JPH08311145A - Aqueous resin or aqueous cross-linked particle and their production - Google Patents

Abstract

PURPOSE: To produce an aqueous resin, consisting essentially of a specific prepolymer, a compound containing epoxy group and a polyamide compound, having ultrahigh solvent resistance under low-temperature baking conditions and further toughness of a urethane itself and useful as a coating material, etc. CONSTITUTION: This aqueous resin is obtained by mixing (A) a prepolymer, having isocyanate groups and capable of being solubilized or dispersible in water with (B) a compound containing epoxy group (e.g. bisphenol A glycidyl ether), dispersing the resultant mixture in water, then reacting the prepared mixed dispersion with (C) a polyamine compound having active hydrogen (e.g. ethylenediamine). Furthermore, each average number of isocyanate groups in the component (A), epoxy groups in the component (B) and primary or secondary amino groups in the component (C) in one molecule is preferably >=1.5 and at least one thereof is preferably >=2.5.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous resin or aqueous crosslinked fine particles, and a novel and useful method for producing the aqueous resin or aqueous crosslinked fine particles, respectively. More specifically, the present invention is a so-called epoxy / urethane / urea obtained by reacting a water-soluble or water-dispersible prepolymer having an isocyanate group, an epoxy group-containing compound, and a polyamine compound having active hydrogen. The present invention relates to a resin, which is a specific aqueous resin or aqueous crosslinked fine particles, and a novel method for producing the aqueous resin or aqueous crosslinked fine particles.

The epoxy / urethane / urea resin obtained by the method of the present invention is widely used for paints, inks, adhesives and paper fiber finishing agents. , Can be used and applied.

[0003]

2. Description of the Related Art A self-water-dispersible resin having an isocyanate group at the molecular end is dispersed in water, and a so-called polyfunctional active hydrogen compound such as polyamine is used to extend the chain inside the dispersed particles. For example, Japanese Patent Publication S54-
No. 22236, Japanese Patent Publication No. 63-8141, Japanese Patent Publication No. 64-11227, and the like.

Further, in JP-A-3-128912 or JP-A-4-249517, for the purpose of improving water resistance or solvent resistance, a hydrophobic polyisocyanate compound is used together with a self-water-dispersible resin. A method is also disclosed in which, after being dispersed in water, the inside of dispersed particles is crosslinked with a so-called polyfunctional active hydrogen compound such as polyamine, thereby increasing the crosslinking density of the dispersed particles. Has been done.

[0005]

Urethane resins generally form extremely tough films, but they cannot be said to have sufficient solvent resistance. Particularly, in the case of the aqueous urethane resin, JP-A-3-128912 or JP-A-4-249517 is used.
Even with the method disclosed in the publication, satisfactory solvent resistance can only be obtained by baking at a high temperature of about 150 ° C. or higher.

However, urethane resins are generally
It is prone to thermal decomposition, and baking at high temperature causes other problems such as yellowing and deterioration of physical properties.

Therefore, when a film is formed with such a urethane resin, it is rather desired that it exhibits sufficient solvent resistance under baking conditions at a so-called low temperature of 130 ° C. or lower. However, under such a low temperature baking condition, even if the above-mentioned cross-linked particles having an improved degree of cross-linking are used, they alone have sufficient solvent resistance. It's not that you can get things.

In addition to this, when an aminoplast resin such as a melamine resin or a water-soluble epoxy resin is used together as a cross-linking agent in order to impart such solvent resistance, this solvent resistance is very high. Although it becomes higher, the resulting coating is apt to be brittle, and the toughness characteristic of the polyurethane resin coating is impaired.

[0009] Therefore, the problem to be solved by the present invention is excellent without impairing the original toughness of the urethane resin film, and even if it is baked at a low temperature, the crosslinking agent of the class is not used in combination. Having solvent resistance,
It is to provide an extremely highly practical aqueous resin or aqueous crosslinked fine particles, and also to provide a method for producing the same.

[0010]

Means for Solving the Problems Accordingly, the present inventors have:
As mentioned above, focusing on the problem to be solved by the invention, as a result of earnestly studying, the urethane resin film has toughness peculiar to the film, and at the time of low temperature baking, no crosslinking agent is added. In particular, the present invention is completed by finding an extremely practical aqueous resin or aqueous crosslinked fine particles having excellent solvent resistance without using them, and also finding a manufacturing method thereof. Came to.

That is, the present invention basically comprises a water-soluble or water-dispersible prepolymer (A) having an isocyanate group, an epoxy group-containing compound (B), and a polyamine compound (C) having active hydrogen. ) And, as an essential reaction component, to provide an aqueous resin or aqueous crosslinked fine particles obtained by reacting

In addition, a water-soluble or water-dispersible prepolymer (A) having an isocyanate group and an epoxy group-containing compound (B) are mixed and dispersed in water, and then this mixed dispersion is obtained. The present invention also provides a method for producing an aqueous resin or aqueous crosslinked fine particles, which comprises reacting a polyamine compound (C) having active hydrogen.

Here, the above-mentioned "aqueous resin" and the above-mentioned "aqueous crosslinked fine particles" are basically the term "aqueous resin", which has a relation that can be unified. However, it is considered necessary to use both of these terms properly depending on whether or not they are cross-linked in the case of accurately grasping the substance.

In the present invention, also from this point of view, the term "aqueous resin or aqueous crosslinked fine particles" is intentionally written in a slightly long term, but in short, the resin is crosslinked. In the form of fine particles, the so-called aqueous crosslinked fine particles are referred to as "aqueous resin", and also referred to as "aqueous crosslinked fine particles". , It has a relationship of being integrated and unified in relation to the aqueous medium.

