JPH09255867A - Aqueous composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous composition, capable of manifesting high bonding characteristics in the original state, high quality and excellent executability and useful as a coating material, a tacky agent, an adhesive, etc., by dispersing a mixture comprising a urethane (pre)polymer having self emulsifiability and a specific tackifying resin in water. SOLUTION: This aqueous composition is obtained by dispersing a mixture comprising (A) a urethane polymer and/or a urethane prepolymer having self emulsifiability and (B) a tackifying resin having 130-200 deg.C softening point in water. Furthermore, (C) a compound having >=2 functional groups having the reactivity with the carboxyl group in the component A (preferably an aziridine- based, an epoxy-based or carbodiimide-based cross-linking agent) is preferably added to the composition. The amount of the added component B is preferably 5-150 pts.wt. based on 100 pts.wt. component A. The amount of the added component C is preferably 0.5-50 pts.wt. based on 100 pts.wt. component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous composition, and more particularly to an aqueous composition suitable for a paint, a viscous / adhesive agent and a coating agent.

[0002]

2. Description of the Related Art Conventionally, solvent-based paints, adhesives, adhesives, coating agents, etc. have been widely used because of their excellent adhesion and adhesiveness. However, with the increase in demand for the above paints, adhesives, adhesives, coating agents, etc., the working environment deteriorates due to the volatilization of the organic solvents used, the risk of fire increases, the air pollution area For reasons such as increased risk, paints that do not use organic solvents such as water-based
Actively studying conversion to adhesives, coatings, etc.
It is currently being implemented.

However, in general, water-based paints have the drawback of low adhesive strength as compared with solvent-based paints, adhesives, adhesives, coatings and the like. Although there are many proposals for improving the above-mentioned drawback of low adhesive strength, for example, in JP-A-5-222288, a tackifying resin is uniformly dissolved in an organic solvent solution of a urethane prepolymer before chain extension. After that, a method for producing a urethane-based aqueous dispersion containing a tackifying resin by dispersing in water is disclosed. The urethane-based aqueous dispersion obtained by the method for producing a urethane-based aqueous dispersion disclosed in JP-A-5-222288 has a drawback that sufficient heat resistance cannot be obtained.

[0004]

SUMMARY OF THE INVENTION The present invention is to provide an aqueous composition having both sufficient adhesiveness and excellent heat resistance which cannot be solved by the above-mentioned prior art.

[0005]

The present invention according to claim 1 provides a mixture of a self-emulsifying urethane polymer and / or urethane prepolymer and a tackifying resin having a softening point of 130 to 200 ° C in water. The gist of the present invention is an aqueous composition characterized by being dispersed.

The present invention according to claim 2 is characterized in that the aqueous composition according to claim 1 is further provided with two or more functional groups reactive with a carboxyl group of the urethane polymer and / or the urethane prepolymer. The gist of the invention is an aqueous composition to which a compound having the above is added.

The self-emulsifying urethane polymer and / or urethane prepolymer used in the present invention is a compound having two or more active hydrogens capable of reacting with a polyisocyanate compound and an isocyanate and an ionic or nonionic compound in the molecule. Or a potentially ionic hydrophilic group, and a reaction product with a compound having two or more active hydrogens capable of reacting with isocyanate. The above reaction product, if necessary, in forming the aqueous composition,
Prior to water dispersion, during water dispersion, or after water dispersion, a chain extender may be used to increase the molecular weight.

The polyisocyanate compound is not particularly limited, but for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, 3-isocyanate methyl-3,
5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate,
Fats such as methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, transcyclohexane-1,4-diisocyanate Group diisocyanates, 2,4
-Aromatic diisocyanates such as toluylene diisocyanate, 2,6-toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,5-naphthene diisocyanate, tolidine diisocyanate, tetraalkyldiphenylmethane diisocyanate and paraphenylene diisocyanate. . The polyisocyanate compound may be used alone or in combination of two or more.

