JP2002294020A - Aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion excellent in adhesiveness and close adhesion with various base materials, storing stability, weather resistance, waterproofness, solvent resistance, etc. SOLUTION: This aqueous dispersion is obtained by blending (I) an aqueous dispersion obtained by dispersing a block copolymer (1) constituted by (A) a polymer block consisting mainly of an olefin-based monomer unit with (B) a polymer block consisting of 2-100 mole% vinyl-based monomer unit having carboxyl group or carboxylic acid anhydride group and 98-0 mole% another vinyl-based monomer unit copolymerizable with the above vinyl-based monomer in an aqueous solution of >=0.05 equivalent basic substance based on the above carboxyl or carboxylic acid anhydride groups, with (II) a tackiness-imparting agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous dispersion. The aqueous dispersion of the present invention is excellent in adhesiveness and adhesion to various substrates, storage stability, weather resistance, and the like.

[0002]

2. Description of the Related Art Polyolefin resins, such as polypropylene, are used in large quantities as plastics for home appliances and automobile parts because they are inexpensive and have excellent resin properties such as processability, water resistance and oil resistance. In order to increase the added value, painting on the surface of a polyolefin molded product or forming a laminate with another resin has been attempted, but polyolefin has low polarity, and general paint and other resins are used. There is a problem that the adhesiveness with the adhesive is low.

In order to solve this problem, the surface of a polyolefin molded product is treated in advance with chromic acid, flame, corona discharge, plasma, a solvent, etc. to increase the polarity of the surface of the molded product, so that a paint or other resin can be used. Attempts have been made to improve the adhesiveness of these materials, but in these treatments, there are problems such as the necessity of a complicated process and the use of a large amount of corrosive chemicals. there were.

Under such circumstances, a method has been proposed in which the surface of a polyolefin molded article is primed with a primer containing a chlorinated polyolefin as a main component, but the chlorinated polyolefin is harmful to the human body such as toluene and xylene. Since it is used after being dissolved in an aromatic organic solvent, there is a drawback that safety and environmental problems occur. Therefore, a method for dispersing a chlorinated polyolefin in an aqueous solution (Japanese Unexamined Patent Application Publication No.
JP-A-256556 and JP-A-4-218548) have been proposed. However, even in this method, it is difficult to completely eliminate the use of the aromatic organic solvent, and the weather resistance of the coating film obtained is also difficult. And poor water resistance. Further, an aqueous dispersion-type adhesive containing no chlorine has been desired from the viewpoints of hydrochloric acid gas generation during waste incineration, recycling, and the like.

[0005]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide an aqueous dispersion having excellent adhesion and adhesion to various substrates, storage stability, weather resistance, water resistance and the like. .

[0006]

According to the present invention, an object of the present invention is to provide a polymer block (A) mainly composed of an olefin monomer unit and a vinyl monomer having a carboxyl group or a carboxylic anhydride group. A polymer block (B) consisting of 2 to 100 mol% of a unit of the above and 98 to 0 mol% of a unit of another vinyl monomer copolymerizable with the vinyl monomer.
A tackifier is added to an aqueous dispersion (I) obtained by dispersing a block copolymer (I) composed of the following in an aqueous solution of a basic substance in an amount of 0.05 equivalent or more based on the carboxyl group or carboxylic anhydride group. (II) and, if necessary, a polyurethane resin or a vinyl polymer (III)
This is achieved by providing an aqueous dispersion or an aqueous solution of the above, an aqueous dispersion containing a curing agent (IV).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer (I) of the present invention comprises a polymer block (A) and a polymer block (B) described below.
Type diblock copolymer, ABA type triblock copolymer, BAB type triblock copolymer and the like. Of these, AB-type diblock copolymers are preferred.

[0008] The polymer block (A) constituting the block copolymer (I) is a polymer block mainly composed of olefin-based monomer units. The content of the olefin-based monomer unit in the polymer block (A) is from 50 to 50 based on the total number of moles of all the structural units in the polymer block (A).
It is preferably in the range of 100 mol%,
It is more preferably in the range of 00 mol%,
More preferably, it is within the range of 100 mol%. The content of the olefin monomer unit in the polymer block (A) is most preferably 100 mol% based on the total number of moles of all the structural units in the polymer block (A).

The olefinic monomer unit includes, for example, ethylene; propylene, 1-butene, 2-methyl-
1-butene, 3-methyl-1-butene, 1-pentene,
Α-olefins such as 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-octadecene; 2-butene; conjugated dienes such as isobutylene, butadiene, isoprene and cyclopentadiene; vinylcyclohexane; -A unit derived from pinene, etc., and the polymer block (A) is one of these.
Species or two or more species may be contained. The polymer block (A) preferably contains a unit derived from ethylene or propylene, and includes a polymer block composed of a unit derived from propylene, a copolymer block composed of a unit derived from propylene and a unit derived from ethylene. Polymer block, a copolymer block consisting of units derived from propylene and units derived from other α-olefins other than propylene, a polymer block consisting of units derived from ethylene or units derived from ethylene, and More preferably, it is a polymer block containing a copolymer block composed of a unit derived from an α-olefin other than propylene. When the olefin monomer unit is a unit derived from a conjugated diene such as butadiene, isoprene, or cyclopentadiene, the remaining unsaturated bonds may be hydrogenated.

[0010] The polymer block (A) may be, if necessary,
Units derived from the vinyl monomers copolymerizable with the olefin monomers can be contained in a proportion within the range of 0 to 50 mol%. The content of the monomer unit is 0
Preferably in the range of 0 to 30 mol%,
More preferably, it is within the range of mol%. Examples of the vinyl monomer copolymerizable with the olefin monomer include, for example, (meth) acrylonitrile; vinyl acetate,
Vinyl esters such as vinyl pivalate; methyl (meth)
(Meth) acrylic esters such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (meth) acrylamide; N
-Vinyl-2-pyrrolidone and the like, and one or more of these can be used.
Of these, methyl acrylate, ethyl acrylate and acrylonitrile are preferred.

In the present invention, the polymer block (B) constituting the block copolymer is composed of a unit of a vinyl monomer having a carboxyl group or a carboxylic anhydride group, and a mole of the total structural unit of the polymer block (B). 2-10 based on the number
0 mol%, from the viewpoint of the water resistance of the coating layer formed from the aqueous dispersion, the content of the unit is 2 to 2
It is preferably in the range of 50 mol%, more preferably in the range of 2 to 45 mol%, and still more preferably in the range of 2 to 30 mol%.

Examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid. The above can be used. Of these, acrylic acid and methacrylic acid are preferred.

Examples of the vinyl monomer having a carboxylic anhydride group (group represented by the formula: -CO-O-CO-) include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, butenyl succinic anhydride , Tetrahydrophthalic anhydride and the like, and one or more of these can be used. Of these, maleic anhydride is preferred.

