JPH029049B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an emulsion composition containing a resin (hereinafter also referred to as "polar resin") having at least one type of bond selected from urethane bonds, urea bonds, and amide bonds, and more specifically, it relates to an emulsion composition containing a resin (hereinafter also referred to as "polar resin") that can be used as a coating composition and a substrate. Contains a polar resin that, when applied on top, can form a coating film that has a non-tacky surface, feels good on the skin, and has excellent water resistance, yellowing resistance, gasoline resistance, abrasiveness, and other physical properties. The present invention relates to emulsion compositions. In recent years, aqueous emulsion compositions have come to be widely used as resource-saving, non-polluting paints to replace oil-based paints in fields where oil-based paints have traditionally been used. However, in conventional emulsion compositions obtained by using ionic or nonionic low-molecular or high-molecular surfactants as aqueous emulsion compositions, the emulsion system becomes unstable when a large amount of coalescent agent is used. Furthermore, when the emulsion composition is used in the paint field, a water-soluble resin is usually added to the emulsion composition in order to make the film formed very dense. Neutralizing agents and water-soluble organic solvents are included, and these components tend to make the emulsion system highly unstable.In addition, conventional aqueous emulsion compositions generally contain Since it uses ionic or nonionic low-molecular or high-molecular substances, it has various drawbacks such as poor water resistance of the film, so it has not been able to be put to practical use so far. In addition, the above conventional aqueous emulsion composition is
When used as a component of an adhesive, the disadvantage is that the surfactant contained in the emulsion composition leaches onto the applied adhesive surface, staining the surface. Therefore, attempts have been made to obtain an aqueous emulsion composition that does not have the above-mentioned drawbacks of conventional aqueous emulsion compositions containing ordinary ionic or nonionic low-molecular or high-molecular surfactants as dispersion stabilizers. Various attempts have been made, one of which has been proposed to use a water-soluble resin as a dispersion stabilizer. For example, it has been proposed to use water-soluble resins such as water-soluble acrylic resins, maleated polybutadiene, maleated oils, and maleated alkyd resins as dispersion stabilizers. However, although the above-mentioned water-soluble acrylic resin is preferable in terms of performance, on the other hand, the hydrophilic part and the non-hydrophilic part in the above-mentioned molecular skeleton are not clearly separated, so
It is difficult to obtain an emulsion composition with excellent stability using this water-soluble acrylic resin as a dispersion stabilizer. For this purpose, various attempts have been made to modify the water-soluble acrylic resin into a block copolymer or graft copolymer, but to date no block copolymer or graft copolymer having the desired performance has been found. It has not been found. On the other hand, water-soluble resins such as maleated polybutadiene, maleated oil, and maleated alkyd resins are themselves soft resins and have many oxidative hardening groups, so it is difficult to disperse and stabilize these water-soluble resins. The aqueous emulsion composition used as the agent is difficult to use because the surface of the cured coating film formed from it exhibits tackiness in the initial stage, and the coating film yellows due to long-term exposure. The big drawback is that it is limited. The present inventors have developed an aqueous emulsion composition that does not have the above-mentioned drawbacks, that is, it has excellent dispersion stability, water resistance, yellowing resistance, photoresponsiveness, etc., and has a coating film surface that remains stable even in the early stage of curing. Forms a cured coating that does not have a sticky feel and feels good on the skin, and also has the property of not softening due to the heat of friction when the coating is polished (hereinafter referred to as abrasiveness), gasoline resistance, etc. With the aim of providing an aqueous emulsion composition that provides a coating film with excellent physical properties, a water-soluble resin of a type different from the conventional oxidation-curing type water-soluble resin is used as a dispersion stabilizer, and the emulsion particles obtained are We conducted intensive studies on introducing a polar resin with strong intermolecular cohesive force into the emulsion without destroying the stability of the emulsion. However, it has been proposed in the past to introduce a polymer compound into emulsion particles (see Japanese Patent Application Laid-Open No. 51-28188). That is, in the above publication, water, a surfactant, at least one polymer, and at least one monomer are mixed to form an aqueous dispersion of polymer-monomer particles, and then It is disclosed that monomers within the particles are radically polymerized to produce an aqueous emulsion composition. However, in this method, it is necessary to thoroughly emulsify the polymer-monomer before polymerization until the emulsion unit, that is, the average particle size is 0.01 to 5 μm, and for this purpose, a relatively large amount of surface An activator substance must be used, which necessarily has the disadvantage that the films formed from the aqueous emulsion compositions thus obtained have poor water resistance. Moreover, the urethane bond used in the present invention,
A resin having a urea bond and/or an amide bond is
In general, many of the monomers used in emulsion polymerization are insoluble, making it difficult to apply the above method. Furthermore, an aqueous emulsion composition obtained by the above method using a polar resin with strong intermolecular cohesion is generally useless as a coating composition unless a film-forming agent is added. However, as in the conventional example, an aqueous emulsion composition obtained using a conventional ionic or nonionic low-molecular or high-molecular surfactant substance as a dispersion stabilizer,