The compound having two or more active hydrogens capable of reacting with the above-mentioned isocyanate is not particularly limited, but, for example, as a polyol compound having a molecular weight of 500 to 10000, polyene such as polyethylene glycol or polypropylene glycol is used. Dicarboxylic acids such as ether polyols, adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid and isophthalic acid, and ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, Polyester polyols obtained from diols such as tripropylene glycol and neopentyl glycol, polycaprolactone diol, polytetramethylene ether diol, polybutadiene diol, hydrogenated polybutane Diol, polycarbonate diol, polythioether diol, polyacrylate diol. The compound having two or more active hydrogens capable of reacting with the above-mentioned isocyanate is a single
Seed may be used, or two or more may be used in combination.

When a single compound having two or more active hydrogens capable of reacting with the above isocyanate is used, the molecular weight of the compound is 500 to 10,000, preferably 8
It is from 00 to 7,000, more preferably from 1000 to 5000. When the molecular weight is less than 500, the dry film obtained from the aqueous composition becomes too hard, and when the molecular weight exceeds 10,000, the viscosity of the urethane polymer and / or urethane prepolymer before water dispersion becomes too high,
Dispersion work during water dispersion becomes difficult.

The compound having two or more active hydrogens capable of reacting with the above isocyanate has a molecular weight of 500 to 1000.
The above compound in the range of 0 has a molecular weight of less than 500,
For example, a compound having two or more active hydrogens capable of reacting with the above isocyanate such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol may be mixed and used.

The compound having a hydrophilic group having ionic, nonionic or latent ionicity in the molecule and having two or more active hydrogens capable of reacting with isocyanate is the urethane polymer and / or urethane. It has a role of imparting self-emulsifying property to an aqueous composition containing a reaction product with a prepolymer. The hydrophilic group is not particularly limited, but examples of the ionic hydrophilic group include a sulfonate group, a carboxylate group, an ammonium group, and the like, and the nonionic hydrophilic group includes: For example, a polyoxyethylene group, a hydroxyl group, etc. are mentioned.

The above-mentioned latent ionic hydrophilic group means the above-mentioned latent ionic hydrophilic group before or during the dispersion of the mixture of the urethane polymer and / or urethane prepolymer in water. And a hydrophilic group capable of converting the hydrophilic group into a hydrophilic group having complete or partial ionicity by adding an activator which acts on the hydrophilic group to dissociate the hydrophilic group into ions. For example, a free acid group (latent anionic group) such as a carboxylic acid group or a sulfonic acid group can be mentioned and is preferably used.

The compound having a hydrophilic group having an ionic, nonionic or latent ionic property in the molecule and having two or more active hydrogens capable of reacting with isocyanate has the general formula: RC (CH ₂ OH) ₂ COOH [In the formula, R represents an alkyl group having 1 to 20 carbon atoms. ], For example, dimethylolalkanoic acids such as dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolvaleric acid. The above compounds may be used alone or in combination of two or more.

The compound having an ionic, nonionic or latent ionic hydrophilic group in the molecule and having two or more active hydrogens capable of reacting with an isocyanate is preferably the urethane polymer or / Or 0.1 to 2.0 mmol per 1 g of the urethane prepolymer is added. When the addition amount is less than 0.1 mmol per 1 g of the obtained urethane polymer and / or urethane prepolymer, sufficient hydrophilicity is not imparted to the urethane polymer and / or urethane prepolymer, and a stable aqueous dispersion is obtained. Difficult to do. On the other hand, if the amount added exceeds 2.0 mmol, the hydrophilicity of the urethane polymer and / or urethane prepolymer increases, and the water resistance of the dry film of the resulting aqueous composition decreases.

As a compound having a hydrophilic group having ionic, nonionic or latent ionicity in the molecule and having two or more active hydrogens capable of reacting with isocyanate, the hydrophilicity having latent ionicity When a compound having a functional group is used, it is necessary to neutralize the acid group in the urethane polymer and / or urethane prepolymer with a neutralizing agent. The neutralizing agent is not particularly limited, but examples thereof include alkali metal hydroxides such as NaOH and KOH, and tertiary amines such as ammonia, trimethylamine and triethylamine, which scatter during drying. Removed from the dry film formed from the above aqueous composition,
Among them, volatile tertiary amines are preferably used because they improve the water resistance of the dry film.