<< Structure >>

The above-mentioned water-soluble or water-dispersible prepolymer (A) having an isocyanate group, which is used for carrying out the method of the present invention, has the ability to be water-soluble or water-dispersible. As is well known, it is said that the prepolymer has a so-called hydrophilic group in the molecule, such as an ionic group in the form of a cationic group or anionic group or a nonionic group. It may be of any type.

Therefore, the prepolymer (A) is
Basically, for example, having two or more active hydrogen groups,
Moreover, the compound (a-1) having also an ionic group in the same molecule and / or a so-called nonionic group such as polyethylene glycol or polypropylene glycol chain and two or more active hydrogens as described above. Using the compound (a-2) having a group together as an essential reaction component,

The essential reaction component and the polyisocyanate compound (a-3) are used, and if necessary, the compound (a-4) having two or more active hydrogens is also used.
The thing obtained by carrying out a urethanization reaction and / or a urea formation reaction is referred to.

Here, only the particularly representative compounds (a-1) having two or more active hydrogen groups described above and also having an ionic group in the same molecule will be exemplified. As a ionic group, first of all, those having a cationic group include various N-alkyldihydroxyalkylamines such as N-methyldiethanolamine or N-ethyldiethanolamine.

Next, examples of the compound having an anionic group as the ionic group include various diol carboxylic acids such as dimethylolpropionic acid or tartaric acid, and further 5-sulfobis (β-hydroxyethyl). ) Compounds having an anionic functional group other than a carboxyl group, such as a so-called sulfoxyl group, such as isophthalate.

Further, the compound (a-4) having two or more active hydrogens and the polybasic acid or polybasic acid anhydride (a
-5) and so-called acid group-containing polyester polyols, which are obtained by subjecting them to a condensation reaction by a conventional method, also have two or more active hydrogen groups and, in the same molecule, It is exemplified as a representative example of the compound (a-1) also having an ionic group.

On the other hand, a compound (a) having two or more active hydrogens in the molecule and also having a nonionic group
As only 2), only typical examples are polyethylene glycol and the like.

The polyisocyanate compound (a-
As only 3), only typical ones are exemplified by 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate or p-phenylene diisocyanate, 4,4 ′.
-Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4 ' -Biphenylene diisocyanate, 3,3'-dichloro-4,
4'-biphenylene diisocyanate or 1,5-
Including various aromatic diisocyanates such as naphthalene diisocyanate,

Further, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate,
1,3-cyclohexylene diisocyanate or 1,
4-cyclohexylene diisocyanate, or isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate (hydrogenated xylylene diisocyanate), 3, Various aliphatic or cycloaliphatic diisocyanates such as 3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate or dimer acid diisocyanate;

Further, as described above, a multimer of various aromatic diisocyanates represented by tolylene diisocyanate and the like; as described above, represented by hexamethylene diisocyanate, isophorone diisocyanate and the like. A multimer of various aliphatic- or alicyclic diisocyanates; various aromatic-, aliphatic- or alicyclic diisocyanates as described above, and trimethylolpropane,
Examples thereof include adducts with various polyhydric alcohols (polyols) and polyisocyanates containing an isocyanurate ring.

Further, only the particularly representative examples of the compound (a-4) having two or more active hydrogens mentioned above are exemplified, ethylene glycol, 1,2-propanediol (1,2) -Propylene glycol),
1,3-propanediol (1,3-propylene glycol), 1,3-butanediol, 1,4-butanediol (1,4-butylene glycol), neopentyl glycol, 1,6-hexanediol, 3- Methyl-
1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol,
Dipropylene glycol, tripropylene glycol,
Various diol compounds such as cyclohexane-1,4-diol or cyclohexane-1,4-dimethanol or hydrogenated bisphenol A;

Various polyol compounds such as compounds having a plurality of hydroxyl groups so as to be trifunctional or more, represented by glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc .; ethylenediamine, diethylenetriamine, Various polyamine compounds such as triethylenetetramine or tetraethylenepentamine; Various polythiol compounds such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol or 2,3-butanedithiol ;

Further, as represented by thioglycerol, dithioerythritol or 1,4-dimercapto-2,3-butanediol, etc., respectively,
It is a so-called low-molecular compound such as various compounds having two or more functional groups such as a hydroxyl group, an amino group and / or a mercapto group, and in addition to these,

Condensates of various low molecular weight compounds such as those mentioned above with polybasic acids or polybasic acid anhydrides (a-5),
Alternatively, using the above-mentioned polyols as an initiator,
A polyester polyol which is a ring-opening polymerized product with various lactones, represented by γ-valerolactone or ε-caprolactone.

As described above, one or two or more kinds of compounds having two or more active hydrogens selected from various polyol compounds or polyamine compounds, polythiol compounds and the like are used as an initiator to prepare ethylene oxide. , Propylene oxide, butylene oxide,
Various cyclic ether compounds such as styrene oxide, epichlorohydrin or tetrahydrofuran, alone or in a form obtained by addition polymerization of two or more kinds by a conventional method; polyester amide polyol; poly Thioether polyols; polycarbonate polyols; polyacetal polyols; or polyolefin polyols, and also polysiloxane polyols.