The polymer block (B) comprises a unit of another vinyl monomer copolymerizable with the above-mentioned vinyl monomer having a carboxyl group or a carboxylic anhydride group as a whole of the polymer block (B). 0 to 98 mol%, preferably 50 to 98 mol%, more preferably 5 to 98 mol%, based on the number of moles of the structural unit.
5 to 98 mol%, more preferably 70 to 98 mol% can be contained. Examples of the other vinyl monomers include styrene monomers such as styrene, p-styrenesulfonic acid and its sodium and potassium salts;
(Meth) acrylonitrile; vinyl esters such as vinyl acetate and vinyl pivalate; and methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. (Meth) acrylic acid ester; (meth) acrylamide; N-vinyl-2-
Pyrrolidone and the like can be mentioned, and one or more of these can be used. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, styrene, and acrylonitrile are preferred.

The number average molecular weight of the polymer block (A) is preferably in the range of 1,000 to 100,000, and more preferably in the range of 1,000 to 20,000. The number average molecular weight of the polymer block (B) is preferably in the range of 1,000 to 100,000, and more preferably in the range of 1,000 to 20,000. Block copolymer (I)
Has a number average molecular weight of 2,000 to 200,000.
2,000 to 40,0
More preferably, it is within the range of 00. In addition, the number average molecular weight referred to in the present specification is a value determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC). The weight ratio of the polymer block (A) and the polymer block (B) in the block copolymer (I) is such that polymer block (A) / polymer block (B) = 3/1 to 1/3. Is preferable, and it is more preferable that it is in the range of polymer block (A) / polymer block (B) = 2/1 to 1/2.

The block copolymer (I) in the present invention
Can be produced, for example, by subjecting a monomer component constituting the polymer block (B) to radical polymerization in the presence of a polymer block (A) having a mercapto group at a terminal. According to this method, the block copolymer (I) having the target number average molecular weight and molecular weight distribution can be easily and efficiently produced.

The polymer block (A) having a mercapto group at the terminal can be produced by various methods. For example, a polyolefin polymer having a double bond at the terminal can be prepared by adding thio-S-acetic acid, thio- S-benzoic acid, thio-S-
After addition of propionic acid, thio-S-butyric acid or thio-S-valeric acid, a method of treating with an acid or an alkali, a method of using ethylene sulfide as a terminator when producing a polyolefin by an anionic polymerization method, or the like. Can be manufactured.

In the aqueous dispersion of the present invention, when the olefin polymer is blended at a ratio of 1 to 200 parts by weight with respect to 100 parts by weight of the above block copolymer (I), the olefin polymer is formed from the aqueous dispersion. In some cases, the strength of the applied coating layer is improved. The amount of the olefin polymer is in the range of 1 to 100 parts by weight based on 100 parts by weight of the block copolymer (I) from the viewpoint of the balance between the storage stability of the aqueous dispersion and the strength of the obtained coating layer. And more preferably within a range of 1 to 50 parts by weight. When the amount of the olefin polymer is 2
If it exceeds 00 parts by weight, the average particle size of the dispersing substance in the obtained aqueous dispersion becomes large, and the storage stability of the aqueous dispersion decreases.

Examples of the olefin polymer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, and ethylene-acryl. Ethyl acid copolymer, ethylene-methyl acrylate copolymer, propylene-α-olefin copolymer, ethylene-α-olefin copolymer, ethylene-propylene-diene (or triene) terpolymer, and the like. And one or more of these can be used. Examples of the α-olefin in the ethylene-α-olefin copolymer include propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 1-octene, 1-decene, and the like. Examples of the diene (or triene) in the ethylene-propylene-diene (or triene) terpolymer include 1,4-hexadiene, 1, Chain non-conjugated dienes such as 6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,6-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene;
Dichloropentadiene, methyltetrahydroindene,
5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5
Cyclic non-conjugated dienes such as -isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, And trienes such as 3,3,7-octatriene and 1,4,9-decatriene. Further, the olefin polymer may be modified, the modification is,
Halogenation such as chlorination and bromination; chlorosulfonation; epoxidation; hydroxylation; carboxylic anhydride oxidation;

The above-mentioned block copolymer (I) and an olefin polymer blended if necessary are added to the carboxyl group or carboxylic anhydride group in the polymer block (B) of the block copolymer (I). The aqueous dispersion (I) according to the present invention can be produced by dispersing in a 0.05 equivalent or more aqueous solution of a basic substance at a temperature not lower than the melting point of the block copolymer. In the case of producing the aqueous dispersion (I) containing the olefin polymer, the temperature of the block copolymer (I) or the olefin polymer is not lower than the melting point of the higher melting point polymer. Is preferably dispersed in the above aqueous solution. When the above-mentioned dispersion is performed at a temperature lower than the above-mentioned melting point, the average particle size of the dispersed substance increases, and the stability of the aqueous dispersion (I) decreases.

The above-mentioned dispersion can be performed using a pressure vessel equipped with a stirring means. The stirring means is not particularly limited, but from the viewpoint of generating a large shearing force, a turbine-type stirrer, a colloid mill, a homogenizer, etc. Mixers and homogenizers are preferred. For dispersion, use a line mixer equipped with a movable stirrer or a "static mixer".
This may be performed by using a non-movable line-type mixer such as (trade name, manufactured by Noritake Co., Ltd.).

As the above basic substance, ammonia,
Hydroxyamine, ammonium hydroxide, hydrazine,
Hydrazine hydrate, (di) methylamine, (di) ethylamine, (di) propylamine, (di) butylamine,
(Di) hexylamine, (di) octylamine, (di)
Ethanolamine, (di) propanolamine, N-methyldiethanolamine, triethylamine, N, N-
Amine compounds such as dimethylethanolamine, N, N-diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, cyclohexylamine and tetramethylammonium hydroxide; Metal oxides such as sodium oxide, sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide and barium oxide; metals such as barium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and strontium hydroxide Hydroxide; carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and calcium bicarbonate; and acetates such as sodium acetate, potassium acetate and calcium acetate. Among these, from the viewpoint of availability and stability of the aqueous dispersion, ammonia, (di) methylamine, (di) ethylamine,
(Di) propylamine, (di) butylamine, N-methyldiethanolamine, triethylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino -2-methyl-1-propanol,
Sodium hydroxide and potassium hydroxide are preferred, and ammonia, sodium hydroxide and potassium hydroxide are more preferred.

These basic substances are used as an aqueous solution. The amount of the basic substance used depends on the amount of the block copolymer (I).
It is 0.05 equivalent or more with respect to the carboxyl group or the carboxylic anhydride group in the polymer block (B) of the above, and is in the range of 0.2 to 5.0 equivalents from the viewpoint of reducing the dispersion particle diameter. Is more preferable, and it is more preferable that it is in the range of 0.3 to 1.5 equivalents. In addition, 1 equivalent with respect to 1 mol of carboxyl groups is 1 mol equivalent of a basic substance, and 1 equivalent with respect to 1 mol of carboxylic anhydride groups is 2 mol equivalent of a basic substance.

The mixing ratio of the block copolymer (I) and the aqueous solution of the basic substance in the aqueous dispersion (I) is such that the aqueous solution of the basic substance is mixed with 5 to 70 parts by weight of the block copolymer (I). It is preferable that the amount be in the range of 30 parts by weight.

