R B24, R B26 and R ^B27 is,
Each independently may be the same or different; a hydrogen atom,
Or a hydrocarbon group having 1 to 20 carbon atoms. R ^B21b and R ^B22b represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkene group or an aromatic group having 1 to 20 carbon atoms. R ^B23b each independently may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^B25 represents a saturated or unsaturated hydrocarbon group having a side chain having 1 to 10 carbon atoms or having no side chain. )

[Polymerization Method for Copolymer Particles (B)] In the present invention, the polymerization method for the copolymer particles (B) is not particularly limited. In a preferred embodiment of the present invention, an ethylenically unsaturated monomer (b-1) having an epoxy group side chain and an epoxy group side chain are present in the presence of a copolymer particle (A) having a carboxyl group side chain. It is produced by radical polymerization of an ethylenically unsaturated monomer mixture (b) containing an ethylenically unsaturated monomer (b-2) to be removed. Ethylenically unsaturated monomer having an epoxy group side chain (b-1) and ethylenically unsaturated monomer having no epoxy group side chain (b-2) The mixture (b) undergoes radical copolymerization in the presence of the copolymer particles (A), and the preferred polymerization mode is emulsion polymerization.

In a preferred embodiment of the present invention, the weight ratio of the copolymer particles (A) to the copolymer (B) is 1:99 to 9
The range is 5: 5, more preferably 5:99 to 90:10, and still more preferably 10:90 to 80:20.

When the weight ratio of the copolymer (B) exceeds 99, not only the effects described in the section of [Effects of the Invention] described below are reduced, but also the emulsion polymerization may not proceed stably. is there. In this case, when the aqueous dispersion composition is applied to a paint, the rust prevention property is particularly reduced.

When the weight ratio of the copolymer (B) is less than 5, the effects described in the section of [Effects of the Invention] will be reduced. In this case, when the aqueous dispersion composition is applied to a paint, the rust prevention and the adhesion of the top coat are particularly deteriorated.

Thus, it contains the ethylenically unsaturated monomer (b-1) having an epoxy group side chain and the ethylenically unsaturated monomer (b-2) having no epoxy group side chain. Emulsion polymerization of the ethylenically unsaturated monomer mixture (b) in the presence of the copolymer particles (A) produces the composite resin particles of the present invention.

The mode of emulsion polymerization is not particularly limited, but is generally carried out by a usual emulsion polymerization method.

For example, in the presence of a copolymer particle (A) and a polymerization initiator, an ethylenically unsaturated monomer (b-1) having an epoxy group side chain and ethylene having no epoxy group side chain The polymerization is carried out in a reaction system in which the ethylenically unsaturated monomer mixture (b) containing the ethylenically unsaturated monomer (b-2) is added all at once, dividedly or continuously.

A surfactant, a buffer and the like may be added to this reaction system as needed. At that time, the ethylenically unsaturated monomer mixture (b) may be previously mixed with water and a surfactant and added as an emulsion. The polymerization initiator and the like may be added all at once, dividedly or continuously, similarly to the method of adding the ethylenically unsaturated monomer mixture (b). If necessary, a chain transfer agent such as mercaptans such as t-dodecyl mercaptan may be used.

The use amount of the chain transfer agent is not particularly limited, but is usually about 0 to 5% by weight based on the weight of the ethylenically unsaturated monomer mixture (b). Usually, the polymerization is carried out at a polymerization temperature of 30 to 90 ° C. under a nitrogen purge.

[Composite Resin Particles Obtained by Copolymerizing Copolymer (B) in the Presence of Copolymer Particles (A)] In the present invention, the average particle diameter of the obtained composite resin particles is as follows: In this case, it depends on the average particle diameter of the copolymer particles (A) and the weight ratio of the copolymer particles (A) and the copolymer (B).

In the present invention, the average particle diameter of the composite resin particles is not particularly limited.
Assuming that the aqueous dispersion composition according to the present invention is applied to an adhesive composition or a coating composition, when the average thickness of a desired adhesive layer or coating film is 1 to 3 μm, about 10 nm
Preferably, it is in the range of about to about 1.0 μm.

