JPH0834897A - Water-based resin composition - Google Patents

Abstract

PURPOSE:To provide a water-based resin composition which has excellent storage stability and provides a coating film excellent in water resistance, chemical resistance, mechanical strength, etc. CONSTITUTION:The composition comprises 1-85wt.% polyurethane resin and 1-85wt.% acrylic resin, the total amount of both being 2-90wt.% on a solid basis. The acrylic resin is obtained by polymerizing a mixture of unsaturated acrylic monomers in the presence of a reactive emulsifying agent having a copolymerizable unsaturated bond.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition containing a polyurethane resin and an acrylic resin. More specifically, the acrylic resin is suspended in the presence of a reactive emulsifier having a copolymerizable unsaturated bond. By using a product obtained by polymerization or emulsion polymerization, it is excellent in storage stability, and after forming a film, a water-based resin that gives a film excellent in water resistance, chemical resistance, film strength, etc. It relates to a composition.

[0002]

BACKGROUND OF THE INVENTION Synthetic resins such as polyurethane resin and acrylic resin are used in various paints,
In addition to being used as an adhesive, it is also used in a wide variety of applications such as processing agents for paper or textile products such as paper, fibers, woven fabrics, nonwoven fabrics, sizing agents for glass fibers, mortar modifiers, and floor polishes. There is. Conventionally, these applications have been used as a solvent-based varnish in which a synthetic resin is dissolved in an organic solvent, but this solvent-based varnish has drawbacks such as toxicity of the organic solvent, fire risk, and environmental pollution. In recent years, water-based resins, which use water instead of an organic solvent, are becoming mainstream.

Typical examples of the above water-based resin are water-based urethane and acrylic emulsion in which synthetic resin such as polyurethane resin and acrylic resin is emulsified and dispersed in water, and the above-mentioned drawbacks of the solvent-based varnish are eliminated. is there. However, while water-based urethane has excellent film-forming properties, elasticity (strength, elongation), abrasion resistance, cold resistance, and adhesion to polar substances, it has hydrolysis resistance, alkali resistance, stain resistance, and non-polarity. Has the disadvantage of poor adhesion to substances,
Also, acrylic emulsion is excellent in hardness, hydrolysis resistance, alkali resistance, stain resistance, gloss and adhesion to non-polar substances, but it is inferior in film forming property, so it is essential to use a film forming auxiliary together. Not only elasticity (strength, elongation),
There are drawbacks such as poor abrasion resistance, water resistance (especially hot water resistance), solvent resistance and adhesion to polar substances.

In order to compensate for these drawbacks, it has been proposed to use an aqueous resin composition in which a polyurethane resin and an acrylic resin are used together as film forming components. By using these resin components in combination, mechanical strength, adhesion, abrasion resistance, etc. are improved to some extent, but the effect of improving water resistance, especially hot water resistance, chemical resistance, etc., is only insufficient at all. Moreover, both of them had drawbacks in many cases.

The cause of adversely affecting the water resistance, chemical resistance, etc. of such an aqueous resin composition lies in the emulsifier used when emulsion polymerizing an unsaturated monomer to produce an acrylic resin emulsion. Although it is known that it is difficult to produce an acrylic resin emulsion without using an emulsifier, conventionally, reduction of the amount of the emulsifier used, selection of an emulsifier with less adverse effect, production of an acrylic resin emulsion in aqueous urethane Attempts have been made to improve these characteristics by such means.

For example, Japanese Patent Laid-Open No. 63-132975 proposes to solve the above-mentioned drawbacks by using polyoxyethylene-styrenated phenyl ether, which has less adverse effects, as an emulsifier.
JP-A-54-77795 and JP-A-59-1382.
11, JP-A-59-138212, JP-A-59-210978, JP-A-62-230863.
Japanese Patent Laid-Open No. 4-222802, Japanese Patent Laid-Open No. 5-3
No. 20299 gazette proposes to eliminate the above-mentioned drawbacks by polymerizing an ethylenically unsaturated monomer such as an acrylic monomer in aqueous urethane. Further, a proposal has been made to solve the above-mentioned drawbacks by chemically bonding a polyurethane resin and an acrylic resin, for example, JP-A-3-16621.
JP-A-3-195737 proposes a method of grafting an ethylenic monomer onto a polyurethane macromonomer having an ethylenic terminal group, and JP-A-3-195737 discloses a method of reacting with the reactive group in an aqueous urethane having a reactive group. A method of polymerizing an ethylenic monomer having a possible group has been proposed.