Further, various hydroxyalkyl vinyl ethers typified by hydroxybutyl vinyl ether and the like; typified by hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like. Various hydroxyalkyl (meth)
Acrylates;

Various (poly) alkylene glycol mono (meth) acrylates represented by ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc .; or (meth) allyl alcohols, etc. And

Further, it is represented by a so-called hydroxyl group-containing vinyl copolymer, which is an adduct of these hydroxyl group-containing vinyl monomers and various lactones such as γ-valerolactone or ε-caprolactone. In addition, various hydroxyl group-containing vinyl monomers (a-6), other vinyl monomers as required, and a hydroxyl group-containing vinyl polymer obtained by radical polymerization by a conventional method also have two or more active groups. Compound having hydrogen (a-
It is exemplified as a representative example of 4).

As the polybasic acid or the polybasic acid anhydride (a-5) mentioned above, only the representative ones are exemplified by (anhydrous) succinic acid, (anhydrous) glutaric acid,
Adipic acid, suberic acid, azelaic acid, sebacic acid,
Phthalic acid, isophthalic acid, terephthalic acid, maleic acid (anhydrous), tetrahydrophthalic acid (anhydrous) or (anhydrous)
Including various dicarboxylic acids or dicarboxylic acid anhydrides such as hexahydrophthalic acid,

Further, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, trimellitic acid triglyceride or 5-sulfoisophthalic acid. And so on.

Alternatively, the prepolymer (A) may be a polymerizable monomer (a-7) having an isocyanate group and a polymerizable monomer (a- having an amphiphilic group which is an ionic group or a nonionic group). And 8) as essential reaction components and, if necessary, with other various polymerizable monomers (a-9) that can be copolymerized, can also be obtained by a method such as a polymerization reaction. That is.

As the polymerizable monomer (a-7) having an isocyanate group, only typical ones will be exemplified, including (meth) acryloyl isocyanate or (meth) acryloyloxyethyl isocyanate, and further, The polyisocyanate compound (a-3) as described above, preferably a diisocyanate compound, and the hydroxyl group-containing vinyl monomer (a-6) described above are obtained by addition reaction at a molar ratio of 1. Such as compounds.

A polymerizable monomer having a hydrophilic group (a-
As only 8), only typical ones are exemplified as (8), (meth) acrylic acid, crotonic acid, itaconic acid,
(Anhydrous) various carboxyl group-containing vinyl monomers such as maleic acid, fumaric acid, monobutyl itaconate or monobutyl maleate;

Various phosphoric acid group-containing vinyl monomers such as acid phosphooxyethyl methacrylate; or various sulfonic acid group-containing vinyl monomers such as 2-chloro-2-acrylamido-2-methylpropanesulfonic acid;

Alternatively, various sulfate group-containing vinyl monomers such as 2-sulfoethyl (meth) acrylate; or various tertiary groups such as represented by dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate. Examples include amino group-containing vinyl monomers.

Other typical copolymerizable monomers (a-9) which can be copolymerized are only representative ones. Styrene, vinyltoluene, 2-methylstyrene, tert-butylstyrene or Various styrenic monomers (aromatic vinyl monomers) such as chlorostyrene;

Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, ( Meta)
N-Amyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Various (meth) acrylic acid esters such as decyl acrylate or dodecyl (meth) acrylate;

Various hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; or N-methylol (meth) acrylamide or N-butoxy (meth)
Various N-substituted (meth) acrylic monomers such as acrylamide, acrylonitrile, and the like.

To exemplify only the representative epoxy group-containing compound (B) used for carrying out the method of the present invention, bisphenol A diglycidyl ether or its oligomer, bisphenol F diglycidyl Ethers or oligomers thereof, or various glycidyl ethers having a bisphenol skeleton such as "VG3101" [trade name of Mitsui Petrochemical Co., Ltd.];

Various aromatic epoxy resins such as resorcin diglycidyl ether or cresol novolac type epoxy resin; glycidyl of various alicyclic polyols such as hydrogenated bisphenol A or its oligomer, hydrogenated bisphenol F or its oligomer ether;

1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether,
Glycidyl ethers of various aliphatic polyols such as diglycerol polyglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether or sorbitol polyglycidyl ether;

Various glycidyl ester compounds such as "Celoxide 2021" [trade name of Daicel Chemical Industries, Ltd.] and "Eporide" (trade name of the same company);
Various polyglycidyl compounds having a tertiary amino group, such as N, N, N ′, N′-tetraglycidyl-m-xylenediamine or 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, or Starting with various polyglycidyl compounds having a triazine ring, such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate,

Further, an epoxy resin obtained by polymerizing various polymerizable monomers having various epoxy groups, such as glycidyl (meth) acrylate or styrene oxide, as an essential component together with various polymerizable monomers, if necessary. Group-containing vinyl copolymers; further, various polyisocyanate compounds (a-
3) and a glycidol condensate.

As will be described later, the epoxy group-containing compound (B) is dispersed in water together with the prepolymer (A), but at that time, in order to prevent the whole system from gelling, The vulcanized epoxy group-containing compound (B) is
It is desirable that the epoxy group-containing compound (B) has a structure such that it is encapsulated by the prepolymer (A), and that the epoxy group-containing compound (B) itself is hydrophobic so as to have such a structure. .

As the above-mentioned particularly representative polyamine compounds (C) having active hydrogen, which are used for carrying out the method of the present invention, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene In addition to ethylenepentamine, pentaethylenehexamine, propylenediamine, tetramethylenediamine, hexamethylenediamine or polyalkylenepolyamines, various primary or secondary amino acids such as piperazine or hydrazine. A compound in the form of having two or more groups in the molecule.