If a large amount of a coalescing agent is used, the emulsion system may become unstable, and if a water-insoluble coalescing agent is used as a coalescing agent, the emulsion composition may become flammable. Disadvantages include that the emulsion composition tends to become loose, and when a water-soluble resin is added to an emulsion composition, the emulsion system becomes unstable due to the neutralizing agent and water-soluble organic solvent contained therein. Because of this, it has not been put to practical use. Therefore, the present inventors used a generally known water-soluble resin as a dispersion stabilizer that does not impair the stability of the emulsion by adding a membrane-forming agent, etc., to form a polar resin-radically polymerizable unsaturated monomer. We conducted intensive research with the aim of introducing a polar resin with strong intermolecular cohesive force into emulsion particles by emulsion polymerization of a mixed system. As a result, if a generally known water-soluble resin is used as it is as a dispersion stabilizer, the above objective cannot be achieved. , a type of water-soluble resin obtained by adding a glycidyl group-containing vinyl monomer to the carboxyl group of a carboxyl group-containing vinyl polymer, or a diisocyanate compound and a hydroxyl group-containing vinyl polymer containing a carboxyl group and a hydroxyl group. Uses water-soluble resins that have graft-polymerizable unsaturated groups in their side chains, such as water-soluble resins obtained by adding monoaddition products with acrylic monomers, and are resistant to water. The present invention was completed based on the discovery that the object of the present invention can be achieved when used in combination with a polar resin that exhibits affinity. Thus, according to the present invention, at least one radically polymerizable unsaturated monomer (A) and a polar resin (B) having at least one bond selected from a urethane bond, a urea bond, and an amide bond. A polar resin-containing emulsion obtained by emulsion polymerizing the system consisting of A composition is provided. The polar resin-containing emulsion composition of the present invention includes:
The water-soluble resin used as a dispersion stabilizer has an unsaturated group in its side chain that has a large grafting effect and a small chain transfer effect, so even if it is used in a small amount, the water-soluble resin will not be absorbed during emulsion polymerization. Appropriate graft reaction with the radically polymerizable unsaturated monomer forms a long side chain, and the thus formed grafted product and the coexisting polar resin polymerize on the spot, so they are well intertwined and have very stable dispersion. It has excellent properties. Moreover, the emulsion composition of the present invention does not use ordinary ionic or nonionic low-molecular or high-molecular surfactant substances and water-soluble oxidation-curing water-soluble resins as dispersion stabilizers; Since the emulsion particles contain a polar resin with strong intermolecular cohesive force in a stable state, the coating surface does not feel sticky and feels soft even when applied to a substrate as a coating composition. It has the excellent feature of being able to form a coating film with good water resistance, yellowing resistance, gasoline resistance, abrasiveness, and other physical properties. In addition, the polar resin-containing emulsion composition of the present invention has the advantage that even when used as a component of an adhesive, the dispersion stabilizer does not ooze out onto the surface and stain the adhesive surface. Hereinafter, the polar resin-containing emulsion composition of the present invention will be explained in more detail. Polar resin (B) In the polar resin-containing emulsion composition of the present invention, the "polar resin" introduced into the emulsion particles is such that the surface of the coating film exhibits a sticky feeling when the resulting emulsion composition is applied to a substrate. It must provide a coating film that is smooth and feels good on the skin, and has excellent abrasiveness and other physical properties. Polar resins that can achieve this purpose include resins containing urethane bonds, urea bonds, and/or amide bonds in the resin skeleton and having strong hydrophilic and intermolecular cohesive forces, generally about 500 to about 100,000, preferably about 100,000. The resin has an average molecular weight within the range of about 1,000 to about 20,000. These polar resins are compatible with a water-soluble resin used as a dispersion stabilizer and/or are compatible with a grafted product of a water-soluble resin and a radically polymerizable unsaturated monomer produced by emulsion polymerization. This is highly desirable. The following are representative examples of polar resins used in the present invention. (i) Resin containing urethane bond and/or urea bond: diisocyanate compound with polyol compound,
A diisocyanate-, -hydroxyl-, or amino-terminated resin obtained by reacting with a polyamine compound or an alkanolamine compound by a conventional method, and preferably, the resin is further blocked with a monoisocyanate compound, a monohydroxy compound, or a monoamine compound. This can be obtained by Specific examples of diisocyanate compounds that can be used in the production of such resins include the following. OCN( _-CH2 ) _-dNCO (d=2~12), OCN- _CH2 - _CH2- S- _CH2 - _CH2- NCO, OCN―CH ₂ ―CH ₂ ―CH ₂ ―O―CH ₂ ―CH ₂ ―CH ₂ ―NCO, Lysine diisocyanate, isophorone diisocyanate, etc. These diisocyanate compounds can be used alone, or in combination of two or more. Moreover, the following can be mentioned as specific examples of polyol compounds, polyamine compounds, and alkanolamine compounds that can be used to form the polar resin by reacting with the diisocyanate compound described above. (a) As the polyol compound, a known polyol compound having two or more hydroxyl groups in one molecule, especially at the end of the molecule and having a number average molecular weight generally in the range of about 60 to about 10,000, preferably about 60 to about 2,000, is used. Any polyol compound may be used, representative examples being ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, pentanediol, Dihydric alcohols such as hexanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, and ester diol 204 (manufactured by Union Carbide, trade name);