However, even by these methods, the effect of improving water resistance, chemical resistance, etc. is still insufficient, and in some cases, the polyurethane resin and the acrylic resin become non-uniform, and the formed film becomes non-uniform. Since it became opaque or lacked in storage stability, it was not practically satisfactory.

Therefore, an object of the present invention is to provide an aqueous resin composition which is excellent in storage stability and gives a film excellent in water resistance, chemical resistance and film strength.

[0009]

Means for Solving the Problems As a result of various studies, the present inventors have found that in an aqueous resin composition containing a polyurethane resin and an acrylic resin, as an emulsifier used in emulsion polymerization of the acrylic resin, By using a reactive emulsifier having a copolymerizable unsaturated bond, an aqueous resin composition using this acrylic resin is a polyurethane resin and It has been found that the above object can be achieved without impairing both properties of the acrylic resin.

The present invention has been made based on the above findings, and contains 1 to 85% by weight of a polyurethane resin and 1 to 85% by weight of an acrylic resin, and a resin solid content of 2 to 90% by weight, which is the total of both. An aqueous resin composition containing, wherein the acrylic resin is obtained by polymerizing a mixture of acrylic unsaturated monomers in the presence of a reactive emulsifier having a copolymerizable unsaturated bond. The present invention provides an aqueous resin composition characterized by being present.

The aqueous resin composition of the present invention will be described in detail below.

The polyurethane resin used in the present invention is
It can be produced by a well-known method, for example, a polyisocyanate compound, a polyol, another polyol having a carboxyl group or a sulfonic acid group or another polyol having a basic group in the molecule, is inert to the reaction and treated with water. It is produced by subjecting the prepolymer to a prepolymer by urethanization reaction in an organic solvent having a high affinity, and then neutralizing and chain extending the prepolymer and adding water to obtain an aqueous urethane.

Examples of the polyisocyanate compound used for producing the above-mentioned polyurethane resin (aqueous urethane) include aliphatic, alicyclic and aromatic polyisocyanates, and specifically, 2,4-tolylene diisocyanate. Isocyanate, 2,6-tolylene diisocyanate, 4,4
-Diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3 ' -Dimethoxy-4,4 '
-Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate and the like.

The amount of the above polyisocyanate compound used is preferably 0.8 to 3 times the equivalent of the total amount of the active hydrogens of the polyol, the other polyol having a carboxyl group or a sulfonic acid group and the chain extender described later, and further. It is preferably 1-2 times equivalent. If the amount used is less than 0.8 equivalents, excess polyol and the like will remain, and if it exceeds 3 equivalents, a large amount of urea bonds will be formed when water is added. In any case, the characteristics may be deteriorated.

Examples of the polyol used for producing the polyurethane resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and 1,2-butylene. Glycol, 1,
Low molecular weight polyols such as 3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, hydrogenated bisphenol A, ethylene oxide and / or propylene oxide adduct of bisphenol A,
Polyethylene glycol, polypropylene glycol,
Polyether / polypropylene polyols such as polyethylene / propylene glycol, polytetramethylene glycol, the low molecular weight polyols and succinic acid, glutaric acid, adipic acid,
Sebacic acid, phthalic acid, isophthalic acid, terephthalic acid,
Examples thereof include polyester polyols, polycarbonate polyols and polycaprolactone which are condensation products with polybasic acids such as tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid or carbonic acid.

Examples of other polyols having a carboxyl group or a sulfonic acid group used for producing the polyurethane resin include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid,
2,2-dimethylol valeric acid, 1,4-butanediol-2-sulfonic acid and the like can be mentioned. Further, as the other polyol having a basic group in the molecule used for producing the urethane, for example, methyldiethanolamine, butyldiethanolamine, triethanolamine, triisopropanolamine and the like basic group in the molecule The polyol etc. which it has are mentioned. Of these,
Particularly, when a polyol having a carboxyl group is used, a polyurethane resin (aqueous urethane) having excellent dispersibility can be obtained, which is preferable.

The amount of the other polyol having a carboxyl group or sulfonic acid group or the other polyol having a basic group in the molecule depends on the kind of the polyisocyanate compound and the polyol, but is usually polyurethane. It is 0.5 to 50% by weight, preferably 1 to 30% by weight, based on all the reaction components constituting the resin. If the amount used is less than 0.5% by weight, the storage stability is poor, and if it exceeds 50% by weight, the characteristics may be adversely affected.