When the above-mentioned prepolymer (A), that is, the water-soluble or water-dispersible prepolymer (A) having an isocyanate group is obtained by a urethanization reaction, it goes without saying that it is used in the absence of a solvent. However,
It is desirable to use an appropriate solvent because the viscosity increases as the urethanization reaction proceeds, the reactivity decreases, and the subsequent workability also decreases.

Since any solvent having a relatively low reactivity with an isocyanate compound can be used as such a solvent,
Although not particularly limited, it is preferable to use a solvent having a relatively high hydrophilicity and a solubility in water of 5% by weight or more in order to disperse well in the subsequent water-solubilization or water-dispersion step. Furthermore, it is preferable to use a solvent having a vapor pressure higher than that of water in the subsequent desolvation step in order to facilitate the separation of the solvent and water.

Specific examples of such a solvent include acetone, methyl ethyl ketone, and ethyl acetate.

Further, the present urethanization reaction may be carried out in the absence of a catalyst, or may be carried out using various known and commonly used urethanization catalysts. As examples of this type of catalyst, only typical ones are exemplified: cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra n-butyl tin, tri n-butyl tin acetate, Examples include n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin acetate, dibutyltin dilaurate and tin octenoate.

When the prepolymer (A) is obtained by a polymerization reaction, if necessary, a suitable solvent is used, and a carboxyl group and an isocyanate group are added in the presence of a suitable polymerization catalyst. In order to avoid gelation due to the above reaction, it is desirable to carry out the polymerization reaction at 100 ° C. or lower, preferably 80 ° C. or lower.

As such a solvent, it is possible to use a solvent which can be utilized in the above-mentioned urethanization reaction. Further, only representative ones of the above-mentioned polymerization catalysts will be exemplified. , Various ethyl peroxides such as methyl ethyl ketone peroxide or methyl isobutyl ketone peroxide; various acyl peroxides such as lauroyl peroxide, benzoyl peroxide or p-chlorobenzoyl peroxide;

2,4,4-Trimethylpentyl-2-hydroperoxide, cumene hydroperoxide (cumene hydroperoxide) or tert.
Various hydroperoxides such as butyl hydroperoxide;

Dicumyl peroxide or diter
Various dialkyl peroxides such as t-butyl peroxide; butyl-4,4-di (tert-butyloxy) pentate or ethyl-3,3-di (t
various peroxyketals such as ert-amylperoxy) butyrate;

Alkyl peresters; or percarbonates, as well as various other compounds such as 2,2′-azobisisobutyronitrile or 1,1′-azobis (cyclohexane-1-carbonitrile). Azonitriles; or 2,2'-azobis (2-amidinopropane) dihydrochloride or 2,2 '
Various azoamidines such as azobis [2- (2-imidazolin-2-yl) propane].

Although the amount of the epoxy group-containing compound (B) used with respect to the prepolymer (A) is not particularly limited, it means that the epoxy group-containing compound (B) is used as the crosslinking agent. Therefore, a small amount does not sufficiently crosslink, while a large amount reduces the water-solubilizing or water-dispersing ability of the mixed solution.

The epoxy group in the epoxy group-containing compound (B) is about 5 to 100 mol% with respect to the isocyanate group in the prepolymer (A), and further, to 100 parts of the prepolymer (A). Therefore, it is desirable to use the epoxy group-containing compound (B) within the range of about 0.5 to 100 parts by weight, and more preferably within the range of 1 to 50 parts by weight.

Further, in order that the obtained aqueous resin has toughness, the molecular weight between crosslinks is about 500.
It is desirable that the average number of the isocyanate groups in the isocyanate prepolymer (A) in one molecule is approximately 1.7 to approximately 2.3. In addition, the isocyanate equivalent weight in the prepolymer (A) is about 400 to about 4,000.
It is desirable to be within the range of 0.

For the same reason, the epoxy group-containing compound (B) has a number average molecular weight in the range of about 300 to about 3,000. ) Is about 200 to about 3.0
It is desirable to have an epoxy equivalent in the range of 00.

The above-mentioned prepolymer (A) has an ionic group, and the prepolymer (A) itself has an ionic group.
When the ionic group is an anionic group,
At a desired point of time, that is, before or after the urethanization reaction, or before or after the polymerization reaction, a part or all of the anionic group is treated with a known and commonly used suitable basic compound. By being soaked, if it is appropriately made into a form such as an alkali metal salt, an alkaline earth metal salt, or an amine salt, it has a water-solubilizing or water-dispersing ability.

Of course, in the case of neutralizing at the time of dispersion, the prepolymer (A) may be neutralized and then dispersed in water, or the basic compound may be dissolved or dispersed in water. It is also possible to disperse the mixed solution containing the prepolymer (A) in this so that it is dispersed in water at the same time as the neutralization.

When the prepolymer (A) has an ionic group and the ionic group is a cationic group, at a desired time, that is, before the urethanization reaction. Alternatively, after the reaction, or before or after the polymerization reaction, a part or all of the cationic groups are neutralized with a suitable acidic compound which is well known and commonly used. It has the ability to be converted or dispersed in water.

Further, in the case where the prepolymer (A) has an ionic group and the ionic group has a tertiary amino group as a cationic group, at a desired time, That is, before or after the urethanization reaction,
Alternatively, before or after the polymerization reaction, the amino group is quaternized with a known and appropriate appropriate alkylating agent, so that, for example, a tertiary ammonium salt or a quaternary ammonium salt is appropriately used. With such a form, it becomes a process having water-solubilizing or water-dispersing ability.