Trihydric or higher polyhydric alcohols such as trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, glycerin, diglycerol; In addition to these alcohols, alkyd resins and epoxy resins containing these alcohols as terminal components , or ester compounds and ether compounds used in making elastomers for urethane resins (e.g., polyoxypropylene glycol, polyoxybutylene glycol, polyoxyethylene glycol, polyoxytetramethylene glycol, diol adipate, glycol dimer acid, adipic acid-phthalic acid-triol-diol, etc.). (b) The polyamine compound is any known compound having two or more amino groups in one molecule, especially at the end of the molecule, and has a number average molecular weight of about 60 to about 5000, preferably about 60 to Compounds within the range of about 2000 can be used, typical examples of which include hydrazine, ethylenediamine, N-alkyl (particularly lower alkyl groups such as methyl and ethyl, the same applies hereinafter)-substituted ethylenediamine, tetramethylenediamine, N- Alkyl-substituted tetramethylene diamine, pentamethylene diamine, N-alkyl substituted pentamethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, octadecamethylene diamine, bis(4-aminocyclohexyl)methane, bis(4-amino- 1,
Examples include 2-methylcyclohexyl)methane. (C) As the alkanolamine compound, any known compound having both an amino group and a hydroxyl group at the molecular end and having a molecular weight in the range of about 60 to about 5,000, preferably about 60 to about 2,000 is used. For example, ethanolamine, N-alkyl (especially lower alkyl groups such as methyl and ethyl), substituted ethanolamine, diethanolamine, isopropanolamine, 1-aminobutan-4-ol, 1-aminopentane-5
- Examples include oars. In addition, the monoisocyanate compound, monohydroxy compound, and monoamine compound that can constitute the terminal component of the resin skeleton in the resin (i) containing the urethane bond and/or urea bond are not particularly limited, and are generally known. Any can be used. Examples of monoisocyanate compounds include aliphatic and aromatic monoisocyanate compounds such as methyl isocyanate, ethyl isocyanate, isopropylisocyanate, and phenyl isocyanate; examples of monoalcohol compounds include methyl alcohol, ethyl alcohol, and propyl alcohol. , aliphatic saturated monohydric alcohols such as butyl alcohol; aliphatic unsaturated monohydric alcohols such as allyl alcohol; aromatic monohydric alcohols such as benzyl alcohol;
Examples include cellosolve alcohols; carbitol alcohols; examples of monoamine compounds include aliphatic or aromatic amines such as methylamine, isopropylamine, and benzylamine. The above urethane bond and/or used in the present invention
Alternatively, the resin (i) containing a urea bond is prepared by combining the above diisocyanate compound and a polyol compound, a polyamine compound or an alkanolamine compound in a non-reactive solvent or in the absence of a solvent, usually at a concentration of 0 to 150%.
The equimolar reaction is carried out for about 0.5 to about 20 hours at a temperature within the range of about ℃, and then, if necessary, a monoisocyanate compound, a monoalcohol compound, or a monoamine compound is reacted under the same reaction conditions to stop the reaction. It can be synthesized by In order for the resin (i) containing the urethane bond and/or urea bond to exhibit sufficient hydrophilicity and intermolecular cohesion, the amount of the diisocyanate compound to be used is 5 to 90% based on the weight of the resulting resin. % by weight, preferably in the range of 10 to 80% by weight. (ii) Resin containing an amide bond: The terminal of a resin formed by a condensation reaction of a polyamine compound and a polycarboxylic acid compound or its reactive derivative or an amino acid compound, ring-opening polymerization of a lactam compound, acrylamide transfer polymerization, etc.
It is blocked with a monoamine compound or a monocarboxylic acid compound. Examples of polyamine compounds that can be used in the production of such resins include those mentioned in (i) above. In addition, the polycarboxylic acid or its reactive derivative and the amino acid compound that can be used to react with this polyamine compound to form a polar resin generally have a number average molecular weight of about 100 to about 10,000, preferably about 100 to about 2,000. Any known compound within the range can be used. Typical examples of polycarboxylic acids include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and brasilinic acid. Acid, dimer acid, ethyl glutaric acid, fumaric acid, maleic acid, methyl fumaric acid, phthalic acid, isophthalic acid, terephthalic acid,
Examples include hexahydrophthalic acid, hemicic acid, trimellites, pyromellites, and itaconic acid. Examples of reactive derivatives of these polycarboxylic acids include anhydrides, halides, and esters. Examples of amino acid compounds include glycine, alanine, imidodipropionic acid, aminobutyric acid, lysine, glutamic acid, δ-aminovaleric acid, ε-aminocaproic acid, ζ-aminoenanthate, η-aminocaprylic acid, θ- Examples include aminopelargonic acid, ι-aminocapric acid, aminoundecanoic acid, and 13-aminotridecanoic acid. Further, lactam compounds include, for example, propiolactam, caprolactam, laurolactam, and the like. On the other hand, the monoamine compound and monocarboxylic acid compound that provide the terminal component of the resin skeleton in the resin (ii) containing an amide bond are not particularly limited, and any commonly known compounds can be used; In general, monoamine compounds include, for example, the aliphatic or aromatic amines shown in the synthesis of resin (i) containing urethane bonds and/or urea bonds. Examples of monocarboxylic acid compounds include _C1 to _C26 aliphatic monocarboxylic acids such as acetic acid, propionic acid, caproic acid, lauric acid, and stearic acid; benzoic acid, pt-butylbenzoic acid, etc. Examples include aromatic monocarboxylic acids. The above resin (ii) containing an amide bond can be produced by polymerizing the above-mentioned reaction components according to a conventional method. For example, it can be synthesized by carrying out a dehydration reaction at a temperature of 100 to 250°C for 1 to 20 hours while measuring oxidation and viscosity. In order for the amide bond-containing resin (ii) to exhibit sufficient hydrophilicity and intermolecular cohesion, the polyamine component should be present in an amount of 5 to 90% by weight, preferably 10 to 90% by weight of the resulting resin.