[Ethylenically unsaturated monomer (b-1) having an epoxy group side chain] In a preferred embodiment of the present invention,
Ethylenically unsaturated monomer having an epoxy group side chain (b-
1) and the ethylenically unsaturated monomer mixture (b) containing the ethylenically unsaturated monomer (b-2) having no epoxy group side chain, the ethylenically unsaturated monomer mixture ( b)
(B-31), (B-31)
32) and (B-33) 0.1 to 80% by weight of an ethylenically unsaturated monomer (b-1) having at least one epoxy group side chain selected from the group consisting of

[0102]

Embedded image (General formulas (B-31), (B-32) and (B-33)
In formulas, R ^B11 , R ^B12 and R ^B13 each independently may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ) Ethylenically unsaturated monomer having an epoxy group side chain (b-
Specific examples of 1) include, for example, epoxy derivatives such as glycidyl (meth) acrylate and allyl glycidyl ether, and these can be used alone or as a mixture of two or more. . Among these, glycidyl methacrylate is preferably used.

As described above, the position of the ethylenically unsaturated monomer (b-1) having an epoxy group side chain is 0.1% based on the total weight of the ethylenically unsaturated monomer mixture (b).
It is preferably from 1 to 80% by weight, more preferably from 1 to 50% by weight, even more preferably from 2.5 to 30% by weight. When this value is less than 0.1% by weight, it cannot be generally said that the epoxy group is substantially introduced into the copolymer particles (B), and it is difficult to obtain a sufficient effect. When the content exceeds 80% by weight, aggregates increase during polymerization, or the stability of the resin particles in the aqueous dispersion composition (for example, dispersibility capable of maintaining uniform dispersion, maintaining characteristics as an emulsion for a certain period of time) Storage stability, etc.) may be impaired.

[Ethylenically unsaturated monomer having no epoxy group side chain (b-2)] In a preferred embodiment of the present invention, the ethylenically unsaturated monomer having an epoxy group side chain (b-1) And the ethylenically unsaturated monomer mixture (b) containing the ethylenically unsaturated monomer (b-2) having no epoxy group side chain, the ethylenically unsaturated monomer mixture (b) Formula (B-41) based on the total weight of
(B-42), (B-43), (B-44), (B-4)
5) at least one ethylenically unsaturated monomer (b-2) having no epoxy group side chain selected from the group consisting of (B-46) and (B-47) 9
It contains 9.9% by weight.

[0105]

Embedded image (General formulas (B-41), (B-42), (B-43),
(B-44), (B-45), (B-46) and (B-44)
The symbols in -47) are as follows.
R ^B21a , R ^B22a , R ^B23a , R ^B24 , R ^B26 and R
^B27 is each independently the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R ^B21b and R ^B22b represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkene group or an aromatic group having 1 to 20 carbon atoms. R ^B23b is each independently:
Hydrogen atoms which may be the same or different, or 1-2 carbon atoms
Represents a hydrocarbon group of 0. R ^B25 has 1 to 10 carbon atoms.
Represents an ethylenically unsaturated monomer having a side chain or having no side chain. ) Ethylenically unsaturated monomer having no epoxy group side chain (b
As specific examples of -2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate,
N-butyl (meth) acrylate, i (meth) acrylate
-Butyl, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate,
N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate,
N-decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 2 (Meth) acrylates such as -hydroxyethyl, hydroxypropyl (meth) acrylate, vinyl esters such as vinyl acetate and vinyl propionate, aromatic vinyls such as styrene, α-methylstyrene, and vinyltoluene; (Meth) vinyl cyanides such as acrylonitrile, vinyl chlorides such as vinyl chloride and vinylidene chloride, (meth) acrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its Unsaturated carboxylic acids such as monoalkyl esters , Unsaturated sulfonic acids such as sodium styrenesulfonate, (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane trimethacrylate, etc. And the like. These can be used alone or as a mixture of two or more.