The aqueous dispersion of the present invention can be produced by adding the tackifier (II) to the aqueous dispersion (I). Tackifiers are generally used in the fields of pressure-sensitive adhesive tapes, paints, hot melt adhesives, etc., and include, for example, petroleum resins such as C4, C5, C9, C4 to C9 copolymers and the like. Hydrogenated saturated petroleum resins, rosin derivatives (rosin, polymerized rosin, hydrogenated rosin and its esters with glycerin, pentaerythritol, etc., resin acid dimer, etc.), terpene resins (α, β
-A terpene resin obtained by polymerizing pinene, a terpene phenol resin, an aromatic modified terpene resin, a hydrogenated terpene resin, etc.), a cumarone-indene resin, a phenol resin, a xylene resin, and a styrene-based resin. Generally, tackifiers have a number average molecular weight in the range of 500-3000 and a ring and ball softening point in the range of 50-140C. Among these, saturated petroleum resins are preferred because they have excellent compatibility with the block copolymer (I), and the resulting aqueous dispersion has high stability and high adhesion and adhesion to various substrates. As the saturated petroleum resin, commercially available resins can be used. For example, “Rigaletz”, “Rigalight” (all manufactured by Rika Hercules), “Alcon”
(Arakawa Chemical Industries), "Escolets" (Tonex), "Quinton" (Zeon Japan), "Imarb" (Idemitsu Petrochemical), and the like. When the tackifier (II) is blended with the aqueous dispersion (I), the weight ratio of the solids in the aqueous dispersion (I) to the tackifier (II) is 9
It is preferably in the range of 9.9: 0.1 to 50:50, and more preferably in the range of 99: 1 to 70:30.

In the aqueous dispersion of the present invention, if necessary, a polyurethane resin or a vinyl polymer (II
It is possible to incorporate an aqueous dispersion or aqueous solution of I).

As the aqueous dispersion or aqueous solution of the polyurethane resin, known ones can be used, for example, those containing a carboxyl group obtained by reacting an organic polyisocyanate, a polymer polyol and a carboxyl group-containing polyol. An aqueous dispersion of a polyurethane resin obtained by neutralizing the terminal isocyanate prepolymer with a tertiary amine or the like and emulsifying and dispersing in water at the same time and / or emulsifying and dispersing, and then increasing the molecular weight with a chain extender such as a polyamine; After the terminal isocyanate prepolymer obtained by reacting the organic polyisocyanate and the polymer polyol is emulsified and dispersed in water in the presence of a surfactant and / or simultaneously emulsified and dispersed, the molecular weight is increased by a chain extender such as polyamine. Aqueous content of polyurethane resin obtained by Liquid, an organic polyisocyanate, a polymer polyol, a carboxyl group-containing polyol and a carboxyl group-containing polyurethane obtained by reacting a chain extender are neutralized with a tertiary amine or the like and emulsified and dispersed in water. Dispersion,
An aqueous dispersion of a polyurethane-based composite resin obtained by emulsion polymerization of a vinyl monomer in the aqueous dispersion of a polyurethane resin described in the above, an organic polyisocyanate, a polymer polyol containing a polyoxyalkylene glycol, and a chain extender. And an aqueous dispersion or aqueous dispersion of a polyurethane resin obtained by dissolving or emulsifying and dispersing a polyoxyalkylene group-containing polyurethane obtained by reacting with water.

As the organic polyisocyanate which can be used for producing the polyurethane resin, any of the organic polyisocyanates conventionally used for producing ordinary polyurethane can be used. One or more of aromatic diisocyanates and aromatic diisocyanates are preferably used. Examples of these include hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, p -Phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,5-naphthylene diisocyanate, and the like, and one or more of these can be used. Further, a tri- or higher functional polyisocyanate such as a trimer of hexamethylene diisocyanate can be used in combination.

The polymer polyols that can be used in the production of polyurethane resins include poly (ethylene glycol),
Polyether polyols such as poly (propylene glycol), poly (tetramethylene glycol) and poly (methyltetramethylene glycol); polybutylene adipate diol, polybutylene sebacate diol, polyhexamethylene adipate diol, poly (3-methyl-1) , 5-pentylene adipate) diol, poly (3
-Methyl-1,5-pentylene sebacate) diol,
Polycaprolactone diol, poly (β-methyl-δ-
Polyester polyols such as valerolactone) diol; polycarbonate polyols such as polyhexamethylene carbonate diol and poly (3-methyl-1,5-pentylene carbonate) diol; polyester polycarbonate polyols;
Known polymer polyols such as polypropylene polyols, polyisobutene polyols, polybutadiene polyols and hydrogenated products thereof, and polyolefin polyols such as polyisoprene polyols and hydrogenated products thereof can be given. Polyurethane-based resins include one of these polymer polyols. It can be formed using a kind or two or more kinds.

The number average molecular weight of the high molecular polyol is 300
Preferably from 10,000 to 10,000, and from 400 to 8,000.
Is more preferable, and it is still more preferable that it is 500-6000. In addition, the number average molecular weight of the high molecular polyol referred to in this specification refers to a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1577. Further, the high molecular polyol used for producing the polyurethane resin has a number of hydroxyl groups of 1 to 3 per molecule.
It is preferred that

As the chain extender component which can be used for producing a polyurethane resin, any of chain extenders conventionally used for producing ordinary polyurethane can be used.
It is preferable to use a low molecular weight compound having a molecular weight of 300 or less and having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
Diols such as hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β-hydroxyethyl) terephthalate and xylylene glycol; triols such as trimethylolpropane; Pentaols such as erythritol; hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, adipic dihydrazide, isophthalic acid Diamines such as dihydrazide; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol; and one or more of these are used. Can be Among them, diamines such as hydrazine, ethylenediamine, piperazine, adipic dihydrazide and isophthalic dihydrazide are preferably used. In addition, a monoamine compound such as n-butylamine, 4-aminobutanoic acid, or 6-aminohexanoic acid may be used in combination with a bifunctional or higher polyamine compound during the chain extension reaction.

The polyurethane resin used in the present invention preferably has a neutralized carboxyl group in the polyurethane resin skeleton in order to emulsify and disperse or dissolve in water. The neutralized carboxyl group is introduced into the polyurethane resin skeleton by using a compound having a carboxyl group or a salt thereof and containing at least one active hydrogen atom such as a hydroxyl group or an amino group in the polyurethane reaction. And, if necessary, neutralization with a basic substance such as a tertiary amine or an alkali metal hydroxide. Such compounds include, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid,
2,2-dimethylolvaleric acid and the like. Further, polyester polyols or polyester polycarbonate polyols obtained by copolymerizing the above compounds can also be used. Above all, a polyurethane prepolymer is produced using 2,2-dimethylolpropionic acid or 2,2-dimethylolbutyric acid, and after completion of the prepolymer reaction or when the prepolymer is emulsified in water, trimethylamine, triethylamine, N, N Preferred is a method of adding a basic substance such as -dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine and the like to convert the compound into a carboxylate.