It can be in the range of 80% by weight. The polar group-containing resins described above can be used alone, or in combination of two or more. Water-soluble resin (C) "Water-soluble resin having a graft-polymerizable unsaturated group in its side chain" used as a dispersion stabilizer in the polar resin-containing emulsion composition of the present invention
The resin itself can be water-solubilized and can be a resin capable of forming a film having sufficient durability. Such water-soluble resins are typically obtained by adding a glycidyl group-containing vinyl monomer to a carboxyl group-containing vinyl polymer [hereinafter referred to as
"Water-soluble resin (C-)"] or by adding a monoaddition product of a diisocyanate compound and a hydroxyl group-containing acrylic monomer to a vinyl polymer containing a carboxyl group and a hydroxyl group. [hereinafter referred to as “water-soluble resin (C-
)”. First, the "carboxyl group-containing vinyl polymer" used to prepare the former water-soluble resin (C-) is composed of α,β-ethylenically unsaturated carboxylic acid and radically polymerizable unsaturated monomer. It is obtained by copolymerizing by a conventional method. Such α,β-ethylenically unsaturated carboxylic acids are unsaturated aliphatic mono- or polycarboxylic acids having an addition-polymerizable double bond between the carbon atom to which a carboxyl group is bonded and the carbon atom adjacent thereto. Those containing 3 to 8 carbon atoms, especially 3 to 5 carbon atoms, and having 1 or 2 carboxyl groups are suitable, and in particular those having the following general formula () In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ represents a hydrogen atom, a lower alkyl group, or a carboxyl group, and R ₃ represents a hydrogen atom, a lower alkyl group, or a carboxy lower alkyl group. things are included. In the above formula (), the lower alkyl group is preferably one having 4 or less carbon atoms, particularly a methyl group. Examples of such α,β-ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, monoalkyl (C _1-3 ) maleate.
Examples include esters, and these can be used alone or in combination of two or more. The "radically polymerizable unsaturated monomer" that can be radically copolymerized with the above α,β-ethylenically unsaturated carboxylic acid is particularly limited as long as it has a radically polymerizable ethylenically unsaturated bond (C=C). can be selected from a wide range depending on the desired performance of the final emulsion composition. Representative examples of such unsaturated monomers are as follows. (a) Esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate,
Propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate,
Acrylics such as octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc. C _1-18 alkyl or cycloalkyl ester of acid or methacrylic acid; acrylic acid or methacrylate such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. Alkoxyalkyl ester of acid; _C2-8 hydroxyalkyl ester _of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate;
Monoester of acrylic acid or methacrylic acid with polyethylene glycol or polypropylene glycol, such as polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate; glycidyl acrylate or glycidyl methacrylate and C _2-18 monocarboxylic acid Adducts with compounds (eg acetic acid, propionic acid, oleic acid, stearic acid, lauric acid, etc.). (b) Vinyl aromatic compounds: e.g. styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, vinylpyridine. (c) Polyolefin compounds: for example, butadiene, isoprene, chloroprene. (d) Amides of acrylic or methacrylic acid: for example acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide. (e) Others: acrylonitrile, methacrylonitrile, ethylene, propylene, butene, methyl isopropenyl ketone, vinyl acetate, vinyl esters (vinyl esters of aliphatic or aromatic monobasic acids or polybasic acids), beoba monomer,
dialkyl (C _1-8 ) esters of maleic acid, etc. These unsaturated monomers are appropriately selected depending on the desired physical properties, and may be used alone or in combination of two or more. In addition, in the present invention, in order to form the water-soluble resin (C-), a "glycidyl group-containing vinyl monomer" is added to the carboxyl group of the carboxyl group-containing vinyl polymer prepared from the above-mentioned monomers. is the following formula in the molecule A monomer containing one glycidyl group represented by the formula and one ethylenically unsaturated bond (>C=C<) is used, and examples thereof include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like. The copolymerization of the above α,β-ethylenically unsaturated carboxylic acid and a radically polymerizable unsaturated monomer is as follows:
The acrylic copolymer can be produced according to a method known per se, such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, etc.
Advantageously, the polymerization is carried out according to a solution polymerization method, in which the above two components are mixed in a suitable inert solvent in the presence of a polymerization catalyst, usually at about 0 to about 180°C, preferably at about 40 to about At a reaction temperature of 170°C, about 1 to about
This can be carried out by continuing the reaction for 20 hours, preferably about 4 to about 10 hours. As the solvent used, it is desirable to use a solvent that can dissolve the copolymer to be produced and is miscible with water so that gelation does not occur during the copolymerization reaction. Examples of such solvents include cellosolve solvents, carbitol solvents, glyme solvents, cellosolve acetate solvents, and alcohol solvents. Further, as the polymerization catalyst, used are conventional radical initiators for radical polymerization, such as azo compounds, peroxide compounds, sulfides, sulfines, diazo compounds, nitroso compounds, and redox compounds. The carboxyl group-containing vinyl polymer thus obtained generally has an acid value in the range of 10 to 300, preferably 30 to 200, and also has an acid value in the range of about 300 to about 100,000, preferably about 800 to about 50,000. It can have a number average molecular weight. The carboxyl group-containing vinyl polymer produced as described above is directly subjected to an addition reaction with a glycidyl group-containing vinyl monomer in a solvent to form a water-soluble resin (C-) used as a dispersion stabilizer.