In general, as the ethylenically unsaturated monomer (b-2) having no epoxy group side chain, unnecessary ethylenically unsaturated monomer (b-1) with epoxy group-containing ethylenically unsaturated monomer is used. In order to avoid the reaction, those having reactivity with the epoxy group-containing ethylenically unsaturated monomer (b-1), such as unsaturated carboxylic acids, are the total weight of the ethylenically unsaturated monomer mixture (b). Is preferably suppressed to 10% by weight or less based on In general, when the content is 10% by weight or less, the occurrence of aggregates during polymerization is small, which is industrially preferable.

[Glass transition point of copolymer (B) (T
g)] The glass transition point (Tg) of the copolymer (B) is not particularly limited. Glass transition point (Tg) of copolymer (B)
Assuming that the aqueous dispersion composition according to the present invention is applied to an adhesive composition or a coating composition, for example, when the base of the adhesive layer or coating is a metal surface, a general In consideration of use conditions and the like, the temperature is preferably in the range of −20 to 80 ° C. Generally, when the glass transition point (Tg) of the copolymer (B) is lower than −20 ° C., fluidity, tackiness, blocking property, and the like are easily generated on the surface of the adhesive layer or the coating film, If the temperature is higher than 80 ° C., the film-forming property may be reduced, and a problem that a uniform adhesive layer or coating film may not be obtained may occur.

[Polymerization Initiator] The polymerization initiator is not particularly limited, and for example, those used in known and ordinary emulsion polymerization can be used. Specific examples of the polymerization initiator include, for example, peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate, organic peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Can be mentioned. If necessary, it can be used as a redox initiator in combination with a reducing agent. The amount of the polymerization initiator is not particularly limited, but is usually about 0.1 to 3% by weight based on the ethylenically unsaturated monomer mixture (b).

[Surfactant] The surfactant is not particularly limited. Specific examples of the surfactant include, for example, sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium alkyl diphenyl ether disulfonate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene alkyl phenyl ether sulfate, formalin condensate of naphthalene sulfonic acid,
Anionic surfactants such as polyoxyethylene alkyl ether type phosphate ester and polyoxyethylene alkyl phenyl ether type phosphate ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, ethylene oxide-propylene oxide block copolymer And nonionic surfactants such as sorbitan fatty acid esters, and these can be used alone or in combination. The amount of the surfactant used is not particularly limited, but is usually about 0 to 10% by weight based on the ethylenically unsaturated monomer mixture (b).

[Additives] The aqueous dispersion composition according to the present invention may contain, if necessary, a film-forming aid, a plasticizer, a thickener, a pigment, a pigment dispersant, an antifreezing agent, a pH adjuster, Defoamers, preservatives, wetting agents and the like can be added.

[Use] The aqueous dispersion composition according to the present invention can be applied to an adhesive composition and a coating composition. Such an adhesive composition or a coating composition can be diluted with a diluent such as water, if necessary. Further, it can be applied by a conventional application method such as brush application, roller application, spray application, doctor blade application and the like. The base on which the adhesive composition or the coating composition is applied is not particularly limited. Specific examples of the base on which the adhesive composition and the coating composition are applied include a metal plate such as a galvanized steel plate (electrogalvanized steel plate, hot-dip galvanized steel plate, etc.). [Copolymer] The term "copolymer" used in the specification of the present application is synonymous with a copolymer. There is no particular restriction on the mode of arrangement of the repeating units in the copolymer (copolymer), and the copolymer may be any of random copolymer, alternating copolymer, block copolymer, graft copolymer and the like. May be. In the specification of the present application, the "copolymer" is at least partially linear, cyclic, macrocyclic,
Branched, star-shaped, three-dimensional mesh, IPN (interpe
networking polymer network
s) and PIC (polyion complex).

[Particle] The term "particle" used in the specification of the present application completely includes, but is not necessarily equivalent to, the concept that these terms generally have in polymer chemistry. As for aspects of the scanning electron microscopic form of the “particles” used in the specification of the present application, for example, an aspect having a number of projections in the form of raspberries or gold rice sugar (confinito in Portuguese), flattened erythrocytes And a rugby ball-like spheroid-like form, an Escherichia coli-like spindle-like form, a hollow particle, and a mode in which particles are further present in the hollow particles. The term “particles” used in the specification of the present application includes, for example, polymer emulsions, latexes,
The invention also includes microspheres constituting a polymer suspension, and these examples are general embodiments in the invention according to the present application. As described above, the term “particle” used in the present application is not necessarily equivalent to the concept that these words generally have in polymer chemistry, but the essence of the heteropolymer system according to the present invention is For convenience, the term “aspect” is frequently used when referring to it.