The urethane polymer and urethane prepolymer having self-emulsifying property may be prepared by any of bulk polymerization method and solution polymerization method, but the reaction temperature is preferably 50 to 150 ° C. Is. When a solution polymerization method is adopted as the above-mentioned polymerization method, the solvent used is preferably inert to isocyanate groups such as acetone, methyl ethyl ketone, tetrahydrofuran, and methyl acetate, has high miscibility with water, and has a boiling point. Is 100 ° C. or lower. The boiling point of the solvent is 10
If the temperature exceeds 0 ° C, it will be difficult to remove only the solvent from the obtained water dispersion to the outside of the system in a step after water-dispersing a mixture of a urethane polymer, a urethane prepolymer and the like having self-emulsifying property.

In the above polymerization method, a polymerization catalyst such as an amine compound or an organometallic compound may be used to adjust the polymerization reaction rate. As the amine compound,
For example, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylguadinine,
Examples include triethylenediamine, dimethylaminoethanol, bis (2-dimethylaminoethyl) ether and the like. Examples of the organometallic compound include stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, phenylmercuric propionate, lead octenoate and the like. The polymerization catalyst may be used alone, or two or more kinds may be used in combination.

The softening point of the tackifying resin is 130 to 2
The temperature is 00 ° C, preferably 130 to 180 ° C. If the softening point of the tackifying resin is less than 130 ° C, the heat resistance of the resulting aqueous composition is lowered, and if it exceeds 200 ° C, the tackifying resin has a sufficiently large molecular weight, so that the tackifying effect is sufficient. I can't get it.

Examples of the tackifying resin include gum rosin, tall oil rosin, wood rosin, polymerized rosin,
Hydrogenated rosin, disproportionated rosin, rosin ester, hydrogenated rosin ester, disproportionated rosin ester, rosin-modified phenol resin, rosin-based resin such as maleic acid-modified rosin resin, terpene resin, phenol resin, phenol such as alkylphenol resin Resin, terpene phenolic resin,
Xylene resin, phenol-modified xylene resin, ketone resin, aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin, coumarone resin, styrene resin and the like,
Among them, xylene resin, ketone resin, and novolac type alkylphenol resin are particularly preferable. The tackifier resins may be used alone or in combination of two or more.

The tackifying resin is added in an amount of 5 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 parts by weight based on 100 parts by weight of the self-emulsifying urethane polymer and / or urethane prepolymer. ~ 100
Parts by weight. If the amount added is less than 5 parts by weight, the adhesiveness of the resulting aqueous composition will not be sufficiently imparted, and if the amount added exceeds 200 parts by weight, the hydrophobic properties of the dispersed particles of the obtained aqueous composition will be poor. The ratio of the components increases, and the stability of dispersed particles decreases.

In the aqueous composition of the present invention according to claim 1, a mixture of the self-emulsifying urethane polymer and / or urethane prepolymer and the tackifying resin having a softening point of 130 to 200 ° C. is dispersed in water. Obtained. Mixing of the self-emulsifying urethane polymer and / or urethane prepolymer and the tackifying resin having a softening point of 130 to 200 ° C. is required to be sufficiently mixed and mutually melted to form a homogeneous system. Is.

When a urethane polymer is used as the self-emulsifying urethane polymer and / or urethane prepolymer, the softening point is 130 to 20.
When mixed with a tackifying resin at 0 ° C., the urethane polymer and the tackifying resin having a softening point above 130 ° C. are dissolved in a hydrophilic organic solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, N-methylpyrrolidone. , And they are mixed well until they mix with each other to form a clear solution. The above-mentioned two-component solution is preferably prepared so that the viscosity in its normal state is 50,000 cps or less. The two-component solution prepared in the above viscosity range has no risk of aggregation in the water dispersion step.