form. The addition reaction is carried out at a reaction temperature of about 60 to about
This can be carried out by subjecting both components to an addition reaction under conditions of 220°C, preferably about 120 to about 170°C, and a reaction time of about 0.5 to about 40 hours, preferably about 3 to about 10 hours. At that time, the ratio of the glycidyl group-containing vinyl monomer to the carboxyl group-containing vinyl polymer is not strictly limited, but in general, the ratio of the vinyl polymer to the glycidyl group-containing vinyl monomer is Quantity weight ratio 99.9:
0.1 to 70:30, preferably 99.5:0.5 to 90:10
It is advantageous to have a range of . In the production of the water-soluble resin (C-) of the present invention, the polymerization reaction between the α,β-ethylenically unsaturated carboxylic acid and the radically polymerizable unsaturated monomer and the resulting carboxyl group-containing vinyl polymer are performed. Both addition reactions of glycidyl group-containing vinyl monomers can be carried out continuously in an organic solvent, making production extremely easy.Also, the resulting resin solution can be used as it is to stabilize the dispersion of the emulsion. It has the advantage of being able to be used as an agent. Next, the "vinyl polymer containing a carboxyl group and a hydroxyl group" used to prepare the latter water-soluble resin (C-) is, for example, a monomer component of the water-soluble resin (C-). α,β-ethylenically unsaturated carboxylic acids as described above, especially those represented by the formula (), and hydroxyl group-containing acrylic monomers, such as representative examples of the radically polymerizable unsaturated monomers (a ) using _C2-8 hydroxyalkyl ester of acrylic acid or methacrylic acid as an essential component and, if necessary, using other radical polymer unsaturated monomers as mentioned above as a copolymerization component, and a solvent. It can be produced by copolymerization in exactly the same manner as in the case of the carboxyl group-containing vinyl polymer described above, except that a hydroxyl group-containing solvent is not used. The vinyl polymer containing carboxyl groups and hydroxyl groups produced in this manner generally has a molecular weight of 10 to
300, preferably from 30 to 200 and generally from 2 to
150, preferably 5 to 50, and its number average molecular weight is about 300 to about
100,000, preferably in the range of about 800 to about 50,000. A monoaddition product of a diisocyanate compound and a hydroxyl group-containing acrylic monomer (hereinafter referred to as "isocyanate-modified acrylic monomer") is added to the thus obtained vinyl polymer containing carboxyl groups and hydroxyl groups. By this, a water-soluble resin (C-) is formed. Such "isocyanate-modified acrylic monomer" is obtained by reacting a hydroxyl group-containing acrylic monomer with a diisocyanate compound, and the hydroxyl group-containing acrylic monomer used is the carboxyl group-containing vinyl monomer Typical examples of radically polymerizable unsaturated monomers used in the production of polymers: _C2-8 hydroxyalkyl esters of acrylic acid or methacrylic acid shown in (a), and acrylic acid or methacrylic acid and polyethylene glycol or Monoesterified products with polypropylene glycol are suitable. On the other hand, the diisocyanate compound to which the hydroxyl group-containing acrylic monomer is added is as follows:
Any type of diisocyanate compound commonly used in the production of polyurethane, such as aliphatic, alicyclic, aromatic, and aromatic-aliphatic, can be used. Specific examples of such diisocyanate compounds include those mentioned above for the resin (i) containing urethane bonds and/or urea bonds. Among the diisocyanate compounds, those having excellent yellowing resistance include 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, xylene diisocyanate, and hydrogenated toluene diisocyanate. It will be done. The hydroxyl group-containing acrylic acid monomer is usually 0.6 to 1.4 mol per mol of the isocyanate compound,
It is advantageous to use preferably a proportion of 0.9 to 1.1 mol. The reaction can be carried out by a generally known method. Generally, it can be carried out at a temperature within the range of about 20-150°C, and the reaction time is generally about 0.5-40°C.
It's time. In addition, when reacting the hydroxyl group-containing acrylic monomer with the diisocyanate compound, a polymerization inhibitor such as hydroquinone, tertiary butyl hydroxytoluene, methoxyphenol, tertiary butylcatechol, benzoquinone, etc. may be used as necessary. It is advantageous to use The isocyanate-modified acrylic monomer thus produced has a free isocyanate group in its molecule, and the interaction between this free isocyanate group and the hydroxyl group of the vinyl polymer having carboxyl and hydroxyl groups described above is The water-soluble resin (C-) of the present invention is formed by the addition reaction between. The reaction can be carried out in a conventional manner in an inert solvent, and is generally carried out at a temperature in the range of about 20 DEG to 150 DEG C. and for a reaction time of about 0.5 to 40 hours.
Known reaction catalysts and polymerization inhibitors are used as necessary. In the above addition reaction, the addition ratio of the isocyanate-modified acrylic monomer to be reacted with the vinyl polymer containing carboxyl groups and hydroxyl groups is generally 99.9 in weight ratio of the polymer to the isocyanate-modified acrylic monomer. :0.1 to 70:30, preferably 99.5:0.5 to 90:10. The water-soluble resin (C
-) and (C-) to make them water-soluble,
It is desirable that the final acid value is 10 to 250, preferably 30 to 200, and the water-soluble resin (C
-) and (C-) have a number average molecular weight of about 500 to about 100,000, preferably about 800 to about
50000 is advantageous. For this purpose, water-soluble resin (C-
) or (C-) has the above acid value, the copolymerization ratio of α,β-unsaturated carboxylic acid (amount of carboxyl group) is adjusted, and the number average molecular weight is within the above range. It is important to prepare the reaction conditions in advance. The water-soluble resin thus produced is made water-soluble as it is or after distilling off the solvent. This water solubility can be achieved by a conventional method, for example, using a conventionally known neutralizing agent (such as amine, ammonia, alkali metal hydroxide, etc.) to neutralize the carboxyl groups present in the resin.