The polyurethane resin used in the present invention has the following features: (1) having 5 carbon atoms because of its high compatibility with the block copolymer (I) and excellent adhesion to the substrate.
It is preferably a resin having a monovalent or divalent aliphatic hydrocarbon group of 0 to 1000, or (2) a composite resin of a polyurethane resin and a polymer comprising a vinyl monomer.

The polyurethane resin having a monovalent or divalent aliphatic hydrocarbon group having 50 to 1000 carbon atoms may be, for example, a monovalent or divalent having 50 to 1000 carbon atoms as at least a part of a high molecular polyol. And a polyurethane resin produced by using a polyolefin polyol having an aliphatic hydrocarbon group.
The proportion of the aliphatic hydrocarbon group in the polyurethane resin is preferably 10 to 50% by weight, and 15% by weight.
The content is more preferably from 45 to 45% by weight, and still more preferably from 20 to 40% by weight.

Examples of the polyurethane-based composite resin include a composite resin obtained by polymerizing a vinyl-based monomer in the presence of a polyurethane resin. Examples thereof include a method in which a vinyl monomer is emulsion-polymerized in a solvent, and a method in which a vinyl monomer is polymerized in the presence of a polyurethane resin, and then emulsified and dispersed or dissolved in water. As the vinyl monomer, those described above as the raw material of the polymer block (B) of the block copolymer (I) can be used. The amount of the vinyl monomer used is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and more preferably 30 to 70% by weight based on the total weight of the polyurethane-based composite resin. Is more preferable.

The aqueous dispersion or aqueous solution of the polyurethane resin used in the present invention may contain a surfactant. The content of the surfactant is as follows.
It is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 3 parts by weight or less, because the adhesion to a substrate is more excellent with respect to 00 parts by weight.

On the other hand, the aqueous dispersion or aqueous solution of the vinyl polymer may be prepared, for example, by adding one or more vinyl monomers which can be polymerized in an aqueous medium using a polymerization initiator in the presence of an emulsifier, and if necessary. In the presence of additives such as a molecular weight regulator, a water-soluble polymer compound, or an inorganic compound, the polymerization temperature is generally 30 to 90 ° C., and the polymerization pressure is atmospheric pressure to 5MPa.
It can be obtained by radical polymerization under the conditions of a for 1 hour to 20 hours.

Examples of the vinyl monomer capable of forming a vinyl polymer include compounds having at least one unsaturated bond capable of radical polymerization or radical copolymerization in a molecule, for example, styrene, α-methylstyrene, vinyl Styrene monomers such as toluene, hydroxystyrene, p-styrenesulfonic acid and its sodium and potassium salts; (meth) acrylonitrile; vinyl ester monomers such as vinyl acetate and vinyl pivalate; methyl (meth)
(Meth) acrylate monomers such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; Meth) acrylamide; N
-Vinyl-2-pyrrolidone; diene monomers such as 1,3-butadiene, isoprene, chloroprene, and 1,5-hexadiene; maleate esters such as maleic acid, diethyl maleate and di-n-butyl maleate; Monomer;
Fumaric acid monomers such as fumaric acid and di-n-butyl fumarate; vinyl chloride; vinylidene chloride;
One or more of these can be used. Of these, styrene monomers, vinyl ester monomers, and (meth) acrylate monomers are preferably used.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile; peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, hydrogen peroxide, and antimony peroxide. Persulfates such as potassium persulfate; and redox initiators obtained by combining these peroxides or persulfates with reducing agents such as sodium thiosulfate and ferrous chloride. Examples of the emulsifier include anionic surfactants such as aliphatic salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, and sorbitan alkyl esters. Is used.

In the present invention, the aqueous dispersion (aqueous emulsion) of the vinyl polymer obtained as described above can be used, but after adjusting the viscosity with ammonia water or the like, if necessary, a filler, You may use what added the crosslinking agent etc. Also, as an aqueous dispersion of a vinyl polymer, an aqueous dispersion of a vinyl polymer which is commercially available as an aqueous emulsion adhesive, for example, an acrylic aqueous emulsion adhesive containing acrylates as a main vinyl monomer It is also possible to use a vinyl acetate aqueous emulsion adhesive using vinyl acetate as a main vinyl monomer, a styrene aqueous emulsion adhesive using styrene as a main vinyl monomer, and the like. There are many types of these aqueous emulsion-type adhesives depending on the vinyl monomer used, and an optimum one may be selected according to the material to be bonded. When the vinyl polymer is water-soluble, it is blended as an aqueous solution. Examples of the water-soluble vinyl polymer include polyvinyl alcohol.

The weight ratio of the polyurethane resin or vinyl polymer (III) to the total amount of the solid content and the tackifier (II) in the aqueous dispersion (I) depends on the adhesiveness, aqueous From the viewpoint of the water resistance and the like of the coating layer formed from the dispersion, the ratio is preferably in the range of 5:95 to 95: 5.

The aqueous dispersion of the present invention may further contain a curing agent (IV). As the curing agent (IV), a water-soluble or water-dispersible compound having two or more functional groups in one molecule that reacts with a carboxyl group or an acid anhydride group in the block copolymer (I) is used. Examples of the functional group of the curing agent include an epoxy group, an aziridine group, an oxazoline group, a carbodiimide group, and an isocyanate group.

The curing agent (IV) is preferably an epoxy compound, more preferably a polyfunctional epoxy compound having an epoxy equivalent (weight per equivalent of epoxy group) of 50 to 2500, and more preferably a polyfunctional epoxy compound having an epoxy equivalent of 100 to 1000. Epoxy compounds are more preferred. The molecular weight of the epoxy compound is preferably in the range of 150 to 5,000, more preferably in the range of 200 to 3,000.

Specific examples of epoxy compounds include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate. ,
Glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol Diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (ethylene oxide) glycidyl ether, pt-butylphenyl glycidyl ether, lauryl alcohol (ethylene oxide) glycidyl ether, adipic acid diglycidyl ester, o-Glycidyl phthalate, hydroquino Diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether, terephthalic acid diglycidyl ester, glycidyl phthalimide, dibromophenyl glycidyl ether, dibromo neopentyl glycol diglycidyl ether. In particular, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and bisphenol A diglycidyl ether are preferred from the viewpoint that an aqueous dispersion having excellent adhesion to a paint can be obtained, and the preparation of an aqueous dispersion is easy. . These epoxy compounds can be easily obtained as commercial products. For example, from Nagase Kasei Kogyo Co., Ltd., product names such as Denacol and Denacast, Kanebo N
Examples include those commercially available from SC under the trade name of Eporsion.

Examples of curing agents other than epoxy compounds include aziridine compounds such as PZ-33 (trade name, manufactured by Nippon Shokubai Co., Ltd.); and Epocros WS-500 (trade name,
Oxazoline compounds such as Nippon Shokubai Co., Ltd.) and Epocros K-2030E (trade name, manufactured by Nippon Shokubai Co., Ltd.);
Carbodiimide compounds such as Carbodilite E-01 (trade name, manufactured by Nisshinbo Industries, Ltd.) and Carbodilite V-02 (trade name, manufactured by Nisshinbo Industries, Ltd.); CR-60N (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) , Takerak WD (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) and the like.