As only basic compounds to be used in the neutralization, only representative ones are exemplified, and various hydroxides of various alkali metals such as sodium hydroxide and potassium hydroxide; barium hydroxide. And various hydroxides of alkaline earth metals; various amines such as triethylamine, dimethylethanolamine or tributylamine; or aqueous ammonia.

On the other hand, if only representative examples of acidic compounds used for neutralization are given,
Various mineral acids such as hydrochloric acid, nitric acid or sulfuric acid; or various organic acids such as formic acid, acetic acid, butyric acid or oxalic acid.

In order to disperse a solution of a mixture of the prepolymer (A) and the epoxy group-containing compound (B) in water, the prepolymer (A) having a water-solubilizing or water-dispersing ability is used. , The epoxy group-containing compound (B), and the polymer solution is diluted with a solvent, if necessary.
Water may be added to the mixture with stirring, or conversely, the polymer solution may be added to water with stirring.

The stirring at that time may be carried out by using a known and commonly used high shear type agitator such as a homogenizer or a homodisper, or a known and commonly used so-called general-purpose agitator. Good.

Generally, in the case where the water dispersibility of such a prepolymer is low, a well-known and commonly used high-share type agitator such as homodisper is used, while the water dispersibility is high. In the case of one, it is desirable to use a so-called low-share type stirrer such as a general-purpose stirrer in order to simply and stably obtain an aqueous dispersion of a polymeric substance of this type.

Prepolymer (A) and epoxy-containing compound (B) obtained by carrying out the process of the invention
The dispersion consisting of is particularly good in dispersion stability, and can be sufficiently dispersed without using a dispersant or the like, and can withstand use. For further improvement, a relatively hydrophilic solvent such as acetone, methyl ethyl ketone (MEK) or isopropyl alcohol may be used as a co-solvent.

Needless to say, a dispersant, an emulsifying agent, a protective colloid, or the like may be used in a slight amount in combination in order to improve the dispersion stability.

Specific examples of such emulsifiers include, but are not limited to, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, and polyoxyethylene sorbitol tetraoleate. , Various nonionic emulsifiers;

Various fatty acid salts such as sodium oleate, various alkyl sulfate ester salts, various alkylbenzene sulfonates, various alkyl sulfosuccinates, naphthalene sulfonates, various alkane sulfonate sodium salts or Examples include various anionic emulsifiers represented by various sodium salts of alkyldiphenyl ether sulfonate; and various nonionic anionic emulsifiers represented by polyoxyethylene alkylphenyl sulfate.

The dispersion of the prepolymer (A) and the epoxy group-containing compound (B) dispersed in water was crosslinked inside the dispersion with a polyamine compound (C) having active hydrogen. Furthermore, by removing the solvent and appropriately concentrating, the desired aqueous resin can be obtained.

More specifically, when the polyamine compound (C) having active hydrogen is used, the polyamine compound is diluted with water and then added to the water dispersion, whereby the prepolymer ( The isocyanate group in A), the amino group having active hydrogen in the polyamine compound (C), and the epoxy group-containing compound (B)
The epoxy group therein and the amino group having active hydrogen in the polyamine compound (C) react with each other to crosslink the inside of the dispersion resin and form a crosslinked particle.

The amount of the polyamine compound (C) used is
It can be appropriately adjusted depending on the desired degree of cross-linking, but in general, one of isocyanate group and epoxy group
A ratio of about 0.5 to about 1 equivalent is appropriate for the equivalent,

Considering that the remaining isocyanate groups may react with water, and that excess polyamine causes so-called unfavorable problems such as deterioration of dispersion stability, yellowing and offensive odor.

It can be said that an appropriate amount of the polyamine compound (C) used is a ratio of about 0.8 to about 0.95 equivalent to 1 equivalent of the isocyanate group and the epoxy group.

In the present invention, the secondary amine 1
Both the isocyanate group and the epoxy group are defined as 1 equivalent by mole, and the isocyanate group is defined as 1 equivalent by mole with respect to the primary amine. In addition, the epoxy group is defined as an equivalent by 0.5 mol.

The aqueous resin obtained according to the method of the present invention is preferably micro-crosslinked in the system, and preferably forms an ultrafine crosslinked particle structure, so-called microgel.

In order to obtain such a crosslinked structure, the functionality of the isocyanate group in the prepolymer (A) having an isocyanate group is set to a, and the functionality of the epoxy group in the epoxy group-containing compound (B) is set to a. Is b, the functionality of the primary amino group in the polyamine compound (C) is c, and the functionality of the secondary amino group is d.

The amount of the prepolymer (A) having an isocyanate group is a'mol, the amount of the epoxy group-containing compound (B) is b'mol, and the amount of the polyamine compound (C) is c '. If the mole is

[0086]

[Equation 1]

It is desirable to satisfy the following.

Further, an isocyanate group in the prepolymer (A), an epoxy group in the epoxy group-containing compound (B),
The average number of active hydrogens in the polyamine compound (C) in one molecule is about 1.5 or more, and at least one of them is about 2.5 or more. Is desirable.

Thus, the crosslinked polyurethane resin solution is
The removal of the solvent and the treatment such as concentration are performed to obtain the aqueous resin which is the object of the present invention.

The target resin obtained according to the method of the present invention has a resin composition of the prepolymer, an acid value, a degree of neutralization, or the like, which is about 5 nano.
With an area of meter (nm) or more, any size,
It can be freely designed and adjusted, but also because it can be stably dispersed in water,

Usually, the average particle size is about 5 microns (μ
m) is suitable, and preferably less than 1 μm. However, although it is possible to obtain particles having a particle size of less than 5 nm, it is difficult to measure the particle size itself, and in that sense, it is not a preferable process.