This can be done by neutralizing with. In addition, as one component of the monomer constituting the vinyl polymer that is the base resin of the water-soluble resin of the present invention,
When a monoester of acrylic acid or methacrylic acid and polyethylene glycol or polypropylene glycol is used, it is hydrophilic in itself and water solubility of the resin can be achieved without necessarily neutralizing carboxyl groups. There are things you can do. For this purpose, the monoesterified product should generally be copolymerized in a proportion of 10 to 90% by weight, preferably 20 to 80% by weight. Of course, in this case, water solubility by neutralization of carboxyl groups may also be used. Radically polymerizable unsaturated monomer (A) According to the present invention, the water-soluble resin (C) described above is used as a dispersion stabilizer, and the radically polymerizable unsaturated monomer (A) and the water-soluble resin (C) described above are used as a dispersion stabilizer. A system consisting of a polar resin (B) is emulsion polymerized in an aqueous medium. The radically polymerizable unsaturated monomer (A) is not particularly limited as long as it is compatible with the water-soluble resin and its hydrophilicity is not as strong as above, but typical examples include the following: That's right. (i) Vinyl aromatic compounds: For example, C _8-10 vinylbenzene derivatives such as styrene, α-methylstyrene, vinyltoluene; vinyl heteroaromatic compounds such as vinylpyridine. (ii) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, lauryl acrylate, cyclohexyl acrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate,
C _1-20 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate; glycidyl acrylate or glycidyl methacrylate and C _2-18 monocarboxylic acid Adducts with compounds (e.g. acetic acid, propionic acid, oleic acid, stearic acid, lauric acid, etc.); methoxybutyl acrylate, methoxyethyl acrylate, ethoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl methacrylate, methacrylate _C2-12 alkoxyalkyl esters of acrylic acid or methacrylic acid such as ethoxybutyl acid; alkenyl esters of acrylic acid or methacrylic acid such as allyl acrylate, allyl methacrylate; acrylic acids such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or _C2-8 hydroxyalkyl ester of methacrylic acid and the above _C2-26
Condensate with monocarboxylic acid compound. (iii) Polyolefins having 2 to 8 carbon atoms such as butadiene, isoprene, chloroprene, etc. (iv) Vinyl carboxylate esters such as vinyl acetate and Beoba monomer (manufactured by Ciel Chemical Co., Ltd.). (v) Others: vinyl chloride, vinylidene chloride, monoolefins (e.g. ethylene, propylene, isobutene, etc.), etc. Among these radically polymerizable unsaturated monomers, particularly preferred in the present invention are vinyl aromatic compounds and esters of acrylic acid or methacrylic acid. These unsaturated monomers are appropriately selected depending on the physical properties desired for the final emulsion composition, and may be used alone or in combination of two or more. Furthermore, in the above monomers, 50% or less of the total amount of monomers used,
Hydrophilic unsaturated monomers may be present, preferably in an amount of up to 30% by weight. Examples of hydrophilic unsaturated monomers that may be present include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
There are 2-hydroxypropyl methacrylate, acrylotrile, methacrylonitrile, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, N-n-butoxymethylacrylamide, N-methylolacrylamide, methacrylamide, etc., and these include two types or More than one can be used in combination. Emulsion polymerization According to the present invention, the above-mentioned water-soluble resin is used as a dispersion stabilizer, and in the presence of the above-mentioned water-soluble resin, the system consisting of the above-mentioned radically polymerizable unsaturated monomer and polar resin is emulsion polymerized in an aqueous medium. It will be done. Generally known methods are used for the emulsion polymerization. For example, the polymerization is carried out in the presence of the above-mentioned dispersion stabilizer, optionally using the above-mentioned polymerization initiator, with stirring or in a stationary state at a temperature between the freezing point and the boiling point of the aqueous medium.
As the aqueous medium which is the reaction medium for the above polymerization, in addition to water, it is also possible to use mixtures of water and the water-miscible organic solvents mentioned above. Here, the amount of the water-soluble resin used as a dispersion stabilizer is generally 2 to 90% by weight, preferably 5 to 90% by weight based on the total solid content in the emulsion to be produced.
The proportion may be 50% by weight. In addition, the amount of the polar resin used to be introduced into the emulsion particles produced in the present invention is determined by subtracting the amount of the water-soluble resin used as a dispersion stabilizer from the total solids in the emulsion produced. Generally 3 to 30% for the remaining solids
The proportion may be 97% by weight, preferably 5 to 70% by weight. Therefore, the amount of the radically polymerizable unsaturated monomer used can be the remaining amount. The amount of the aqueous medium used is such that the solid content of the resulting emulsion is 15 to 60% by weight, preferably 25% by weight.
The amount can range from ~50% by weight. Polar resin-containing emulsion composition The polar resin-containing emulsion composition obtained by the present invention is usually translucent, and the average particle size of the emulsion is generally 1 micron or less, preferably
It can consist of particles as small as 0.5 microns or less. In addition, in the emulsion composition, the water-soluble resin (C), which is a dispersion stabilizer, undergoes radical polymerization with the radically polymerizable unsaturated monomer (A) during emulsion polymerization and is fixed to the emulsion particles. To,
Excellent mechanical stability and stability against organic solvents. Furthermore, since emulsion polymerization is carried out on the spot where the introduced polar resin (B) is present, the resulting grafted product and polar resin are well intertwined, and since the polar resin has hydrophilic groups, it can be easily dissolved in water. It can exist stably without agglomerating and producing lumps. The polar resin-containing emulsion composition obtained in this way is diluted to a viscosity suitable for coating, if necessary.