When a urethane prepolymer is used as the urethane polymer and / or urethane prepolymer having the self-emulsifying property, the softening point is 13
The tackifying resin at 0 to 200 ° C. may be dissolved in the urethane prepolymer and sufficiently mixed until they melt each other to form a transparent solution. However, like the urethane polymer, it is dissolved in a hydrophilic organic solvent. , May be mixed well until the two melt together and form a clear solution.

The above-mentioned self-emulsifying urethane polymer and / or urethane prepolymer has a softening point of 130.
When it is attempted to disperse it in water in the water dispersion step without sufficiently mixing the tackifying resin at ˜200 ° C., agglomeration occurs and the stability of the resulting aqueous composition is low and small, and solid content is low. May cause segregation and sedimentation.

The above-mentioned self-emulsifying urethane polymer and / or urethane prepolymer has a softening point of 130.
The method of dispersing a homogeneous mixture of tackifying resins at ˜200 ° C. in water is not particularly limited, but for example, an acetone method of dispersing an organic solvent solution of the urethane polymer and / or urethane prepolymer in water A self-emulsifying a prepolymer having a terminal isocyanate group, a chain extension prepolymer mixing method, a mixture of a prepolymer having a terminal isocyanate group blocked and a chain extender dispersed in water, deblocked, and a block isocyanate method for chain extension, After dispersing the pre-polymer of the terminal buret group by heating and melting water,
Examples include a melt dispersion method in which methylol is formed with formaldehyde and the chain is extended. In each of the above dispersion methods, a mixture of a self-emulsifying urethane polymer and / or urethane prepolymer and a homogeneous mixture of a tackifying resin having a softening point of 130 to 200 ° C. and water is subjected to mechanical shearing force. While adding, a method of adding water little by little to the above mixture,
Batch type means such as a method of adding the mixture little by little to the water in which mechanical shearing force is applied, the mixture and water are continuously supplied by a constant amount supply device, respectively, rotor-stator type, line mill type, static mixer type, Examples include a vibrating and other continuous means for dispersing using various continuous emulsifying and dispersing machines.

When a urethane prepolymer having a terminal isocyanate group is dispersed in water, a compound and / or water having two active hydrogens capable of reacting with an isocyanate group in the water dispersion step or in the step subsequent to the water dispersion step. The chain is extended by. Examples of the compound having two active hydrogens capable of reacting with the above-mentioned isocyanate group used as a chain extender include ethylenediamine,
1,4-butanediamine, 1,6-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5
-Diamino compounds such as dimethylpiperazine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 And diol compounds such as hexanediol.

The amount of the compound having two active hydrogens capable of reacting with the above isocyanate group used as the chain extender added is preferably equal to or less than the equivalent amount of the isocyanate group serving as the origin of chain extension in the urethane prepolymer. When the amount added exceeds the equivalent amount of the isocyanate group serving as the origin of chain extension in the urethane prepolymer, the molecular weight of the chain extended urethane polymer decreases and the cohesive force of the dry film of the aqueous composition decreases.

The compound having two active hydrogens capable of reacting with the above-mentioned isocyanate group used as a chain extender has a greater nucleophilicity for an isocyanate group than water existing as a dispersion medium. The chain extension reaction preferentially proceeds. The urethane prepolymer is also chain-extended by water in the reaction vessel in the dispersion step. In the chain extension reaction with water, the isocyanate group in the urethane prepolymer reacts with water, and the resulting amine always reacts with a new isocyanate group, so despite the excess water, the water participating in the reaction is isocyanate. It does not exceed the equivalent of the group.