The amount of the curing agent (IV) to be added is within the range of 0.1 to 20% by weight based on the solid content of the aqueous dispersion (I). It is preferable from the viewpoint of a balance between solvent resistance and durability and adhesion or adhesion to various substrates.

In the aqueous dispersion of the present invention, if necessary,
Thickeners, defoamers, leveling agents, penetrants and the like can be added. Examples of the thickener include water-soluble polymers such as carboxymethylcellulose, methylcellulose, sodium polyphosphate, polyvinyl alcohol, sodium polyacrylate, casein, vinyl alcohol-methacrylic acid copolymer, starch, and proteins. .

Further, in order to improve the wettability of the material to be applied, a small amount of an organic solvent may be added to the aqueous dispersion of the present invention. In addition, the aqueous dispersion of the present invention may contain various stabilizers such as an antioxidant, a weather resistance stabilizer, a thermal decomposition inhibitor, and an ultraviolet absorber, if necessary, in addition to the above compounds; titanium oxide, organic pigments, and the like. A coloring agent; a conductivity-imparting agent such as carbon black and ferrite; and an organic or inorganic filler.

Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, ot-butyl-p-cresol, and tetrakis- [methylene-3- (3,5-di-t-cresol). [Butyl-4-hydroxyphenyl) propionate] methane, β-naphthylamine, p-phenylenediamine and the like.

As the ultraviolet absorber, for example, 2,4-
Dihydroxybenzophenone, 2- (2′-dihydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-t
-Butyl-5-methylphenyl) -5-chlorobenzotriazole, bis (2,2 ', 6,6')-tetramethyl-4-piperidine) sebacate and the like.

As the organic filler, for example, wood powder,
Examples include pulp powder, rayon, vinylon, polyamide, polyamideimide, polyimide, and polymer particles such as polytetrafluoroethylene. Examples of the inorganic filler include, for example, silicates such as talc, clay, kaolin, and mica; oxides such as silica, titanium oxide, iron oxide, and zinc oxide; and hydroxides such as aluminum hydroxide and magnesium hydroxide. Products, carbonates such as calcium carbonate and magnesium carbonate, and sulfates such as barium sulfate and calcium sulfate.

The average particle size of the dispersed substance in the aqueous dispersion of the present invention is in the range of 0.05 to 2 μm from the viewpoint of storage stability of the aqueous dispersion, adhesion to various substrates, and adhesion. Preferably, it is more preferably in the range of 0.05 to 1 μm. The aqueous dispersion of the present invention has a small particle diameter of the dispersed substance, so that phase separation hardly occurs and storage stability is good. The aqueous dispersion of the present invention has excellent adhesiveness and adhesion to a nonpolar substrate such as a polyolefin-based resin, particularly to polypropylene. Further, since it has excellent adhesiveness to polar substrates, it is useful as a coating agent (primer, paint, adhesive, surface modifier for painting or bonding) and the like.

The aqueous dispersion of the present invention may be, for example, a high pressure polyethylene, a medium / low pressure polyethylene, a polypropylene,
Polyolefins such as poly-4-methyl-pentene and polystyrene, and polyolefin copolymers such as ethylene-propylene copolymer, ethylene-butene copolymer, propylene-butene copolymer, and ethylene-propylene-diene terpolymer It can be suitably used as a coating agent used for molded articles.

Further, in addition to the above-mentioned polyolefins and other polymers, the aqueous dispersion of the present invention may be a molded article composed of polypropylene and synthetic rubber, a polyamide resin, an unsaturated polyester resin, a polybutylene terephthalate resin,
It can also be used for surface treatment of molded products made of polycarbonate resin and the like, and furthermore, steel plates and electrodeposited steel plates.
In addition, undercoating is applied to a surface to which a coating or an adhesive is applied mainly composed of a polyurethane resin, a fatty acid-modified polyester resin, an oil-free polyester resin, a melamine resin, an epoxy resin, etc., and adhesion of the coating or the adhesive to the surface. It can be used for the purpose of forming a coating film which is excellent in clarity, low-temperature impact resistance and the like while improving the properties.

That is, the aqueous dispersion of the present invention uses molded articles such as automobile bumpers made of polyolefin such as polypropylene, molded articles such as automobile bumpers made of polypropylene and synthetic rubber, unsaturated polyester resin, epoxy resin and the like. Suitable as a primer to improve the adhesion of paints, adhesives, etc. to the surface of these molded products by undercoating SMC molded products, glass fiber reinforced polyamide resin molded products, polyurethane resin molded products, cationic electrodeposition coated steel plates, etc. It is.

In the molded article to which the coating agent containing the aqueous dispersion of the present invention as a main component is applied, the above-mentioned various polymers or resins are prepared by injection molding, compression molding, hollow molding, extrusion molding, rotational molding, or the like. Molded by any of the known molding methods described above.

When the aqueous dispersion of the present invention is applied to the surface of a molded article, a chlorine-based solvent usually used, for example,
It is not necessary to carry out pretreatment with 1,1,1-trichloroethane, 1,1,1-trichloroethylene or the like, or to carry out steam cleaning. What is necessary is just to wash with an acidic or weakly alkaline aqueous solution.

As a method for applying the aqueous dispersion of the present invention to the surface of a molded article, spray coating is suitable. For example, the aqueous dispersion is sprayed on the surface of the molded article by a spray gun. The coating on the molded product may be performed at room temperature. After the coating, the coating is dried by an appropriate method such as natural drying or forced heating drying to form a coating layer.

As described above, after the aqueous dispersion of the present invention is applied to the surface of a molded article and dried, the surface of the molded article is subjected to coating by a method such as electrostatic coating, spray coating, or brush coating. , An adhesive or the like can be applied. Application of a paint, an adhesive, or the like may be performed by a method of applying an undercoat and then an overcoat. The types of paints and adhesives used are not particularly limited, but the aqueous dispersion of the present invention may be a solvent-type thermoplastic acrylic resin paint, a solvent-type thermosetting acrylic resin paint, an acrylic-modified alkyd resin paint, an epoxy resin paint, or a polyurethane. In the case of coating using a resin paint, a melamine resin paint, or the like, a primer layer having high paint adhesion can be formed by previously applying a primer to a molded product, which is preferable. After applying a paint, an adhesive or the like, it is cured according to a normal method of heating with a nichrome wire heater, an infrared heater, a high-frequency heater, or the like, and a molded article having a desired coating film on the surface can be obtained. The method of curing the coating film is appropriately selected depending on the material and shape of the molded product, the properties of the paint and adhesive used, and the like.