[Particle Having Core / Shell Structure] The terms “core”, “shell” and “core / shell” used in the specification of the present application have the concept that these terms generally have in polymer chemistry. Includes but is not necessarily equivalent. For example, the “core / shell” particles according to the present invention include embodiments in which the “core” is at least partially surrounded by the “shell”. Thus, the terms “core”, “shell” and “core / shell” as used in the description of the present application (the claims and the detailed description of the invention) refer to these terms as they are commonly used in polymer chemistry. Although not necessarily equivalent to the concept of the present invention, it is used for convenience in frequently referring to the essential “aspect” of the heteropolymer system according to the present invention. In polymer chemistry, generally,
The term “core” is “core, center, n
ucleus) "," core (center) "
And "seed" are used equivalently, and the term "shell" is used as the term "shell, s
kin, husk), "sheath" and "robe". Accordingly, the term “core” as used in the specification of the present application refers to “core, center, nuc”.
leus), "core, center" and "seed". Similarly, for the word "shell", "shell (sh
ell, skin, husk) "," sheath (seat)
h) "and" robe ".

Although it is not clear, the composite particles obtained by the method of the present invention are presumed from the fact that they are excellent in performance, so that at least a part of the surface of the copolymer particles (A) has the copolymer ( It is considered that the structure of the composite resin particles covered by B) is obtained.

Examples of the structure of the composite resin particles in which at least a part of the surface of the copolymer particles (A) are coated with the copolymer (B) are as follows. . A structure called a general core / shell type in which the surface of a copolymer particle (A) as a core particle is completely covered by a shell of the copolymer (B). A structure in which a shell of the copolymer (B) partially deposits on the surface of the copolymer particles (A) as the core particles and is not completely covered. A so-called salami structure in which a plurality of copolymer particles (A) as core particles are covered by one shell of the copolymer (B). A structure in which at least one particle of the copolymer (B) adheres to the surface of the copolymer particle (A) as a core particle.

[Structure of Particle] In the specification of the present application,
The structure of the copolymer particles may be primary particles or higher-order particles. In addition, morphologically, particles having a special shape such as hollow particles and a structure in which particles are further present in the hollow particles (for example, a structure such as Hakone work or matryoshka of Russian folk art) are also included.

[Higher Order Particles] In the specification of the present application, when the structure of the copolymer particles is higher order particles, as an embodiment, secondary particles which are aggregates of the copolymer particles which are primary particles are used. , Tertiary particles to which a plurality of secondary particles adhere, and even higher-order particles are not particularly limited as long as they are suitable.

[Glass transition point (Tg)] The “glass transition point (Tg)” of the copolymer used in the specification of the present application.
The concept of a conventional method, for example, a differential scanning calorimeter (DS
C) and the like.

[Calculated value of glass transition point to evaluation of glass transition point (Tg) of copolymer] In the case of a copolymer, the glass transition point (Tg) can be evaluated as a calculated value of glass transition point. The glass transition point (Tg) of the copolymer and the methodology for its evaluation are as follows. The glass transition point (Tg) of a copolymer having a specific monomer composition can be obtained by calculation using the Fox equation.
Here, the Fox formula is for calculating the Tg of the copolymer based on the Tg of the homopolymer of the monomer for each monomer forming the copolymer,
See Bulletin of the American Physical Society, Series 2 (Bulletin
of the American Physical So
city, Series 2) Vol. 1, No. 3, page 123 (1956). The concept of the term "calculated glass transition point" used in the specification of the present application includes:
It also includes the glass transition point calculated by the Fox equation. The Tg of a homopolymer of various monomers which is the basis for calculating the Tg of the copolymer according to the Fox equation can be found, for example, in Polymer Data Handbook Basic Edition (edited by the Society of Polymer Science), pp. 525-546. Or the actually measured value measured by a usual method can be adopted.