Examples of the organic solvent which is inert to the reaction and has a high affinity for water used for producing the polyurethane resin include, for example, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-
2-pyrrolidone etc. can be mentioned. The amount of the organic solvent used is usually the above-mentioned raw materials (polyisocyanate compound, polyol, other polyol having a carboxyl group or a sulfonic acid group, or other basic group in the molecule) used for producing the prepolymer. 10 to 100% by weight based on the polyol).

Further, as a neutralizing agent for neutralizing the prepolymer in producing the polyurethane resin,
Examples thereof include organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine and triethanolamine, and inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia. Is an amount sufficient to neutralize the carboxyl groups or sulfonic acid groups.

When producing the polyurethane resin, the chain extender for extending the chain of the prepolymer includes, for example, polyols such as ethylene glycol and propylene glycol, ethylenediamine, propylenediamine, hexamethylenediamine and tolylenediamine. , Xylylenediamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, 2
-Methylpiperazine, isophoronediamine, melamine,
Examples thereof include amines such as succinic acid dihydrazide, adipic acid dihydrazide, and phthalic acid dihydrazide, and water. The amount of the chain extender used depends on the molecular weight of the target polyurethane resin, but is usually 0.5 to 10% by weight based on the prepolymer.

It is well known that the polyurethane resin used in the present invention is produced as an aqueous urethane from the above-mentioned raw materials, as described above. However, by appropriately changing the order of charging the above-mentioned raw materials or by charging the raw materials in a divided manner. It is also possible to manufacture.

The polyurethane resin is usually adjusted so that the resin solid content is 1 to 90% by weight, preferably 5 to 80% by weight.

As the polyurethane resin, it is also possible to use commercially available water-based urethane as it is. For example, "Adeka Bontiter" series manufactured by Asahi Denka Co., Ltd., Mitsui Toatsu Chemicals, Inc. "Olestar" series, Dainippon Ink and Chemicals Co., Ltd. "Bondic" series, "Hydran" series, Bayer "Implanyl" series, Japan Soflan Co., Ltd. "Sofranate" series, Kao's Poise series, Sanyo Chemical Co., Ltd.'s Sampren series, Hodogaya Chemical Co., Ltd.'Izelax 'series, Daiichi Kogyo Co., Ltd.'s Supermarket The "Flex" series, the "Neorets" series manufactured by Zeneca Co., Ltd., etc. can be used.

Next, the acrylic resin used in the present invention is obtained by polymerizing a mixture of acrylic unsaturated monomers in the presence of a reactive emulsifier having a copolymerizable unsaturated bond. is there. The mixture of acrylic unsaturated monomers preferably contains an ester of acrylic acid or methacrylic acid. Here, the above-mentioned reactive emulsifier having a copolymerizable unsaturated bond is one having an unsaturated bond copolymerizable with the mixture of the acrylic unsaturated monomer. Further, the above-mentioned polymerization is preferably carried out by emulsifying or dispersing in an aqueous solvent.

Examples of the acrylic ester or methacrylic ester in the mixture of acrylic unsaturated monomers used for producing the above acrylic resin include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Tert-butyl, amyl, hexyl, cyclohexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl, 2
Examples thereof include esters such as hydroxyethyl and glycidyl.

The content of the above acrylic acid ester or methacrylic acid ester can be arbitrarily set, but usually all monomers (the entire mixture of acrylic unsaturated monomers) are used.
It is 30% by weight or more, preferably 50% by weight or more.
When the content is less than 30% by weight, the effect obtained by using the acrylic acid ester or the methacrylic acid ester is hardly exhibited. In addition, as a particularly preferable use mode of the acrylic acid ester or the methacrylic acid ester, methacrylic acid glycidyl ester or acrylic acid glycidyl ester in all monomers, preferably 0.1 to
The content is 50% by weight, more preferably 1 to 30% by weight, and by using the unsaturated monomer containing the glycidyl methacrylic acid ester or the glycidyl acrylate acrylic acid, the water resistance of the film, Chemical resistance etc. is remarkably improved.