As described above, a homogeneous mixture of the self-emulsifying urethane polymer and / or urethane prepolymer and the tackifying resin having a softening point of 130 to 200 ° C. is dispersed in water. In the aqueous dispersion, a hydrophilic property added as necessary in the step of preparing the urethane polymer and the urethane prepolymer, the step of preparing a homogeneous mixture with the above tackifying resin, or the step of dispersing the homogeneous mixture in water. Although the organic solvent is dissolved, these hydrophilic organic solvents dissolved in the water of the dispersion medium are removed to the outside of the aqueous composition by means such as heating, reduced pressure or reduced pressure heating.

When the hydrophilic organic solvent remains in the aqueous composition, the solvent resistance and heat resistance of the obtained dry film are deteriorated. Further, when the residual hydrophilic organic solvent is present in a large amount, the quality of the dry film is deteriorated, the environment at the time of using the aqueous composition is deteriorated, and further the air is contaminated.

The aqueous composition of the present invention according to claim 2 has reactivity with the aqueous composition obtained as described above, and further with respect to the carboxyl group of the urethane polymer and / or the urethane prepolymer. It is an aqueous composition to which a compound having two or more functional groups is added.

The compound having two or more functional groups reactive with the carboxyl group of the urethane polymer and / or urethane prepolymer functions as a crosslinking agent for the urethane polymer and urethane prepolymer. It is not particularly limited as long as it has the function, but examples thereof include isocyanate-based, melamine-based, aziridine-based, epoxy-based, oxazoline-based, carbodiimide-based, and metal-based crosslinking agents. Among the aziridine-based, epoxy-based, and carbodiimide-based cross-linking agents, aqueous solution-type, water-dispersion-type or self-emulsifying cross-linking agents are particularly preferably used. The compound having two or more functional groups reactive with the carboxyl group of the urethane polymer and / or urethane prepolymer may be used alone or in combination of two or more. . The addition amount of the compound having two or more functional groups reactive with the carboxyl group of the urethane polymer and / or urethane prepolymer is preferably 100 parts by weight of the urethane polymer and / or urethane prepolymer. The amount is 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight.

The aqueous composition of the present invention may further contain, if necessary, an elastomer, a plasticizer, a synthetic resin other than the above, a tackifying resin dispersion, a colorant, an inorganic filler, a coupling agent, a stabilizer, and an additive. A viscous agent, a defoaming agent, an antifungal agent, an anticorrosive agent, etc. are added within a range not departing from the spirit of the present invention.

Examples of the above elastomer include styrene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, styrene thermoplastic elastomer,
Examples thereof include synthetic rubber such as olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and natural rubber. These elastomers may be used alone or in combination of two or more.

The elastomer may be mixed with the urethane polymer and / or the urethane prepolymer as a powder or a solution of an organic solvent before the water dispersion step, and the synthetic resin may be used as an aqueous dispersion such as an emulsion or a latex.
A uniform mixture composed of the urethane polymer and / or urethane prepolymer and a tackifying resin having a softening point of 130 to 200 ° C. may be added to and mixed with the water-dispersed aqueous composition.

The added amount of the elastomer or the elastomer aqueous dispersion is preferably 0. 100 parts by weight based on 100 parts by weight of the urethane polymer and / or urethane prepolymer.
1 to 300 parts by weight.

Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, dibutyl phthalate and dioctyl phthalate, tributyl phosphate, triphenyl phosphate, and phosphoric acid such as tris (β-chloropropyl) phosphate. Esters, fatty acid esters such as butyl oleate, dibutyl adipate, di-n-hexyl adipate, dibutyl sebacate, dihydric alcohol esters such as diethylene glycol dibenzoate, butyl acetylricinoleate, tributyl acetylcitrate, etc. Examples thereof include oxyacid esters. These plasticizers are
Although it may be used in one kind, two or more kinds may be used in combination. The amount of the plasticizer added is preferably 0.5 to 100 parts by weight based on 100 parts by weight of the urethane polymer and / or urethane prepolymer.