[Emulsion polymerization] The term "emulsion polymerization" used in the specification of the present application refers not only to ordinary emulsion copolymerization, but also to special emulsion copolymerization, protective colloid copolymerization, and miniemulsion copolymerization. And techniques such as microemulsion copolymerization. In addition, a method of self-emulsifying or forcibly emulsifying a polymer by mixing a solvent and an emulsifier is also included in the concept of “emulsification” used in the specification of the present application.

[0121]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited to these examples. The ethylenically unsaturated monomers, polymerization initiators and surfactants used are indicated by the following abbreviations. ST: styrene, MMA: methyl methacrylate, n-BA: n-butyl acrylate, 2EHA: 2-ethylhexyl acrylate, n-BMA: n-butyl methacrylate, MAc: methacrylic acid, GMA: glycidyl methacrylate, APS : Ammonium persulfate, DBS: sodium dodecylbenzenesulfonate. In addition, the following parts and% show a weight part and weight%, respectively.

The test was conducted according to the following method.

[Rust prevention] The rust prevention was determined by subjecting the test specimen to a salt spray test with 5% saline (according to JIS Z-2371).
After 120 hours, the state of rust was observed and evaluated on a scale of 1 to 10 (10 points: excellent to 1 point: poor).

[Adhesion of Topcoat] The adhesion of topcoat was measured by applying a melamine resin baking paint Amirac (manufactured by Kansai Paint) as a topcoat to a test piece and baking at 130 ° C for 20 minutes to obtain a coating film having a thickness of about 30 µm. . Using the coated plate as it was as the primary adhesion, a grid test was performed, and the state of the coating was visually evaluated. Similarly, the coating state after extrusion of 8 mm with Erichsen was visually evaluated. The coated plate similarly prepared for secondary adhesion was immersed in boiling water for 30 minutes, then cross-cut and extruded by Erichsen 8 mm to visually evaluate the coating state. In any case, a maximum of 10 points (10 points: excellent ~
(1 point: poor).

[Solvent resistance] The solvent resistance was evaluated by performing a 10-way rubbing test with a gauze impregnated with methyl ethyl ketone (MEK) and visually observing the surface condition.
The evaluation was based on a perfect score (10 points: excellent to 1 point: poor). Similarly, ethanol was used.

Example 1 In a separable flask equipped with a stirrer, thermometer and reflux condenser, 1 part of ion-exchanged water was added.
Aqueous dispersion of 50 parts, Chemipearl S-650 (manufactured by Mitsui Chemicals, Inc., ethylene-methacrylic acid copolymer having a nonvolatile content of 27% (containing 20% by weight of methacrylic acid, 50% of methacrylic acid is neutralized with sodium ions)) 864 parts of a copolymer having an average particle size of about 50 nm),
The temperature is raised to 75 ° C. while purging with nitrogen while stirring. The internal temperature is maintained at 75 ° C., and 0.5 parts of APS is added and dissolved as a polymerization initiator. Next, a mixture of 40 parts of ST, 40 parts of 2EHA and 20 parts of GMA is continuously added and reacted over 2 hours, and aging is performed for about 2 hours after completion of the addition. Thereafter, the mixture was cooled to obtain an aqueous dispersant composition. The resulting aqueous dispersant composition had a nonvolatile content of 29.9%, as shown in Table 1.

To this aqueous dispersant composition polymer obtained in this example, ion-exchanged water was added to adjust the non-volatile content to 20%. To this, 500 ppm of Surflon S-145 (produced by Asahi Glass) was added and mixed to prepare a rust preventive paint composition. This paint was applied on a 0.8 mm thick electrogalvanized steel plate using a # 5 bar coater,
The coated plate having a cured coating film having a thickness of about 1 to 3 µm was obtained by baking and curing at 2 ° C for 2 minutes, and used as a test piece. Table 2 shows the test results.