Further, the aqueous dispersion of the present invention can be used for paper, wood,
Coating agent for articles of various shapes (molds, films, sheets, etc.) made of metal, plastic, etc. (waterproofing, release, heat sealing, adhesives of different materials in laminating, inks, paints Water-based paints and water-based ink modifiers (pigment dispersion, gloss imparting, abrasion resistance imparting, water resistance, etc.); inkjet ink and color copy binders; toner modifiers; polishing agents; metals It is also useful as a surface treatment agent.

[0061]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, the measurement of the average particle diameter of the dispersed particles, the coating property test, and the heat lamination adhesion test were performed as follows. (Average particle size measurement) "ELS80" manufactured by Otsuka Electronics Co., Ltd.
It measured by the light scattering method using "0".

(Coating property test) Cross-cut test After preparing a test piece with a cross-cut according to the cross-cut test method described in JIS K5400, and pasting a cellotape (trade name, manufactured by Nichiban Co., Ltd.) on the cross-cut , This is quickly pulled in a 90 degree direction to peel off,
The evaluation was made based on the number of grids that were not peeled out of the grids 100. 2. Water resistance test After the coated plate was immersed in warm water of 40 ° C. for 240 hours, the water was wiped off, and one hour later, a grid test was performed in accordance with JIS K5400. 3. Solvent Resistance Test The coated plate was immersed in a mixture of gasoline and ethanol [gasoline / ethanol = 9/1 (weight ratio)] at 25 ° C. for 30 minutes, and the floating state of the coating film was observed. -A film having no change in the coating film was evaluated as "A".-A film having 1-5% of the coating film was peeled off.-A film having a coating film peeled at 5% or more was evaluated as x. 4. Light fastness test Painted plate with fade meter (black panel temperature 83
C) after 400 hours of irradiation at the
A grid test was performed in accordance with IS K5400.

(Heat Laminating Adhesion Test) Thickness 20 μm
The aqueous dispersion was applied to the untreated surface of the OPP film by a No. 32 bar coater, dried at 50 ° C., and then subjected to a lamination test with the following various films by a lamination tester. About the obtained laminate film,
The T-type peel strength was measured at a tensile speed of 50 mm / min in accordance with JIS K6854-3. When no adhesion was observed, the peel strength was set to “0”. In addition, when the material was destroyed without peeling, it was regarded as “material breakage”.・ Film OPP film [Thickness: 20 μm;
“TOCELLO OP-U1” (trade name)] PET film [thickness: 100 μm; manufactured by Diafoil Co., Ltd., “Diafoil S” (trade name)] PA6 film [thickness: 40 μm; manufactured by Toray Industries, Inc.
"Rayfan" (trade name)] Ethylene-vinyl alcohol copolymer film [Thickness:
15 μm; “EVAL F” (trade name) manufactured by Kuraray Co., Ltd.]

Production Example 1: Block copolymer (I-1)
Production of aqueous dispersion (I-1) of (propylene-α-olefin copolymer block / ethyl acrylate-acrylic acid copolymer block) (1) Propylene-α-olefin copolymer [manufactured by Mitsui Chemicals, Inc. "Toughmer XR110T" (trade name)]
500 g is put into a 1 liter reactor and the internal temperature is 390 ° C.
And stirred for 2 hours to obtain a propylene-α-olefin copolymer having a double bond at a terminal. The amount of terminal double bonds was 188.7 μmol / g. (2) 100 parts by weight of a propylene-α-olefin copolymer having a double bond at a terminal obtained in the above (1),
300 parts by weight of xylene and 4.3 parts by weight of thio-S-acetic acid were put into a reactor, and the inside of the reactor was sufficiently purged with nitrogen.
0.1 parts by weight of 2,2′-azobisisobutyronitrile was added and reacted at 90 ° C. for 2 hours to produce a propylene-α-olefin copolymer having a thioacetyl group at a terminal. The amount of terminal thioacetyl groups was 179.2 μmol /
g, and the addition reaction rate was 95%. (3) 100 parts by weight of the propylene-α-olefin copolymer having a thioacetyl group at the terminal obtained in (2) above is dissolved in a mixed solvent of 120 parts by weight of xylene and 30 parts by weight of n-butanol, 4% n- of sodium oxide
A propylene-α-olefin copolymer having a mercapto group at a terminal was produced by adding 5.7 parts by weight of a butanol solution and reacting at reflux temperature of toluene in nitrogen for 1 hour. The amount of terminal mercapto groups was 175.6 μmol /
g, and the addition reaction rate was 98%.

(4) 100 parts by weight of the propylene-α-olefin copolymer having a terminal mercapto group obtained in the above (3) is dissolved in 150 parts by weight of xylene, and 80 parts by weight of ethyl acrylate and acrylic acid are added thereto. 10 parts by weight, and 1,1′-azobis (cyclohexane-1-carbonitrile) were added in nitrogen at 90 ° C. so that the polymerization rate was about 10% per hour, and the polymerization rate was 95%.
The reaction was stopped when it became. After cooling the reaction solution, the solvent was removed, and a propylene-α-olefin copolymer block (A) and an ethyl acrylate-acrylic acid copolymer block (B) [ethyl acrylate: acrylic acid =
90:10 (weight ratio)] to obtain an AB-type diblock copolymer (hereinafter, referred to as “block copolymer (I-1)”). Obtained block copolymer (I-1)
The number average molecular weight of the polymer block (A) is 5,300;
The number average molecular weight of the polymer block (B) was 4,500, and the number average molecular weight of the block copolymer (I-1) was 9,800.
And the melting point was 103 ° C. 50 g of the obtained block copolymer (I-1) and 250 g of xylene were put into a 0.5-liter reaction tank equipped with a stirrer and a condenser, and were dissolved at 100 ° C. Next, 300 g of a 0.1% aqueous sodium hydroxide solution was supplied into the system over a period of 1 hour using a dropping funnel to obtain a xylene-water suspension. Xylene in this suspension was distilled off to obtain a crude aqueous emulsion. 300 g of this crude aqueous emulsion (resin content 50 g) and 28%
3.9 g of aqueous ammonia was charged into a pressurized reaction vessel, and 16
Stirred at 0 ° C. for 1 hour. After stirring, the mixture was cooled to room temperature to obtain an aqueous dispersion (I-1). The resulting aqueous dispersion (I-
The dispersion material of 1) was a true sphere and had an average particle diameter of 0.3 μm. This aqueous dispersion (I-1) was stable without any change in particle diameter even after being allowed to stand for one week.