The mixture of acrylic unsaturated monomers may contain other unsaturated monomers together with the acrylic ester or methacrylic acid ester, and the other unsaturated monomers are copolymerized. You can also let it. Examples of the other unsaturated monomers above include ethylene, propylene, butene, isobutene, butadiene, vinyl chloride,
Aliphatic unsaturated hydrocarbons such as vinylidene chloride and halogenated aliphatic unsaturated hydrocarbons, styrene, α-methylstyrene, aromatic unsaturated hydrocarbons such as vinyltoluene, crotonic acid, itaconic acid, fumaric acid, maleic acid, etc. Other unsaturated carboxylic acid esters (an example of an alcohol component forming an ester is an alcohol component forming an ester of acrylic acid and methacrylic acid), vinyl benzoate, a vinyl ester such as vinyl acetate, acrylamide, methacryl Examples thereof include nitrogen-containing vinyl monomers such as amide, N-methylol acrylamide, N-methylol methacrylamide, and acrylonitrile.

The above-mentioned mixture of acrylic unsaturated monomers is
It is possible to charge it all at once at the beginning of the reaction, or to divide it or to continuously charge it. Furthermore, if necessary, a chain transfer agent such as mercaptans can be added.

A polymerization initiator may be used in the production of the acrylic resin, and the polymerization initiator is not particularly limited, and not only a water-soluble initiator used in ordinary emulsion polymerization, Oil soluble initiators can also be used. As the polymerization initiator, for example,
Examples thereof include potassium persulfate, ammonium persulfate, azobiscyanovaleric acid, azobisisobutyronitrile, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, and the like. It is also possible to use so-called redox-based catalysts which consist of a combination with xylates.

The amount of the above-mentioned polymerization initiator to be used depends on the kind of unsaturated monomer in the mixture of acrylic unsaturated monomers,
Although it varies depending on the concentration, reaction temperature, etc., it is generally preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on all the monomers.

The above polymerization initiator may be added all at once, or may be added dividedly or continuously.

The reaction temperature for producing the acrylic resin varies depending on the type and amount of each of the unsaturated monomer and the polymerization initiator in the acrylic unsaturated monomer mixture. , Usually 0 ℃ ~ 100 ℃
Is.

Further, the reactive emulsifier used for producing the acrylic resin has an unsaturated bond in the molecule which can be copolymerized with the unsaturated monomer in the mixture of the acrylic unsaturated monomer. Any nonionic, anionic or cationic type can be used.

The above-mentioned reactive emulsifier is a compound having at least one hydrophobic group, hydrophilic group and reactive group in the molecule. The hydrophobic group is composed of an aliphatic or aromatic hydrocarbon group, and the hydrophilic group is represented by a nonionic group represented by a polyoxyalkylene ether group, a sulfonate, a carboxylate or a phosphate. It contains a cationic group represented by an anionic group and a quaternary ammonium salt, and the reactive group is a vinyl ether group, an allyl ether group, a vinylphenyl group, an allylphenyl group, an ester or amide of acrylic acid or methacrylic acid. Group, an ester or amide group of an unsaturated dibasic acid such as maleic acid.

Examples of the reactive emulsifiers include those disclosed in JP-A Nos. 62-22803 and 62-1048.
No. 02, No. 62-104803, No. 62-2
No. 21431, No. 62-22143, No. 6
No. 2-225237, No. 62-244430, No. 62-286528, and No. 62-28922.
8 gazette, the same 62-289229 gazette, the same 63-12.
334, 63-54930 and 63-7.
No. 7530, No. 63-77531, No. 63-
77532, 63-84624, 63.
-84625, 63-126535, 63-126536, 63-147530, 63-319035, and Japanese Patent Laid-Open No. 1-1163.
No. 0, No. 1-22338, No. 1-222627.
No. 1,22,628, No. 1-30632, No. 1-344430, No. 1-34431, No. 1-344432, No. 1-99638, No. 1-99639. Examples thereof include those described in JP-A Nos. 4-50204, 4-53802, and 4-55401.

Specific examples of the reactive emulsifier include, for example, 1- (meth) allyloxy or (meth) acryloyloxy or (meth) allyloxycarbonylmethyl-3-alkoxy (polyoxyalkylenoxy).
Or alkylphenoxy (polyoxyalkylenoxy) or acyloxy (polyoxyalkylenoxy)-
2-Hydroxypropane or its alkylene oxide adduct or their sulfuric acid or phosphoric acid ester alkali or ammonium salt, bisphenol compound or glycol compound's alkylene oxide adduct or their sulfuric acid or phosphoric acid ester alkali or ammonium salt, vinyl or allylphenol compound Alkylene oxide adducts or their sulfuric acid or phosphoric acid ester alkali or ammonium salts, sulfosuccinic acid monoallyl-monoalkyl ester alkali or ammonium salts, sulfosuccinic acid mono (3-allyloxy-2-hydroxypropyl) -monoalkyl ester alkali or ammonium Salt and the like.