Example 2 In a separable flask similar to that in Example 1, 300 parts of ion-exchanged water was added to the copolymer particles (A ₂ ) (an ethylene-acrylic acid copolymer (acrylic acid) having a nonvolatile content of 25%. 20 wt% content, in an aqueous dispersion of ammonia 50% of acrylic acid are neutralized with), the average particle size of the copolymer is about 50 nm: hereinafter abbreviated as a ₂₎ 720 parts were charged Then, the temperature is raised to 75 ° C. while stirring and replacing with nitrogen. The internal temperature is maintained at 75 ° C., and 0.5 g of APS is added and dissolved as a polymerization initiator. Next, an emulsion of an ethylenically unsaturated monomer, which was previously prepared by adding 42 parts of MMA, 42 parts of EHA and 36 parts of GMA to an aqueous solution consisting of 40 parts of ion-exchanged water and 0.4 parts of DBS while stirring, was continuously added. After 3 hours, the mixture is aged for about 2 hours. Thereafter, the mixture was cooled to obtain an aqueous dispersion composition shown in Table 1. Using this aqueous dispersion composition, a rust-preventive coating composition was prepared in the same manner as in Example 1 and tested. Table 2 shows the test results.

[Examples 3 to 8] In the same manner as in Example 2, the type and amount of the carboxyl group side chain-containing copolymer,
Polymerization was performed by changing the ratio of (A) :( B) and the composition of the ethylenically unsaturated monomer (B) to obtain a polymer emulsion. The conditions are shown in Table-1-2. Similarly, a rust preventive paint composition was prepared and tested. Table 4 shows the test results.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that GMA was not used and n-BMA was used. The resulting emulsion had a nonvolatile content of 3 as shown in Table 1.
0.0%. Similarly, a rust preventive paint composition was prepared and tested. The test results are shown in Table-5.

[0131] without using [Comparative Example 2] ethylenically unsaturated monomer copolymer (B), it was directly subjected to tests A _2. The test results are shown in Table-5.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

According to the present invention, the copolymer particles (A)
When the aqueous dispersion composition according to the present invention is applied to an adhesive composition by forming the epoxy group side chain-containing copolymer (B) in the presence, the adhesive layer and the surface of the adherend It is particularly noteworthy that the adhesion to (for example, a metal surface) is significantly improved. Further, when the aqueous dispersion composition according to the present invention is applied to a coating composition, the adhesion between the coating film and a base (for example, a metal surface or the like) is remarkably improved. Furthermore, it is noteworthy that when a top coat is formed with a top coat, the adhesion between this coat and the top coat is remarkably improved. A coated film can be obtained. Therefore, it is clear that it is useful as a main component of a rust-preventive paint for a metal, particularly a galvanized steel sheet.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/08 C09D 5/08 163/00 163/00 C09J 163/00 C09J 163/00 (72) Inventor Tadashi Saito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemical Co., Ltd. Address Mitsui Chemicals Co., Ltd.

Claims (26)