Examples of the synthetic resin include (meth)
Acrylic resin, epoxy resin, vinyl acetate resin,
Vinyl acetate-ethylene copolymer resin, ethylene- (meth) acrylic acid ester copolymer resin, ethylene-
(Meth) acrylic copolymer resin, vinyl chloride resin,
Examples include phenoxy resin and styrene resin. These synthetic resins may be used alone or in combination of two or more. The synthetic resin may be mixed with the urethane polymer and / or the urethane prepolymer as a powder or a solution of an organic solvent before the water dispersion step, and the synthetic resin may be used as an aqueous dispersion such as an emulsion or a latex. A uniform mixture of a urethane polymer and / or a urethane prepolymer and a tackifying resin having a softening point of higher than 130 ° C. may be added to and mixed with the water-dispersed aqueous composition. The addition amount of the synthetic resin or the synthetic resin aqueous dispersion is preferably 5 to 200 with respect to 100 parts by weight of the urethane polymer and / or urethane prepolymer.
Parts by weight (solid content).

Examples of the tackifier resin aqueous dispersion include gum rosin, tall oil rosin, wood rosin, polymerized rosin, hydrogenated rosin, disproportionated rosin, rosin ester,
Hydrogenated rosin ester, disproportionated rosin ester, rosin-modified phenol resin, rosin resin such as maleic acid-modified rosin resin, terpene resin, phenol resin, terpene phenol resin, xylene resin, ketone resin, aliphatic petroleum resin, fat Examples thereof include water dispersions of aromatic petroleum resins, aromatic petroleum resins, coumarone resins, styrene resins and the like.
These tackifier resin aqueous dispersions have a softening point of 130 ° C. with the urethane polymer and / or urethane prepolymer.
A homogeneous mixture consisting of a super-tackifying resin is added to and mixed with a water-dispersed aqueous composition, and as the tackifying resin, the above-mentioned urethane polymer and / or urethane prepolymer and a uniform water-dispersing step are used. It may be the same as the tackifying resin having a softening point higher than 130 ° C., which is blended as a mixture, or may be a resin other than these. or,
The tackifier resin aqueous dispersion may be used alone or in combination of two or more. The amount of the tackifier resin aqueous dispersion added is preferably 5 with respect to 100 parts by weight of the urethane polymer and / or urethane prepolymer.
˜150 parts by weight (solid content).

Examples of the above-mentioned coloring agent include mica-like iron oxide, lead white, red lead, yellow lead, silver vermillion, ultramarine blue, navy blue, cobalt oxide, titanium dioxide, titanium dioxide-coated mica, strontium chromate, titanium yellow, titanium black. Inorganic colorants such as zinc chromate, iron black, molybdenum white, litharge and lipoton, azo pigments, dye lakes, organic dyes and pigments such as anthraquinone and phthalocyanine dyes. These colorants may be used alone or in combination of two or more. The amount of the colorant added is preferably 0.1 based on 100 parts by weight of the urethane polymer and / or urethane prepolymer.
２００200 parts by weight.

Examples of the above-mentioned inorganic fillers include oxides such as silica, alumina, titania, zirconia, zinc oxide, magnesium oxide and iron oxide, calcium carbonate,
Carbonates such as magnesium carbonate and zinc carbonate, silicates such as aluminum silicate, magnesium silicate, calcium silicate, kaolin, clay, talc, mica, zeolite and sericite, hydroxides such as aluminum hydroxide and magnesium hydroxide, Sulfuric acid and sulfites such as calcium sulfate, barium sulfate and calcium sulfite, boron nitride,
Examples thereof include nitrides such as silicon nitride, titanates such as potassium titanate and barium titanate, and water glass, dawsonite, carbon black, silicon carbide and the like. These inorganic fillers may be used alone, but 2
More than one species may be used in combination. The addition amount of the inorganic filler is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the urethane polymer and / or urethane prepolymer.

Examples of the coupling agent include silane coupling agents, titanate coupling agents, polyphenol compounds, and the like. Examples of the silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltrioxide. Ethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl −γ−
Examples include aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.

Examples of the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, tetraoctyl bis (dioctyl phosphite) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl. Examples thereof include trioctanoyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tri (dioctyl phosphate) titanate, and the like.