As the above-mentioned reactive emulsifier, it is preferable to use the compound represented by the general formula (I) of the following [Chemical Formula 2] because a film having excellent water resistance and chemical resistance can be obtained.

[0038]

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Examples of the hydrocarbon group having 6 to 30 carbon atoms represented by R ₂ in the above general formula (I) include hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, Undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacyl, and other alkyl groups, octenyl, decenyl, dodecenyl, octadecenyl, and other alkenyl groups, octylphenyl, nonylphenyl, dinonylphenyl, and other alkyl groups. Examples of the phenyl group include an acyl group derived from the above alkyl group and alkenyl group, a hydroxy group such as hydroxystearoyl and chlorostearoyl, and a halogen atom. Acyl groups derived from alkyl groups and alkenyl groups.

The alkylene group having 2 to 4 carbon atoms represented by A includes ethylene, 1,2-propylene,
Examples thereof include 1,3-propylene, 1,2-butylene, 1,3-butylene and 1,4-butylene.

Examples of the nonionic hydrophilic group represented by Z include, for example, 1 to 100 mol of an alkylene oxide having 2 to 4 carbon atoms and an anion of a compound in which Z is a hydrogen atom. Examples of the hydrophilic group of the system include a compound in which Z is a hydrogen atom, or a compound in which Z is a nonionic hydrophilic group described above is salified with sulfuric acid or phosphoric acid ester.

The compound represented by the general formula (I) is a compound (I-1) represented by the following [Chemical Formula 3] in which Z is a hydrogen atom, and Z is a nonionic hydrophilic group, as shown below. The compound (I-2) shown in the following [Chemical formula 4] and the compound (I-3) shown in the following [Chemical formula 5] in which Z is an anionic hydrophilic group are classified. Among these compounds, compounds in which Z is a nonionic or anionic hydrophilic group are more preferable.

[0043]

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[0044]

[Chemical 4]

[0045]

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[In the above compounds (I-1) to (I-3), R ₁ , R ₂ , X, A and m have the same meanings as in the above general formula (I), and n represents 1 to 100. , P represents 0 to 100, Z ′ represents —SO ₃ —M ₁ or —PO (OM ₁ ) (OM ₂ ), and M ₁ and M ₂ are each independently a hydrogen atom, an alkali metal, or an alkaline earth. Represents a metal, ammonium, alkyl ammonium or hydroxyalkyl ammonium. )

The amount of the reactive emulsifier used is preferably 0.1 to the mixture of the acrylic unsaturated monomers.
It is 20% by weight. If the amount used is less than 0.1% by weight, the emulsion stability is insufficient, and if it exceeds 20% by weight, the properties of the coating film obtained from the water-based resin may be adversely affected. .

When producing the acrylic resin, it is possible to use a small amount of a non-reactive emulsifier together with the reactive emulsifier, but the emulsifier remaining in the system adversely affects the characteristics of the coating. , Its usage should be as low as possible.

The water-based resin composition of the present invention contains the above-mentioned polyurethane resin and acrylic resin, but the preparation method is not particularly limited, and the separately prepared aqueous urethane (polyurethane resin) and acrylic resin are used. Either a method of mixing an emulsion (acrylic resin) or a method of adding a mixture of an acrylic unsaturated monomer and a reactive emulsifier to aqueous urethane and polymerizing can be adopted.

In the above-mentioned method of mixing the water-based urethane and the acrylic emulsion, which are separately produced, the order of mixing, the temperature and other conditions are not particularly limited. For example, the water-based urethane is added to the acrylic emulsion little by little and mixed. Method, a method of adding and mixing acrylic emulsion little by little in water-based urethane, or a method of mixing both at once, and when both are cooled and then mixed, when one or both are at high temperature or heated. You may mix underneath.

Particularly when an acrylic emulsion obtained from an unsaturated monomer mixture containing glycidyl methacrylate or glycidyl acrylic acid is used, it is mixed with an aqueous urethane at 50 to 100 ° C. or an aqueous urethane. By using the water-based resin composition of the present invention obtained by polymerizing a mixture of acrylic unsaturated monomers at 50 to 100 ° C., it is recognized that the characteristics of the formed film tend to be improved. It is not clear why the properties of the film formed by using the water-based resin composition produced at such a high temperature are improved, but the carboxyl group or sulfonic acid group contained in the polyurethane resin and the acrylic resin It is presumed that this is because the glycidyl group contained in the resin reacts with each other to form a partial chemical bond between the two, thereby improving the homogeneity of both resins.