Alternatively, after thickening, it can be used as it is in a coating composition as a film-forming component, and can also be used as a component in an adhesive. Also,
The emulsion composition can also contain other water-soluble resins, extender pigments, coloring pigments, rust preventives, plasticizers, organic solvents, etc. in amounts commonly used, if necessary. The polar resin-containing emulsion composition of the present invention includes:
Since the emulsion particles contained therein contain a polar resin with strong intermolecular cohesive force, the surface of a dry coating formed from the emulsion composition does not exhibit tackiness and exhibits an excellent texture. Further, based on the intermolecular cohesive force of the polar resin, the coating film formed using the emulsion composition has the advantage that it has excellent polishability, gasoline resistance, and other physical properties. In addition, since the emulsion composition of the present invention uses the above-mentioned specific water-soluble resin as a dispersion stabilizer, the coating film formed from the emulsion composition has good water resistance, yellowing resistance, etc. It is also very good. Furthermore, the polar resin-containing emulsion composition of the present invention can be used as a general paint as it is or in combination with other water-soluble or water-dispersible resins. Furthermore, although the formed film is sufficiently cured at room temperature, it may be cured by heating if necessary. Furthermore, the emulsion composition of the present invention can be used not only as a paint but also as an adhesive and for processing resins. Next, the present invention will be further explained by examples.
In the examples, "%" indicates "% by weight" unless otherwise specified. Example 1 Into the 2 four-necked flask, add butyl cellosolve.
Add 556g and heat to 120℃. This stuff includes 77g of ethyl acrylate and 173g of methyl methacrylate.
g, 108 g of acrylic acid, 198 g of 2-ethylhexyl methacrylate and 32 g of azobisdimethylvaleronitrile are added dropwise over a period of 2 hours. One hour after the dropwise addition, 5 g of azobisisobutyronitrile was added. Thereafter, the temperature of the contents was gradually raised to 158°C after 2 hours, and a heating reaction was carried out at the same temperature for 1 hour. The temperature of the contents was then lowered to 130° C., and 30 g of glycidyl methacrylate was added dropwise to the contents over 40 minutes. Thereafter, the reaction is carried out at 130-140°C for 2 hours until the acid value becomes constant. After the reaction is complete, a portion of the butyl cellosolve is removed by vacuum distillation. Thus, acid number 108.5 and solids content 80.9
% water-soluble resin solution was obtained. Meanwhile, put 300g of dioxane and 312g of neopentyl glycol into another 4-necked flask.
Heat to 100℃. 666 g of isophorone diisocyanate is added dropwise to this over a period of 2 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 110°C. Next, 400 g of butyl cellosolve was added and reacted, and then dioxane and a portion of butyl cellosolve were removed by vacuum distillation. Thus solids content 87.6
% urethane resin solution was obtained. When this resin solution was diluted with dioxane to a solid content of 50%, the Gardner viscosity was S to R. Next, 99 g of the above water-soluble resin solution, 37 g of butyl cellosolve, 11 c.c. of 30% ammonia water, and 362 g of deionized water were mixed and dissolved in a 4-necked flask (No. 2). A solution of 41 g of the urethane resin solution dissolved in 166 g of n-butyl methacrylate is added to this solution and stirred thoroughly to form an esulsion. This includes 5g of deionized water and 0.5g of ammonium persulfate.
Add the solution dissolved in and heat to 80℃. heating 1
After an hour, 1 g of Kayabutyl H-70 (tert-butyl hydroxy peroxide, manufactured by Nippon Kayaku Co., Ltd.) is added, and the mixture is further heated for 4 hours. The performance of the emulsion composition thus obtained is shown in Table 1 below. Example 2 99 g of the same water-soluble resin solution used in Example 1 and 37 g of butyl cellosolve were placed in the 2 four-necked flask.
g, 30% ammonia water 11 c.c. and deionized water 362 g
Add and mix to dissolve. To this solution is added a solution of 47 g of the urethane resin solution used in Example 1 dissolved in 84 g of n-butyl acrylate and 84 g of styrene, and stirred well to form an emulsion. A solution of 0.5 g of ammonium persulfate dissolved in 5 g of deionized water is added to this and heated to 80°C. After 1 hour of heating, 1 g of Kayabutyl H-70 was added, and the mixture was further heated for 4 hours. The composition properties of the emulsion thus obtained are shown in Table 1 below. Example 3 100 g of dioxane and 111 g of isophorone diisocyanate were placed in the four-necked flask from 1, mixed and dissolved, and heated to 70°C. A mixture of 32.5 g of 2-methylaminoethanol and 50 g of dioxane was added dropwise to this mixture over 1 hour. 110 after completion of dripping
After heating at ~120℃ for 4 hours, butyl cellosolve
150 g of dioxane and butyl cellosolve were removed by vacuum distillation. In this way, a urethane/urea resin solution with a solid content of 77.6% was obtained.
When this urethane/urea resin solution was diluted with butyl cellosolve to a solid content of 50%, the Gardner viscosity was V ⁺ . Next, in a four-necked flask (No. 2), 99 g of the same water-soluble resin solution used in Example 1, 37 g of butyl cellosolve, and 46 g of the above urethane/urea resin solution were added.
Add g and heat to 60℃ to mix and dissolve. To this solution, 362 g of deionized water and 11 c.c. of 30% aqueous ammonia were added and stirred thoroughly to form an emulsion.
Next, 166 g of n-butyl methacrylate was added to this mixture to form an emulsion, and a solution of 0.5 g of ammonium persulfate dissolved in 5 g of deionized water was added and heated to 80°C. After 1 hour of heating, 1 g of Kayabutyl H-70 was added, and the mixture was further heated for 4 hours. The performance of the emulsion composition thus obtained is shown in Table 1 below. Example 4 In the preparation of the emulsion of Example 3, Tomide was used instead of 46 g of urethane/urea resin solution.