When the average particle size is less than 100 nm, the so-called water dispersion, which is almost transparent and has a white color rather than a light white color, is still a water dispersion. It is common to refer to it, and because of this trend, resin solutions of this class are generally not referred to as resin dispersions.

However, even if a polymer mixture in the form of a gelled composition is dispersed in water, the system does not show a gel state, and it has a high fluidity.
It cannot be said to be a water-soluble type, and since a so-called water dispersion, which exhibits a white color around 1 μm, can also be obtained according to the method of the present invention, a resin dispersion having high transparency is intentionally used here. The form including it will be called an aqueous dispersion.

The water-based resin obtained as described above is used in various forms according to the respective purposes and uses, but it may be spray-dried, centrifugal-dried, filtered-dried or It can be used as a fine powder by a conventionally known means such as a freeze-drying method, and further, the fine powder thus obtained is dispersed in a solvent, or the fine powder is re-neutralized. Then, it can be used and applied in the form of redispersion in water.

The aqueous resin obtained by the method of the present invention is
It can be used and applied as it is, and various substances can be included in such a crosslinked polyurethane resin, and further, other dispersions thereof can be blended.

At this time, if only representative examples of substances that can be encapsulated are given, pigments, colorants,
Various industrial materials such as cross-linking agents, catalysts, UV absorbers, antioxidants, rust preventives, plasticizers, adhesives, detergents, enzymes, food additives or fragrances, including various mining industries.

Further, it is various agricultural chemicals such as herbicides, fungicides or insecticides, and further various medical supplies such as medicines and pharmaceuticals.

Actually, in the case of encapsulating various substances as listed above, it is necessary to mix the prepolymer (A), the epoxy group-containing compound (B) and various substances to be encapsulated, and According to the above, after kneading, water dispersion may be carried out by a method similar to the above-mentioned method. Further, the inside of the dispersed particles may be crosslinked with a polyamine compound (C). It can be done by incarnation.

Further, to exemplify only the representative dispersions that can be blended, vinyl acetate-based dispersions,
Various emulsions such as acrylic or acrylic-styrene based; various latexes such as styrene-butadiene based, acrylonitrile-butadiene based or acrylic-butadiene based;

Various ionomers such as polyethylene-based or polyolefin-based; or polyurethane,
Various water dispersions such as polyester, polyamide or polyepoxy type.

The target water-based resin is mainly used by itself, or by incorporating or encapsulating various substances as described above, mainly for indoor / outdoor building materials or industrial use, etc. As a variety of paints, a so-called resin modifier, which can be used by being applied as various inks such as water-based gravure ink, and is added for the purpose of improving various physical properties. As

Alternatively, it can also be used and applied as an adhesive, a surface treatment agent or a fiber treatment agent,
Furthermore, it is extremely practical, being applicable as a film, various molding materials, and various synthetic leathers.

[0103]

EXAMPLES Next, the present invention will be explained more specifically with reference to synthetic examples, examples and comparative examples, but the present invention is never limited to these illustrative examples. It's not like that.

In the following, all parts and% are based on weight unless otherwise specified.

The outline of each evaluation judgment test is as follows.

First, in the solvent resistance test, the obtained aqueous resin was applied onto a glass plate so that the dry film thickness was 40 μm, air-dried for 30 minutes, and then at 120 ° C. for 20 minutes. , A film formed by baking,
Using the "rubbing tester" [trade name of Ohira Rika Kogyo Co., Ltd.], the felt impregnated with MEK
The value until the film was broken was measured by rubbing while applying a load of 1.5 kilogram (kg), and the value was shown.

In the tensile physical property test, the obtained aqueous resin was coated on a tin plate so that the dry film thickness was 40 μm, air-dried for 30 minutes, and then at 20 ° C. for 20 minutes.
During the period of time, the film formed by baking was peeled off to form a film having a predetermined size, and the film was measured with "Autograph AGS-100A" [trade name of Shimadzu Corporation].

Synthesis Example 1 [Preparation Example of Prepolymer (A)] A 2-liter four-necked flask equipped with a thermometer-equipped nitrogen gas introducing tube, a stirrer and a reflux condenser was placed in a nitrogen gas atmosphere and subjected to 212 "[trade name of polycaprolactone diol manufactured by Daicel Chemical Industries, Ltd.] and 333 parts of isophorone diisocyanate were charged in a four-necked flask and heated to 110 ° C to 1 Stirring was allowed to continue for a period of time.

Then, the mixture was cooled to 80 ° C., and 2,2-
Add 67 parts of bis (hydroxymethyl) propionic acid, stir for 30 minutes, then add MEK
And 0.05 part of dibutyltin dilaurate were added, and stirring was continued for 6 hours to obtain a solution of the prepolymer (A) having a dry solid content ratio of 67.0%. Was given. Below, this (A-
Abbreviated as 1).

Synthetic Example 2 (same as above) [0110] The dry solid content ratio was 67.2% in the same manner as in Synthetic Example 1 except that the same amount of ethyl acetate was used instead of MEK as the solvent. A solution of the target prepolymer (A) was obtained. Hereinafter, this is abbreviated as (A-2).

Synthesis Example 3 (Same as above) In a 2-liter four-necked flask equipped with a nitrogen gas inlet tube with a thermometer, a stirrer and a reflux condenser, 625 parts of "Plaxel 212" and 261 of tolylene diisocyanate were added. And 4 parts were placed in a four-necked flask and stirred at 80 ° C. for 1 hour in a nitrogen gas atmosphere.