Examples of the above polyphenol compounds include gallic acid, tannic acid, polytannic acid and the like. These coupling agents may be used alone or in combination of two or more. The amount of the coupling agent added is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the urethane polymer and / or urethane prepolymer.

The above-mentioned stabilizers include, for example, antioxidants, ultraviolet absorbers, ultraviolet stabilizers, etc., and the antioxidants include, for example, 2,6-di-t-butyl-p-cresol and butylated. Hydroxyanisole, 2,6-di-
Monophenol-based antioxidants such as t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-)
6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4 '
Bisphenol-based antioxidants such as butylidene bis (3-methyl-6-t-butylphenol), 1,1,3-
Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4
6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] high molecular weight phenolic antioxidants such as methane, dilauryl 3,3'-thiodipropionate, 3,3'-thiodi Sulfur-based antioxidants such as distearyl propionate, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (2,4-di-t-butylphenyl)
Examples thereof include phosphorus-based antioxidants such as phosphite.

Examples of the ultraviolet absorber include salicylic acid type ultraviolet absorbers such as phenyl salicylate and pt-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-. Benzophenone-based UV absorbers such as 4-dodecyloxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-
Benzotriazole-based UV absorbers such as butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2
Examples thereof include cyanoacrylate-based ultraviolet absorbers such as ethylhexyl-2-cyano-3,3′-diphenylacrylate and ethyl-2-cyano-3,3′-diphenylacrylate.

Examples of the UV stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-4-piperidyl succinate). ) Etc., hindered amine ultraviolet stabilizers, 2,4-di-t-butylphenyl-3,5-di-
Examples thereof include benzoate-based ultraviolet stabilizers such as t-butyl-4-hydroxybenzoate. These coupling agents may be used alone or in combination of two or more. The amount of the stabilizer added is preferably the above urethane polymer and / or urethane prepolymer 1
It is 0.1 to 20 parts by weight with respect to 00 parts by weight.

The method of adding the above-mentioned various additives to the above-mentioned aqueous composition is not particularly limited. For example, the above-mentioned self-emulsifying urethane polymer and / or urethane prepolymer and a softening point of more than 130 ° C are used. A uniform mixture consisting of the tackifying resin may be added to the aqueous composition obtained by dispersing it in water, but it should be mixed in advance with the self-emulsifying urethane polymer and / or urethane prepolymer. Alternatively, the aqueous composition may be prepared by mixing with the tackifying resin having a softening point of higher than 130 ° C. and then dispersing in water.

The self-emulsifying urethane polymer and / or urethane prepolymer and the tackifying resin having a softening point of higher than 130 ° C. and / or the urethane polymer and / or
Alternatively, the viscosity of an aqueous composition containing a compound having two or more functional groups reactive with a carboxyl group of the urethane prepolymer is appropriately set depending on the application of the product or the construction method, but usually the solid content concentration is Is set to about 20 to 75% by weight, and the viscosity is 100,000 cps or less. At the time of use, the above aqueous composition can be appropriately adjusted to a solid content concentration and viscosity according to a construction means such as spraying, a roll coater, a flow coater and a brush coating, using a thickener or a diluent.

The above-mentioned aqueous composition is applied to the surface to be treated and dried, and the drying is suitable for both natural drying and forced drying, and particularly excellent for forced drying. . The above-mentioned forced drying generally has a drying temperature of 30 to 150.
Although performed at 20 ° C. for a drying time of 20 minutes or less, the aqueous composition readily dries under the forced drying conditions and provides a dry film of excellent quality.

When the above aqueous composition is used as an adhesive, it can be applied to a wide variety of adherends, but is particularly preferably used for metals, plastics, inorganic materials, wood, paper and the like. Further, the adherend of the above material is a door, partition, outer wall material, desk top plate, packaging film / sheet for food, etc., and the aqueous composition is suitable for these product manufacturing processes and construction sites. Used for.