The content of the polyurethane resin and the acrylic resin in the water-based resin composition of the present invention can be widely varied depending on the purpose of use, but normally the polyurethane resin is 1 to 85% by weight, The acrylic resin is 1 to 85% by weight, and the total resin solid content of both is 2 to 90% by weight, preferably 5 to 80% by weight. When the resin solid content is less than 2% by weight, it takes a long time to dry, and when it exceeds 90% by weight, not only the viscosity is high and it is inconvenient to handle, but also the storage stability may be deteriorated. is there.

In the water-based resin composition of the present invention,
The ratio of the polyurethane resin and the acrylic resin,
Although not particularly limited, it is usually 1:10 to 1 by weight ratio.
It is 0: 1. If the above ratio is out of this range, the amount of polyurethane resin or acrylic resin becomes too small and desired properties are often not obtained.

The aqueous resin composition of the present invention contains an antioxidant, an ultraviolet absorber, a colorant, a wax, an antiseptic, an antifoaming agent, a plasticizer, a solvent, and a film-forming aid, depending on the purpose. Conventional additives such as a dispersant, a thickener, and a fragrance may be added.

The water-based resin composition of the present invention is used for coating fabrics, paper, leather, metal, wood, plastics moldings, slate boards, and other coating materials, binders, adhesives, floors for impregnating fibers, fabrics and the like. It can be used for various purposes such as a polish and a sizing agent for glass fibers.

[0056]

The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited thereto. In addition, "parts" in the production examples and examples represent "parts by weight" unless otherwise specified.

Production Example 1 [Production Example of Polyurethane Resin (Aqueous Urethane)] Polypropylene glycol having an average molecular weight of 1000 (PP
G1000) 49 parts, dicyclohexylmethane diisocyanate (hydrogenated MDI) 176 parts, dimethylolpropionic acid 70 parts and N-methylpyrrolidone 196 parts were placed in a reaction vessel and reacted while maintaining at 80 to 100 ° C. to produce a prepolymer. .

Then, 48 parts of triethylamine was added to neutralize, 5 parts of hexamethylenediamine was added, and a crosslinking reaction was carried out at 35 ° C. or lower while adding water, and 456 parts of water was added until the reaction was completed. A polyurethane resin (aqueous urethane A) having a solid content of 35% by weight was produced.

Production Example 2 [Production Example of Polyurethane Resin (Aqueous Urethane)] 140 parts of propylene oxide adduct of bisphenol A (BPAPO) having an average molecular weight of 790, 151 parts of xylylene diisocyanate and N-methylpyrrolidone 120
Part is placed in a reaction vessel and the NCO content is 1 at 80 to 85 ° C.
A prepolymer was produced by reacting until it reached 0.3% by weight.

Then, 14 parts of dimethylolpropionic acid and 25 parts of 1,4-butylene glycol were added, and a crosslinking reaction was carried out at the same temperature to react until the absorption of the isocyanate group disappeared in the infrared absorption spectrum. 12 parts of water and 538 parts of water were added for neutralization, followed by aging for 1 hour to produce a polyurethane resin (aqueous urethane B) having a resin solid content of 34% by weight.

Production Example 3 [Production Example of Polyurethane Resin (Aqueous Urethane)] Terephthalic acid and isophthalic acid (weight ratio 1: 1) were used as dibasic acid components, and ethylene glycol and diethylene glycol (weight ratio 2: 1 were used as glycol components.
3) 100 parts of a polyester polyol having a molecular weight of 1000 (polyester polyol 1), 107 parts of isophorone diisocyanate and 90 parts of methyl ethyl ketone
After a portion of the mixture was placed in a reaction vessel and sufficiently mixed at 75 ° C, 20 parts of dimethylolpropionic acid was added, and the mixture was reacted at 70 ° C for 12 hours. After neutralizing by adding 60 parts of 5% aqueous ammonia, methyl ethyl ketone was distilled off under reduced pressure, and water was added to produce a polyurethane resin (aqueous urethane C) having a resin solid content of 23% by weight.

By the same operation as in Production Example 1 above, polyurethane resins (aqueous urethane D to G) obtained from the compounds (amount used) shown in the following [Table 1] were produced. still,
The compounds used in the production of the above-mentioned aqueous urethanes A to C (amount used) are also shown in the following [Table 1].