Production Example 2: Block copolymer (I-2)
Production of Aqueous Dispersion (I-2) of (Polypropylene Block / Ethyl Acrylate-Acrylic Acid Copolymer Block) (1) One liter of 500 g of polypropylene [Mitsubishi Noblen MH8 (trade name) manufactured by Mitsubishi Chemical Corporation] And the temperature was raised until the internal temperature reached 390 ° C.
By stirring for a period of time, a polypropylene having a double bond at a terminal was obtained. The amount of terminal double bonds was 232.5 μmol / g. (2) 100 parts by weight of the polypropylene having a double bond at the end obtained in the above (1), 300 parts by weight of xylene, and 5.3 parts by weight of thio-S-acetic acid were put into a reactor, and the inside was sufficiently nitrogen-containing. After the substitution, 0.2 parts by weight of 2,2′-azobisisobutyronitrile was added and reacted at 90 ° C. for 2 hours to produce a polypropylene having a terminal thioacetyl group. The amount of terminal thioacetyl groups was 218.6.
μmol / g, and the addition reaction rate was 94%. (3) 100 parts by weight of the polypropylene having a terminal thioacetyl group obtained in the above (2) was mixed with xylene 120
In a mixed solvent of 30 parts by weight of n-butanol and 30 parts by weight of n-butanol.
By adding a part by weight and reacting at reflux temperature of toluene in nitrogen for 1 hour, a polypropylene having a mercapto group at a terminal was produced. The amount of terminal mercapto groups is 21
It was 4.2 μmol / g, and the addition reaction rate was 98%.

(4) 100 parts by weight of the polypropylene having a terminal mercapto group obtained in the above (3) was dissolved in 150 parts by weight of xylene, and ethyl acrylate 8 was added thereto.
0 parts by weight and acrylic acid 10 parts by weight,
At 0 ° C., 1,1′-azobis (cyclohexane-1-carbonitrile) was added so that the polymerization rate was about 10% per hour, and the reaction was stopped when the conversion reached 90%. After cooling the reaction solution, the solvent was removed, and AB composed of a polypropylene block (A) and an ethyl acrylate-acrylic acid copolymer block (B) [ethyl acrylate: acrylic acid = 90: 10 (weight ratio)].
Type diblock copolymer (hereinafter, referred to as “block copolymer (I)
-2) "). The number average molecular weight of the polymer block (A) of the obtained block copolymer (I-2) was 4,300, the number average molecular weight of the polymer block (B) was 3,800, and the block copolymer (I- The number average molecular weight of 2) was 8,100 and the melting point was 148 ° C. 50 g of the obtained block copolymer (I-2) and 250 g of xylene were put into a 0.5-liter reaction tank equipped with a stirrer and a condenser, and were dissolved at 100 ° C. Next, 0.
300 g of a 1% aqueous sodium hydroxide solution was supplied into the system over a period of 1 hour using a dropping funnel to obtain a xylene-water suspension. Xylene in this suspension was distilled off to obtain a crude aqueous emulsion. 300 g of this coarse aqueous emulsion (resin content 50
g) and 3.9 g of 28% aqueous ammonia were charged into a pressurized reaction vessel and stirred at 160 ° C. for 1 hour. After stirring, the mixture was cooled to room temperature to obtain an aqueous dispersion (I-2). The dispersion material of the obtained aqueous dispersion liquid (I-2) was a true sphere, and the average particle diameter was 0.3 μm. This aqueous dispersion (I-2) was stable without any change in particle diameter even after being allowed to stand for one week.

Production Example 3: Block copolymer (I-3)
Production of aqueous dispersion (I-3) of (propylene-α-olefin copolymer block / ethyl acrylate-maleic anhydride copolymer block) having a mercapto group at a terminal obtained in Production Example 1 (3) 100 parts by weight of a propylene-α-olefin copolymer was dissolved in 150 parts by weight of xylene, and 80 parts by weight of ethyl acrylate and 10 parts by weight of maleic anhydride were added thereto.
At 90 ° C. in nitrogen, 1,1′-azobis (cyclohexane-1-cyclohexane) is used such that the polymerization rate is about 10% per hour.
(Carbonitrile) was added, and the reaction was stopped when the conversion reached 95%. After cooling the reaction solution, the solvent was removed,
Propylene-α-olefin copolymer block (A) and ethyl acrylate-maleic anhydride copolymer block (B) [ethyl acrylate: maleic anhydride = 9
0:10 (weight ratio)] to obtain an AB-type diblock copolymer (hereinafter referred to as “block copolymer (I-3)”). The number average molecular weight of the polymer block (A) of the obtained block copolymer (I-3) was 5,300, the number average molecular weight of the polymer block (B) was 3,000, and the block copolymer (I- The number average molecular weight of 3) was 8,300 and the melting point was 103 ° C. 50 g of the obtained block copolymer (I-3) and 250 g of xylene were put into a 0.5-liter reaction tank equipped with a stirrer and a condenser, and were dissolved at 100 ° C. Next, 300 g of a 0.1% aqueous sodium hydroxide solution was supplied into the system over a period of 1 hour using a dropping funnel to obtain a xylene-water suspension. Xylene in this suspension was distilled off to obtain a crude aqueous emulsion. 300 g of this crude aqueous emulsion (resin content 50 g) and 28%
3.9 g of aqueous ammonia was charged into a pressurized reaction vessel, and 16
Stirred at 0 ° C. for 1 hour. After stirring, the mixture was cooled to room temperature to obtain an aqueous dispersion (I-3). The resulting aqueous dispersion (I-
The dispersion material of 3) was a true sphere and had an average particle size of 0.2 μm. This aqueous dispersion (I-3) was stable without any change in particle diameter even after being allowed to stand for one week.

Production Example 4: Block copolymer (I-1)
Production of aqueous dispersion (I-4) comprising (propylene-α-olefin copolymer block / ethyl acrylate-acrylic acid copolymer block) and propylene-α-olefin copolymer In Production Example 1, (4) The obtained block copolymer (I-
1) 40 g and 10 g of a propylene-α-olefin copolymer (“Tuffmer XR110T” (trade name) manufactured by Mitsui Chemicals, Inc.) and 250 g of xylene were placed in a 0.5-liter reaction tank equipped with a stirrer and a condenser, and 100 g ° C
And dissolved. Next, 300 g of a 0.18% aqueous sodium hydroxide solution was supplied into the system over a period of 1 hour using a dropping funnel to obtain a xylene-water suspension. Xylene in this suspension was distilled off to obtain a crude aqueous emulsion. 300 g of this crude aqueous emulsion (resin content: 50 g) and 3.4 g of 28% aqueous ammonia were charged into a pressurized reaction vessel.
Stirred for hours. After stirring, the mixture was cooled to room temperature to obtain an aqueous dispersion (I-4). The dispersion material of the obtained aqueous dispersion (I-4) was a true sphere, and the average particle diameter was measured.
m. The aqueous dispersion (I-4) was stable without any change in particle diameter even after being allowed to stand for one week.