[Claims] 1. An aqueous dispersion composition comprising a dispersed phase and a continuous phase, wherein the dispersed phase contains composite resin particles, and the continuous phase contains water. An aqueous dispersion composition, wherein the composite particles are obtained by forming a copolymer (B) containing an epoxy group side chain in the presence of a polyolefin resin particle (A) having a carboxyl group side chain. 2. A main chain skeleton of a copolymer containing a carboxyl side chain constituting the copolymer particles (A), and a main chain skeleton of a copolymer containing an epoxy group side chain constituting the copolymer (B). The aqueous dispersion composition according to claim 1, wherein the composition is a polyolefin-based composition. 3. The copolymer particles (A) are represented by the general formulas (A-01), (A-02) and (A-02), based on the weight of the copolymer constituting the copolymer particles (A). (A-03)
2. The copolymer according to claim 1, comprising a copolymer having 5 to 40% by weight of a repeating unit having at least one carboxyl group side chain selected from the group consisting of [Chem.
Or the aqueous dispersion composition described in 2. Embedded image (In the general formula (A-02), R may be the same or different, and represents H or an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. General formula (A-03)
In the formula, M ⁺ represents a monovalent metal ion. ) 4. The aqueous dispersion composition according to claim 3, wherein M ⁺ is an alkali metal ion. 5. The copolymer (B) comprises the copolymer (B)
Is based on the weight of the copolymer constituting the general formula (B-
And (B-02) 0.1 to 80% by weight of a repeating unit having at least one epoxy group side chain selected from the group consisting of [Chemical Formula 2]. An aqueous dispersion composition according to any one of the above. Embedded image 6. The method according to claim 1, wherein the copolymer particles (A) are the copolymer particles.
Based on the weight of the copolymer constituting the polymer (A)
Formulas (A-11), (A-12), and (A-13)
At least one mosquito selected from the group consisting of
5 to 40 weight of a repeating unit having a ruboxyl group side chain
2% by weight of the copolymer.
Or the aqueous dispersion composition described in 2. Embedded image(General formulas (A-11), (A-12), and (A-1)
In 3), R^A1, R ^A2, And R^A3Is German
May be the same or different, and may be a hydrogen atom or carbon
Represents a hydrocarbon group having 1 to 20 atoms. Formula (A-1)
In 2), R may be the same or different,
H or an alkyl group having 1 to 4 carbon atoms, hydroxyal
Represents a kill group. In the general formula (A-13), M⁺Is
Represents a monovalent metal ion. ) 7. The aqueous dispersion composition according to claim 6, wherein M ⁺ is an alkali metal ion. 8. The copolymer (B) comprises the copolymer (B)
Is based on the weight of the copolymer constituting the general formula (B-
11) A composition comprising 0.1 to 80% by weight of a repeating unit having at least one type of epoxy group side chain selected from the group consisting of (B-12) and (B-13) [Chemical Formula 4]. 8. The aqueous dispersion composition according to any one of 1, 2, 6, and 7. Embedded image (General formulas (B-11), (B-12) and (B-13)
In formulas, R ^B11 , R ^B12 and R ^B13 each independently may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ) 9. The copolymer (B) has a general formula (B-2) based on the weight of the copolymer constituting the copolymer (B).
1), (B-22), (B-23), (B-24),
(B-25), (B-26) and (B-27)
The aqueous dispersion composition according to any one of claims 1 to 8, comprising 20 to 99.9% by weight of at least one repeating unit having no epoxy group side chain selected from the group consisting of: Embedded image (General formulas (B-21), (B-22), (B-23),
(B-24), (B-25), (B-26) and (B-
The symbols in 27) are as follows. R ^B21a ,
R ^B22a , R ^B23a , R ^B24 , R ^B26 or R ^B27 each independently may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^B21b and R
^B22b represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkene group or an aromatic group having 1 to 20 carbon atoms. R ^B23b independently represents a hydrogen atom which may be the same or different, or a hydrocarbon group having 1 to 20 carbon atoms. R ^B25 represents a saturated or unsaturated hydrocarbon group having a side chain having 1 to 10 carbon atoms or having no side chain. ) 10. The copolymer particles (A) and the copolymer (B)
The aqueous dispersion composition according to any one of claims 1 to 9, wherein the weight ratio is in the range of 1:99 to 95: 5. 11. An ethylenically unsaturated monomer (b-1) having an epoxy group side chain and no epoxy group side chain in the presence of a polyolefin resin particle (A) having a carboxyl group side chain. A method for producing an aqueous dispersion composition, comprising radically polymerizing an ethylenically unsaturated monomer mixture (b) containing an ethylenically unsaturated monomer (b-2), wherein the aqueous dispersion The body composition is composed of a dispersed phase and a continuous phase, the dispersed phase contains composite resin particles, and the continuous phase contains water. . 12. The copolymer particles (A) are represented by the general formula (A-01) based on the weight of all monomers used for copolymerization of the copolymer constituting the copolymer particles (A). ), (A-