[0063]

[Table 1]

Production Example 4 [Production Example of Acrylic Resin (Acrylic Emulsion)] 100 parts of ion-exchanged water and 2 parts of a reactive emulsifier (Emulsifier A) represented by the following formula (Chemical Formula 6) were taken and the temperature was raised to 70 ° C. After warming, 0.6 parts of ammonium persulfate was added. A mixed emulsion consisting of 45 parts of methyl methacrylate, 45 parts of n-butyl acrylate, 10 parts of glycidyl methacrylate, 1 part of emulsifier A and 30 parts of ion-exchanged water was added dropwise over 3 hours. 1 at temperature
Allowed to react for hours. After that, adjust the pH to 8-9 with aqueous ammonia.
To prepare an acrylic resin (acrylic emulsion A) having a resin solid content of 44% by weight.

[0065]

[Chemical 6]

Acrylic resins (acrylic emulsions B to F) obtained from the compounds (amount used) shown in the following [Table 2] were produced in the same manner as in Production Example 4 above.
The compounds (amount used) used in the production of the acrylic emulsion A are also shown in the following [Table 2].

[0067]

[Table 2]

Production Examples 5 to 9 [Production Examples of Acrylic Resin (Acrylic Emulsion)] A reactive emulsifier from the emulsifier A is represented by the following [Chemical formula 7] to [Chemical formula 1].
1] in the same manner as in Production Example 4 except that the reactive emulsifiers B, C, D, E and F are changed to acrylic resins (acrylic emulsifiers G, H, I, J and K). ) Was manufactured.

[0069]

[Chemical 7]

[0070]

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[0071]

[Chemical 9]

[0072]

[Chemical 10]

[0073]

[Chemical 11]

Example 1 [Manufacture of Water-based Resin Composition by Mixing Polyethanane Resin (Aqueous Urethane) and Acrylic Resin (Acrylic Emulsion)] Aqueous urethane and acrylic emulsion having the formulations shown in [Table 3] to [Table 5] below. Were mixed at 30 ° C. for 2 hours to prepare aqueous resin compositions No. 1 to No. 21.

The obtained water-based resin composition was applied onto a glass plate so that the thickness of the film when dried was 0.5 mm, naturally dried at 20 ° C. for one day and then dried at 80 ° C. for 5 minutes. A film was formed, and the test pieces obtained were tested for water resistance, alkali resistance, acid resistance and transparency under the following conditions. The results are shown in [Table 3] to [Table 5] below.
Shown in

According to JIS K5400, water resistance is soaked for 30 days, and alkali resistance is soaked in 3.5% sodium hydroxide aqueous solution at 60 ° C. for 1 hour.
The immersion time was 24 hours according to ISK5400.
The results were evaluated according to the following criteria. ⊚: No change from before the test. ◯: No wrinkles, swelling or peeling, but slight discoloration. Δ: Wrinkles, swelling or peeling were observed, and discoloration was observed. X: Wrinkles, swelling or peeling are observed, and discoloration is remarkable.

The transparency of the film was visually observed and evaluated according to the following criteria. ○: The whole is transparent. Δ: Turbidity is partially observed. X: Cloudy.

The storage stability (storage stability) of these aqueous resin compositions when stored at 50 ° C. for 30 days was visually evaluated. The results were evaluated according to the following criteria. ◯: No increase in viscosity and no phase separation Δ: Can be used although viscosity increase or phase separation is observed. X: The viscosity was increased or the phase separation was remarkable, so that it cannot be used.

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

Example 2 [Production of water-based resin composition by polymerization of acrylic monomer in polyurethane resin (water-based urethane)] 126 parts of ion-exchanged water, 3 parts of emulsifier A, water-based urethane E
200 parts was taken and the temperature was raised to 60 ° C. 100 parts (total amount) of a mixture of unsaturated monomers having the composition shown in [Table 6] below and 10% of tertiary butyl hydroperoxide
4 parts of the aqueous dispersion was added dropwise over 3 hours. After completion of dropping 7
The polymerization reaction was completed by keeping it at 0 ° C for 1 hour, and the resin solid content was 3
7% by weight of water-based resin composition (water-based resin composition No. 22 to 2
7) was manufactured.

The same test as in Example 1 was conducted using the obtained water-based resin composition. The results are shown in [Table 6] below.
Shown in

[0084]

[Table 6]

Example 3 In order to see the effect when the water-based resin composition was produced at high temperature, water-based resin compositions No. 5 and No. 5 were prepared in the same manner as in Example 1 except that mixing was carried out at 70 ° C. .6 and No. 12 water-based resin composition (water-based resin composition N
28-30) was produced.