Production Example 5: Polyurethane resin (III-3)
Preparation of an aqueous dispersion of a poly (3- (3- (3-isopropane diisocyanate) having a number average molecular weight of 2000) was placed in a three-necked flask equipped with a cooling tube.
Methyl-1,5-pentylene / hexamethylene carbonate) diol (prepared by reacting with 3-methyl-1,5-pentanediol and 1,6-hexanediol in a 1: 1 weight ratio with diethyl carbonate) 18
0.0 g, 2,2-bis (hydroxymethyl) butyric acid 1
5.3 g and 153.2 g of 2-butanone were weighed, and stirred at 70 ° C. for 4 hours in a dry nitrogen atmosphere to quantitatively react hydroxyl groups in the system.
-A butanone solution was prepared. Then cool to 40 ° C,
An aqueous solution in which 10.5 g of triethylamine was dissolved in 250.6 g of distilled water was added over 1 minute, and the mixture was further stirred for 3 minutes to emulsify. Next, 259.9 g of distilled water was added and the mixture was stirred for 3 minutes, and then piperazine hexahydrate 21.2.
g, 2.5 g of diethylenetriamine and 67.2 g of distilled water
Was added over 1 minute, and the mixture was further stirred for 3 hours to carry out a chain extension reaction. Thereafter, 2-butanone was removed by a rotary evaporator to obtain an aqueous dispersion of a polyurethane resin (III-3) having a solid content of 33% by weight. The average particle size of the dispersed substance in the obtained aqueous dispersion was 0.2 μm. The aqueous dispersion was stable with no change in particle diameter even after standing for one week.

Examples 1 to 9 To the aqueous dispersions (I) produced in Production Examples 1 to 4, an emulsion of the following tackifier (II), polyurethane resin or vinyl polymer (III) was added. The compound was added in the amount shown in Table 1 in terms of solid content, and sorbitol polyglycidyl ether (“Denacol 611” manufactured by Nagase Kasei Co., Ltd.) as an epoxy compound was further added as a curing agent (IV) to the solid content of the aqueous dispersion (I). Table 1 in terms of solid content based on the total amount of polyurethane resin or vinyl polymer (III)
To prepare an aqueous dispersion. 70 ° C
This aqueous dispersion was spray-coated on a polypropylene molded plate washed with hot water so that the film thickness after drying was 10 μm, dried at 50 ° C. for 30 minutes, and dried at a temperature shown in Table 1.
Annealing treatment was performed for 5 minutes. On the other hand, a mixture of 10 parts by weight of a two-part urethane paint ("Retane PG" (trade name), manufactured by Kansai Paint Co., Ltd.) and 1 part by weight of a urethane curing agent was applied as a top coating so that the film thickness became 50 μm. 5
After drying at 0 ° C. for 1 hour, annealing was performed at the heat treatment temperature shown in Table 1. Table 1 shows the results of the paintability test.
Table 2 shows the results of the heat lamination adhesion test for some examples.

As the emulsion of the tackifier (II) and the polyurethane resin or the vinyl polymer (III), the following were used. -Tackifier (II) (II-1) "Alcon P-100" (trade name, manufactured by Arakawa Chemical Co., Ltd.) (II-2) "Escolets 5300" (trade name, manufactured by Tonex Corporation)-Polyurethane Emulsion of resin or vinyl polymer (III) (III-1) Ethylene-vinyl acetate copolymer emulsion ["OM4200" (trade name), manufactured by Kuraray Co., Ltd.] (III-2) Acrylic emulsion [[Yodosol A
D76 "(trade name), manufactured by Kanebo NSC] (III-3) Urethane-based emulsion (aqueous dispersion obtained in Production Example 5)

Comparative Example 1 An aqueous dispersion of a commercially available chlorinated polypropylene [“Hardlen EH202”] was used instead of the aqueous dispersion (I).
(Trade name), manufactured by Toyo Kasei Co., Ltd.], and an aqueous dispersion was prepared in the same manner as in the example, and a coating test and a heat lamination adhesion test were performed. The results are shown in Tables 1 and 2.

Reference Example 1 An aqueous dispersion was prepared in the same manner as in Example 1 except that the tackifier (II) was not used, and a coating property test and a heat lamination adhesion test were performed. The results are shown in Tables 1 and 2.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

According to the present invention, there is provided an aqueous dispersion having excellent adhesiveness and adhesion to various substrates, storage stability, weather resistance, water resistance, solvent resistance and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101: 00) C08L 101: 00 (72) Inventor Yukijun Komiya 2045 Sakurazu, Kurashiki-shi, Okayama Pref. (72) Inventor Kazuhiko Maekawa Inventor Kazuhiko Maekawa United States of America New York Tuckahoe Columbus Avenue 50 F term (reference) FD050 FD070 FD140 FD32X GH00 GH01 GJ01 HA07 4J038 CQ001 KA10 MA08 MA10 4J040 DM001 JA03 KA26

Claims (14)

[Claims] 1. A polymer block (A) mainly composed of an olefin monomer unit and 2 to 100 mol% of a vinyl monomer having a carboxyl group or a carboxylic anhydride group, and 2 to 100 mol% of the vinyl monomer. A block copolymer (I) composed of a polymer block (B) composed of 98 to 0 mol% of a unit of another copolymerizable vinyl monomer with respect to the carboxyl group or carboxylic anhydride group 0.0
An aqueous dispersion comprising a tackifier (II) and an aqueous dispersion (I) dispersed in an aqueous solution of 5 or more equivalents of a basic substance. 2. The aqueous dispersion according to claim 1, wherein the weight ratio of the solid content in the aqueous dispersion (I) to the tackifier (II) is from 99.9: 0.1 to 50:50. 3. The aqueous dispersion according to claim 1, wherein the tackifier (II) is a saturated petroleum resin. 4. The polymer block (A) has a number average molecular weight of 1,000 to 100,000, and the polymer block (B) has a number average molecular weight of 1,000 to 100,000. 4. The aqueous dispersion according to any one of 3. 5. The polymer block (B) comprises 2 to 50 mol% of a vinyl monomer having a carboxyl group or a carboxylic anhydride group and another vinyl monomer copolymerizable with the vinyl monomer. The aqueous dispersion according to any one of claims 1 to 4, which is a polymer block composed of 98 to 50 mol% of units of a monomer. 6. A polymer block (A) comprising polyethylene, polypropylene, propylene-ethylene copolymer,
Propylene-α-olefin copolymer or ethylene-
The aqueous dispersion according to any one of claims 1 to 5, which is a polymer block derived from an α-olefin copolymer. 7. An aqueous dispersion obtained by further mixing an aqueous dispersion or aqueous solution of a polyurethane resin or a vinyl polymer (III) with the aqueous dispersion according to any one of claims 1 to 6. 8. The weight ratio of the total amount of the solid content and the tackifier (II) in the aqueous dispersion (I) to the polyurethane resin or the vinyl polymer (III) is from 5:95 to 95: 5. An aqueous dispersion according to claim 7. 9. The aqueous dispersion according to claim 7, wherein the vinyl polymer is at least one resin selected from the group consisting of a (meth) acrylic resin, a styrene resin, and a vinyl ester resin. . 10. An aqueous dispersion obtained by further adding a curing agent (IV) to the aqueous dispersion according to any one of claims 1 to 9. 11. The aqueous dispersion (I) further contains an olefin polymer in a proportion of 1 to 200 parts by weight based on 100 parts by weight of the block copolymer (I).
The aqueous dispersion according to any one of items 10 to 10. A coating agent comprising the aqueous dispersion according to any one of claims 1 to 11. 13. An adhesive comprising the aqueous dispersion according to claim 1. Description: 14. A primer comprising the aqueous dispersion according to any one of claims 1 to 11.