02) and (A-03) an ethylenically unsaturated monomer containing 5 to 40% by weight of an ethylenically unsaturated monomer having at least one carboxyl group side chain selected from the group consisting of A copolymer obtained by radical copolymerization of a monomer mixture or neutralization of the copolymer containing (A-1) with ammonia, an amine or a monovalent metal ion. The method according to claim 11. Embedded image (In the general formula (A-02), R may be the same or different, and represents H or an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. General formula (A-03)
In the formula, M ⁺ represents a monovalent metal ion. ) 13. The copolymer particles (A) may contain the copolymer
All monomers used for copolymerization of the copolymer constituting the particles (A)
Formulas (A-21) and (A-
22) and (A-23) [Chemical Formula 7].
Has at least one selected carboxyl side chain
Contains 5 to 40% by weight of ethylenically unsaturated monomer
Radical copolymerization of a mixture of ethylenically unsaturated monomers
Claims obtained by
12. The manufacturing method described in 11. Embedded image(General formulas (A-21), (A-22), and (A-2
In 3), R^A1, R ^A2, And R^A3Is German
May be the same or different, and may be a hydrogen atom or carbon
Represents a hydrocarbon group having 1 to 20 atoms. General formula (A-2
In 2), R may be the same or different,
H or an alkyl group having 1 to 4 carbon atoms, hydroxyal
Represents a kill group. In the general formula (A-23), M⁺Is
Represents a monovalent metal ion. ) 14. An ethylenically unsaturated monomer having an epoxy group side chain (b-1) and an ethylenically unsaturated monomer having no epoxy group side chain (b-2). The unsaturated monomer mixture (b) is represented by the general formulas (B-01) and (B-) based on the total weight of the mixture (b).
02) It has 0.1 to 80% by weight of an ethylenically unsaturated monomer (b-1) having at least one epoxy group side chain selected from the group consisting of [Chemical formula 8]. 13. The production method according to any one of the above items 13. Embedded image 15. An ethylenically unsaturated monomer having an epoxy group side chain (b-1) and an ethylenically unsaturated monomer having no epoxy group side chain (b-2). The unsaturated monomer mixture (b) is represented by the general formula (B-31) or (B-32) based on the total weight of the mixture (b).
And (B-33) 0.1 to 80% by weight of at least one ethylenically unsaturated monomer (b-1) having an epoxy group side chain selected from the group consisting of [Chemical formula 9]. A method according to any one of claims 11 to 13. Embedded image (General formulas (B-31), (B-32) and (B-33)
In formulas, R ^B11 , R ^B12 and R ^B13 each independently may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ) 16. An ethylenically unsaturated monomer having an epoxy group side chain (b-1) and an ethylenically unsaturated monomer having no epoxy group side chain (b-2). The unsaturated monomer mixture (b) is represented by the general formula (B-41) or (B-4) based on the total weight of the mixture (b).
2), (B-43), (B-44), (B-45),
20-99. An ethylenically unsaturated monomer (b-2) having no epoxy group side chain selected from the group consisting of (B-46) and (B-47) [Formula 10]. 9
The production method according to any one of claims 11 to 15, wherein the production method has a percentage by weight. Embedded image (General formulas (B-41), (B-42), (B-43),
(B-44), (B-45), (B-46) and (B-44)
The symbols in 47) are as follows. R ^B21a ,
R ^B22a , R ^B23a , R ^B24 , R ^B26 or R ^B27 may each independently be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^B21b and R ^B22b are
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkene group or an aromatic group having 1 to 20 carbon atoms. R ^B23b independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. R ^B25 has a side chain having 1 to 10 carbon atoms,
Alternatively, it represents an ethylenically unsaturated monomer having no side chain. ) 17. Copolymer particles (A) and copolymer (B)
Is in the range of 1:99 to 95: 5 in weight ratio, the production method according to any one of claims 11 to 16, characterized in that: An aqueous dispersion composition obtained by the production method according to any one of claims 11 to 17. 19. A coating composition comprising the aqueous dispersion composition according to any one of claims 1 to 10 and 18. 20. A rust preventive coating composition comprising the aqueous dispersion composition according to claim 1. Description: An adhesive composition comprising the aqueous dispersion composition according to any one of claims 1 to 10 and 18. 22. A coated metal formed by applying a coating composition according to claim 19 or 20 to a surface thereof. 23. A rust-preventive metal coated with the coating composition according to claim 19 or 20 to form a coating film. 24. A coated metal sheet on which a coating film is formed by applying the coating composition according to claim 19 on at least one surface. 25. A rust-preventive metal plate formed by applying the coating composition according to claim 19 or 20 on at least one surface thereof. 26. The metal plate according to claim 24, wherein the metal plate is a galvanized steel plate.