An emulsion was prepared in the same manner as in Example 3, except that 36 g of 90 (manufactured by Fuji Kasei Co., Ltd., polyamide resin) and 10 g of butyl cellosolve were used. The performance of the emulsion composition thus produced is shown in Table 1 below. Example 5 556 g of toluene is added to the 2 four-necked flask and heated to 110-120°C. 77g of ethyl acrylate, 173g of methyl methacrylate, 2
-Ethylhexyl methacrylate 198g, acrylic acid 93g, hydroxyethyl methacrylate 15g
A mixture of 32 g of azobisdimethylvaleronitrile and azobisdimethylvaleronitrile was added dropwise over 2 hours. One hour after the dropwise addition, 5 g of azobisdimethylvaleronitrile was added.
Thereafter, a heating reaction was carried out at the same temperature for 6 hours to obtain an acrylic polymer solution containing carboxyl groups and hydroxyl groups. Meanwhile, 696 g of tolylene diisocyanate was placed in another 4-necked flask and heated to 50°C.
Add 1 g of hydroquinone to 520 g of hydroxyethyl methacrylate to this solution for 4 hours.
Drip over time. Thereafter, the heating reaction was continued for another 3 hours at the same temperature, and then placed in a can and sealed, and left at room temperature for 1 day. In this way, a white waxy isocyanate-modified acrylic monomer was obtained. Next, 60 g of the isocyanate-modified acrylic monomer was added to the acrylic polymer solution at 80°C.
The reaction was carried out for 2 hours. After the reaction is complete, toluene is removed by vacuum distillation. When about half of the toluene has been removed, add 200g of butyl cellosolve.
Remove remaining toluene and some butyl cellosolve. In this way, a water-soluble resin solution with an acid value of 100 and a solid content of 80% was obtained. Next, 100 g of the above water-soluble resin solution, 36 g of butyl cellosolve, 11 c.c. of 30% ammonia water, and 362 g of deionized water were mixed and dissolved in a 4-necked flask (No. 2). To this solution, 41 g of the same urethane resin solution obtained in Example 1 was added to 166 g of n-butyl methacrylate.
Add the solution dissolved in g and stir well to form an emulsion. A solution of 0.5 g of ammonium persulfate dissolved in 5 g of deionized water is added to this and heated to 80°C. After 1 hour, 1 g of Kayabutyl H-70 is added and heated for an additional 4 hours. The performance of the emulsion composition thus produced is shown in Table 1 below. Comparative Example 1 Add butyl cellosolve to 2 four-necked flasks.
Add 500g and 130g of acetone and heat to 85°C. A mixture of 80 g of ethyl acrylate, 180 g of methyl methacrylate, 103 g of acrylic acid, 267 g of 2-ethylhexyl methacrylate and 32 g of azobisdimethylvaleronitrile was added dropwise to this over 2 hours. At the end of dropping, the temperature will be 110°C. 5.2 g of azobisisobutyronitrile was added 1 hour and 2 hours after the completion of the dropwise addition, and
The reaction is heated at 110°C for 2 hours. After the reaction was completed, acetone and some butyl cellosolve were removed by vacuum distillation to obtain a water-soluble resin solution with an acid value of 102 and a solid content of 69.2%. Next, an emulsion composition was synthesized in the same manner as in Example 1, except that the same amount of the above water-soluble resin solution was used in place of the water-soluble resin solution used in the preparation of the emulsion composition in Example 1, but the emulsion composition was stable. It was not possible to obtain a suitable emulsion composition.

【table】

[Table] Test method for emulsion properties and coating performance Emulsion condition: Observe with the naked eye whether or not a precipitate is formed. Viscosity: Using a Burckfield viscometer,
Measured at 6rpm and 30rpm. Adhesiveness: After drying for 10 days, the coated surface-treated steel plate was placed horizontally in an indirect hot air oven adjusted to 70℃, with the painted surface facing upward, and 5 sheets of 50 mm square gauze were stacked in the center of the coated surface. , 40mmφ in the center,
Place a 500g weight on it. After 1 hour, remove the gauze from the coated surface and examine the degree of adhesion between the coated surface and the gauze and the marks on the coated surface. Gloss: Measurement of 20° specular reflection of a paint film painted on a glass plate after drying for 10 days. Hardness: 1 for coatings applied to surface-treated steel sheets
Measurement of pencil hardness after drying for 1 day and 10 days. Water resistance: After 10 days of drying, water was applied to the painted surface of a surface-treated steel plate and the change in the paint film was observed after 1 hour. Abrasiveness: After polishing the painted surface 10 times after drying for 10 days with #400 water-resistant abrasive paper, observe whether there is any smearing on the abrasive paper. Adhesion: Make 100 1mm-wide goblets, stick cellophane adhesive tape on top, and peel it off vigorously. It is expressed as the number of pieces that remain without being peeled off.

Claims (1)

[Claims] 1 At least one radically polymerizable unsaturated monomer selected from (meth)acrylic acid esters and vinyl aromatic compounds, and at least one bond selected from urethane bonds, urea bonds, and amide bonds, with an average molecular weight of A water-soluble resin obtained by adding a glycidyl group-containing vinyl monomer to a carboxyl group-containing vinyl polymer, and a vinyl containing a carboxyl group and a hydroxyl group. In the presence of a water-soluble resin having a graft-polymerizable unsaturated group in its side chain, which is selected from water-soluble resins obtained by adding a monoaddition product of a diisocyanate compound and a hydroxyl group-containing acrylic monomer to a system polymer. A polar resin-containing emulsion composition obtained by emulsion polymerization.