The obtained water-based resin composition was applied so that the film thickness when dried was 150 μm, and the resulting film had tensile strength (Kgf / cm ² ), elongation (%) and 100% modulus (Kgf / Kgf / cm ² ). cm ² ) was measured, and the results are shown in [Table 7] below. Regarding the water resistance, alkali resistance, acid resistance and transparency of the film and the storage stability of the water-based resin composition, no difference was observed between the case where it was produced at room temperature and the case where it was produced at high temperature.

[0087]

[Table 7]

From the results obtained by using the water-based resin compositions Nos. 1 to 7, when the acrylic resin polymerized with the reactive emulsifier was used, the water resistance was improved even when the composition of the polyurethane resin to be combined was changed. It is clear that a film having excellent properties, alkali resistance, acid resistance and transparency is obtained, and that the storage stability of the water-based resin composition is also good.

Similarly, when the combination ratio of the polyurethane resin and the acrylic resin was changed (water-based resin composition Nos. 5 and 8 to 11), when the composition of the acrylic resin was changed (water-based resin composition No. 5). And 13 to 15), when the type of reactive emulsifier used is changed (water-based resin composition No. 5
And 17 to 21), or when the acrylic resin is polymerized in aqueous urethane (water-based resin composition No. 22, 24, 26)
And 27), it is clear that a film excellent in water resistance, alkali resistance, acid resistance and transparency is obtained, and that the storage stability of the water-based resin composition is also good.

In particular, the case of using the water-based resin composition No. 5 and the case of using the water-based resin composition No. 15 or the case of using the water-based resin composition No. 22 and the case of the water-based resin composition No. 24
From the comparison with the case of using, the remarkable effect is exhibited when a monomer mixture containing methacrylic acid glycidyl ester is used as the acrylic resin, and the water-based resin composition No.
From the comparison between the case of using 5 and 17 to 20 and the case of using the water-based resin composition No. 21, the water resistance and the water resistance when the compound represented by the general formula (I) was used as the reactive emulsifier. It is clear that the alkalinity is remarkably excellent.

On the other hand, water-based resin composition No. 5 and water-based resin composition No. 12, water-based resin composition No. 15, water-based resin composition No. 16, water-based resin composition No. 22 and water-based resin composition Object N
o.23 or a comparison between the case of using the water-based resin composition No. 24 and the case of using the water-based resin composition No. 25, water resistance, alkali resistance and acid resistance were observed when a non-reactive emulsifier was used. It is clear that not only the property is insufficient, but also the uniformity (transparency) of the film is poor and the storage stability tends to be poor.

Further, as shown in the above [Table 7], when the water-based resin composition using the reactive emulsifier of the present invention is produced at a high temperature, the water resistance and chemical resistance of the film are adversely affected. While the strength and elongation are improved without any use, the improvement effect is hardly recognized when the non-reactive emulsifier is used.

[0093]

The water-based resin composition of the present invention is excellent in storage stability even though almost no free emulsifier remains. In addition, the film formed from the water-based resin composition of the present invention is not only excellent in water resistance, chemical resistance (alkali resistance, acid resistance) and transparency, but also has the characteristics of high strength and elongation. (Claim 1). Further, the water-based resin composition of the present invention contains an acrylic resin obtained by using a specific reactive emulsifier, and thereby gives a film particularly excellent in water resistance and chemical resistance (claim 2). Further, the water-based resin composition of the present invention contains an acrylic resin obtained by polymerizing a mixture of specific acrylic unsaturated monomers, thereby giving a film particularly excellent in water resistance and chemical resistance ( Claim 3). Therefore, the aqueous resin composition of the present invention is extremely suitable for use as a paint, a binder, an adhesive and the like.

Claims (3)

[Claims] 1. An aqueous resin composition containing 1 to 85% by weight of a polyurethane resin and 1 to 85% by weight of an acrylic resin, and containing 2 to 90% by weight of a resin solid content obtained by adding the two. An aqueous resin composition, wherein the acrylic resin is obtained by polymerizing a mixture of acrylic unsaturated monomers in the presence of a reactive emulsifier having a copolymerizable unsaturated bond. 2. The water-based resin composition according to claim 1, wherein the reactive emulsifier is a compound represented by the following general formula (I). Embedded image 3. The unsaturated monomer mixture containing the acrylic acid glycidyl ester or acrylic acid glycidyl ester in an amount of 0.1 to 50% by weight. Water-based resin composition.