Then, N-methyldiethanolamine 6
A solution of prepolymer (A) having a dry solids ratio of 65.6% was obtained by adding 0 part and 500 parts of MEK and further continuing stirring for 6 hours. Hereinafter, this is abbreviated as (A-3).

Synthesis Example 4 (same as above) A 2-liter four-necked flask equipped with a nitrogen gas inlet tube with a thermometer, a stirrer and a reflux condenser was charged with 1000 parts of polyethylene glycol 2000 and 222 parts of isophorone diisocyanate. , MEK (500 parts) and dibutyltin dilaurate (0.05 parts) were charged in a four-necked flask, heated to 80 ° C. in a nitrogen gas atmosphere, and allowed to continue stirring for 8 hours. As a result, a solution of the prepolymer (A) having a dry solid content ratio of 71.0% was obtained. Hereinafter, this is abbreviated as (A-4).

Synthesis Example 5 [Preparation Example of Epoxy Group-Containing Compound (B)] A 1-liter four-necked flask equipped with a thermometer-equipped nitrogen gas introducing tube, a stirrer and a reflux condenser was charged with "Bernock DN-980". [Product name of polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc .; solid content = 75.2
%], 83 parts of 2,3-epoxy-1-propanol, 100 parts of ethyl acetate and 0.01 parts of dibutyltin dilaurate.

Then, in a nitrogen gas atmosphere, the temperature was raised to 60 ° C., and stirring was continued for 4 hours to obtain a solution of the epoxy group-containing compound (B) having a dry solid content ratio of 64.0%. Was obtained. Hereafter, this (B-1)
Abbreviated.

Example 1 20 of the prepolymer solution (A-1) obtained in Synthesis Example 1
0 part was neutralized with 7.9 parts of triethylamine, and further 52. of "Epiclone 1055" [trade name of diepoxy compound manufactured by Dainippon Ink and Chemicals; solid content = 100%]. 28 parts of 3% MEK solution and ME
80 parts of K were added and mixed well. Next, this mixed solution was slowly added dropwise to 1,200 parts of water over 5 minutes while stirring.

After completion of the dropping, 5.
While stirring an aqueous solution prepared by dissolving 0 part in 50 parts of water,
The particles were crosslinked by slow addition.

Then, the resin dispersion thus obtained was concentrated and the organic solvent and excess water were removed to obtain a desired aqueous resin solution having a solid content of 32.5%.

Thereafter, first, a film was formed from the aqueous resin thus obtained, and then a solvent resistance test was conducted on this film. The results are shown in Table 1.

Example 2 20 of the prepolymer solution (A-1) obtained in Synthesis Example 1
0 part was neutralized with 7.9 parts of triethylamine, and 52.3% ME of "Epiclone 1055" was further added.
28 parts of K solution and 80 parts of MEK were added, and water was added dropwise while stirring with a homomixer.

Although it was observed that the viscosity of this mixed solution gradually increased, the viscosity was remarkably reduced around the point where about 300 parts of water was dropped, and the phase inversion was completed. Further, after adding 200 parts of water, an aqueous solution prepared by dissolving 5.0 parts of diethylenetriamine in 50 parts of water was slowly added with stirring to crosslink the inside of the particles.

Then, the organic solvent and excess water are removed under reduced pressure to obtain a solid content of 31.6%.
A solution of aqueous resin was obtained. Thereafter, first, a film was formed from the thus obtained aqueous resin, and then a solvent resistance test was performed on this film. The results are shown in Table 1.

Example 3 20 of the prepolymer solution (A-1) obtained in Synthesis Example 1
0 part, 28 parts of a 52.3% MEK solution of "Epiclone 1055" and 80 parts of MEK were added and mixed well.

Then, this mixed solution was treated with 1,200 water.
And 8.7 parts of dimethylaminoethanol were slowly added dropwise with stirring over 5 minutes.

After completion of the dropping, the diethylenetriamine of 5.
While stirring an aqueous solution prepared by dissolving 0 part in 50 parts of water,
The particles were crosslinked by slow addition. After that, the resin dispersion thus obtained was concentrated to remove the organic solvent and excess water, whereby a target aqueous resin solution having a solid content of 30.7% was obtained.

Thereafter, first, a film was formed from the thus obtained aqueous resin, and then a solvent resistance test was conducted on this film. The results are shown in Table 1.

Examples 4 to 12 Similar to Example 2, except that the kinds of raw materials and the amounts used were changed as shown in Table 1, various desired aqueous solutions were obtained. A resin solution was prepared.

Then, Table 1 shows the results of the solvent resistance test for the film obtained from this aqueous resin. The abbreviations in the table have the following meanings.

TEA ……………… Triethylamine DMEA ………… Dimethylethanolamine

EP1055 ... "Epiclone 1055"
52.3% MEK solution

IPA ………… isopropyl alcohol EDA ……………… ethylenediamine

DETA ………… diethylenetriamine TETA ………… triethylenetetramine

[0133]

[Table 1]

[0134]

[Table 2]

[0135]

[Table 3]

[0136]

[Table 4]

[0137]

[Table 5]

[0138]

[Table 6]

Comparative Example 1 2 of prepolymer solution (A-1) obtained in Synthesis Example 1
00 parts was neutralized with 7.9 parts triethylamine and water was added dropwise with stirring. Although it was confirmed that the viscosity of the polymer solution gradually increased, the viscosity was remarkably reduced around the point where about 300 parts of water was dropped, and the phase inversion was completed.

Further, after adding 50 parts of water, an aqueous solution in which 4.0 parts of diethylenetriamine was dissolved in 50 parts of water was slowly added with stirring to crosslink the inside of the particles.

Then, the organic solvent and excess water are removed under reduced pressure to obtain a solid content of 33.6%.
A pale white control aqueous resin solution was obtained. Then, a film was formed from this aqueous resin, the results of the solvent resistance test were performed on the film, and the results are shown in Table 2 together.

Comparative Example 2 200 parts of the prepolymer solution (A-1) obtained in Synthesis Example 1 and "Bernock DN-980S" [polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc.] Was mixed with 80 parts of MEK, and 7.9 parts of triethylamine was added thereto.

Although the resin solution gradually thickens by dropping water while stirring, the viscosity of the resin solution is remarkably lowered by further dropping of about 200 parts of water. And the phase inversion was completed.

Further, after adding 50 parts of water, an aqueous solution in which 5.1 parts of diethylenetriamine was dissolved in 50 parts of water was added slowly with stirring,
The inside of the particles was crosslinked.

Next, the organic solvent and excess water were removed under reduced pressure to obtain an aqueous resin solution having a solid content of 32.3%. Thereafter, a film was formed from this aqueous resin, and a solvent resistance test was conducted on the film. The results are shown in Table 2.

Comparative Examples 3 and 4 In the same manner as in Comparative Example 2 except that the kinds of raw materials and the amounts used were changed as shown in Table 2, various aqueous solutions for control were used. A resin solution was prepared. After that, the results are shown in Table 2 including the result of the solvent resistance test for the film obtained from this aqueous resin.

[0147]

[Table 7]

<< Footnote in Table 2 >> DN980S is an abbreviation for "Barnock DN-980S".

[0149]

[Table 8]

Example 13 A film having a predetermined size was obtained from the aqueous resin obtained in Example 1. Then, a tensile physical property test was conducted on this film. The results are collectively shown in Table 3.

Example 14 A tensile property test was conducted on the film in the same manner as in Example 13 except that the aqueous resin obtained in Example 6 was used. The results are collectively shown in Table 3.

Comparative Examples 5 and 6 Tensile physical property tests on the film were carried out in the same manner as in Example 13 except that various aqueous resins obtained in Comparative Examples 1 and 2 were used. I went. The results are collectively shown in Table 3.

[0153]

[Table 9]

[0154]

As described above in detail, the water-based resin according to the method of the present invention has extremely high solvent resistance and the like, and has the toughness of urethane itself under low temperature baking conditions. You can easily understand that it is extremely practical.

Claims (14)

[Claims] 1. A water-soluble or water-dispersible prepolymer (A) having an isocyanate group, an epoxy group-containing compound (B), and a polyamine compound (C) having active hydrogen as essential reaction components. , An aqueous resin or aqueous crosslinked fine particles obtained by reacting. 2. A water-soluble or water-dispersible prepolymer (A) having an isocyanate group and an epoxy group-containing compound (B) are mixed and dispersed in water, and then the mixed dispersion is obtained. A method for producing an aqueous resin or aqueous crosslinked fine particles, which comprises reacting a polyamine compound (C) having active hydrogen. 3. An isocyanate group in the prepolymer (A) having an isocyanate group, an epoxy group in the epoxy group-containing compound (B), and a primary or secondary group in the polyamine compound (C) having active hydrogen. The aqueous resin or aqueous crosslinked fine particles according to claim 1, wherein both of the average number of primary amino groups in one molecule are 1.5 or more and at least one is 2.5 or more. 4. An isocyanate group in a prepolymer (A) having an isocyanate group, an epoxy group in an epoxy group-containing compound (B), and a primary or secondary one in a polyamine compound (C) having active hydrogen. The production method according to claim 2, wherein all of the average number of the primary amino groups in one molecule are 1.5 or more, and at least one of them is 2.5 or more. 5. The aqueous resin or aqueous crosslinked fine particles according to claim 1, wherein the prepolymer (A) having an isocyanate group has an ionic group in its molecule. 6. The production method according to claim 2, wherein the prepolymer (A) having an isocyanate group has an ionic group in its molecule. 7. The above-mentioned prepolymer (A) having an isocyanate group, as an ionic group in the molecule,
The aqueous resin or aqueous crosslinked fine particles according to claim 1, which has a carboxyl group. 8. The above-mentioned prepolymer (A) having an isocyanate group has an ionic group in its molecule as an ionic group.
The production method according to claim 2, which has a carboxyl group. 9. The aqueous resin or aqueous crosslinked fine particles according to claim 1, wherein the average number of isocyanate groups in one molecule of the isocyanate group-containing prepolymer (A) is 1.7 to 2.3. 10. The production method according to claim 2, wherein the average number of isocyanate groups in one molecule of the prepolymer (A) having an isocyanate group is 1.7 to 2.3. 11. The epoxy group-containing compound (B) described above.
Is a resin having a number average molecular weight within the range of 300 to 3,000, and the aqueous resin or aqueous crosslinked fine particles according to claim 1. 12. The epoxy group-containing compound (B) as described above.
Has a number average molecular weight in the range of 300 to 3,000. 13. The epoxy group-containing compound (B) described above.
Has an epoxy equivalent in the range of 200 to 3,000, wherein the aqueous resin or the aqueous crosslinked fine particles according to claim 1. 14. The epoxy group-containing compound (B) described above.
Has an epoxy equivalent within the range of 200 to 3,000.