When the above aqueous composition is used as an adhesive, it is applied to at least one of the adherends, and the coating amount can be in a wide range, but the solid content is 10 to 3.
A coating amount range of about 00 g / m ² is preferable in terms of workability and the like. In the above-mentioned bonding step, depending on the purpose of attachment and the shape of the adherend, pressure may be applied from the back surface of the adhered adherends by a pressure bonding means such as a roll press, a hydraulic press, a turnbuckle, etc., if necessary. , Bonding temperature: normal temperature to 150 ° C, bonding time: 20 minutes, bonding pressure:
Even under the above-mentioned pressure bonding condition of 0.01 to 200 kg / cm ² , excellent adaptability is exhibited, and strong adhesion can be maintained for a long period of time.

Since the aqueous composition of the present invention is constructed as described above, it has high normal state adhesive properties and maintains high quality even under severe use environment such as high temperature and high pressure, and is excellent in construction. Shows sex.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention, but the present invention is not limited to these embodiments. (Example 1) Polypropylene glycol diol (manufactured by NOF CORPORATION, trade name: Nissan Uniall D-2000,
OH number 58, number average molecular weight 2000) 100 parts by weight, 3
Isocyanate Methyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Huls, trade name: Bestanto IPDI) 43.1 parts by weight, dimethylolpropionic acid [manufactured by Trimet Technical Products, trade name: DMPA, (isocyanate group ) / (Hydroxyl group) =
2.0 (equivalent ratio)] 6.1 parts by weight and 37.3 parts by weight of methyl ethyl ketone were subjected to boiling point polymerization with stirring, and when the content of the isocyanate group was 4.3% by weight or less, methyl ethyl ketone 62.1 To adjust the viscosity by weight,
4.6 parts by weight of triethylamine was added as a neutralizing agent,
Furthermore, novolac type alkylphenol resin (manufactured by Showa High Polymer Co., Ltd., trade name: CKM-2400, softening point 150 ° C.,
90 parts by weight (50% by weight methyl ethyl ketone solution) (solid content: 45 parts by weight) were added and mixed to obtain a transparent urethane polymer solution. Next, while vigorously stirring the urethane polymer solution at room temperature, 350 parts by weight of water was added, and immediately after that, 27.5 parts by weight of a 20% by weight ethylenediamine aqueous solution (5.5 parts by weight of solid content) was added, and further 1 part was added. After stirring for an hour at room temperature, the pressure is reduced and the solvent is removed.
A wt% urethane-based aqueous composition was obtained.

(Example 2) Instead of the novolac type alkylphenol resin of Example 1, a novolac type alkylphenol resin (manufactured by Hitachi Chemical Co., Ltd., trade name: Hitanol 11) was used.
40, softening point 135 ° C., 50 wt% methyl ethyl ketone solution) 90 parts by weight (solid content 45 parts by weight) was used in the same manner as in Example 1 to obtain a urethane-based aqueous composition having a solid content of 40% by weight. .

(Example 3) Instead of the novolac type alkylphenol resin of Example 1, xylene resin (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: Nikanol HP-150, softening point 1)
Example 1 except that 90 parts by weight of a 50% by weight methyl ethyl ketone solution (60 ° C.) (45 parts by weight of solid content) was used.
A urethane-based aqueous composition having a solid content of 40% by weight was obtained in the same manner as in.

Example 4 Polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name: Praxel L220)
AL, OH value 58, number average molecular weight 2000) 100 parts by weight, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Huls, trade name: Bestanto IPDI) 31.0 parts by weight, dimethylol propionic acid [Manufactured by Trimet Technical Products, trade name: DMPA, (isocyanate group) / (hydroxyl group) = 1.5 (equivalent ratio)] 5.6 parts by weight and 34.2 parts by weight of methyl ethyl ketone are subjected to boiling point polymerization with stirring. When the isocyanate group content was 2.3% by weight or less, 56.9 parts by weight of methyl ethyl ketone was added as a neutralizing agent in an amount of 4.2 parts by weight of triethylamine in order to adjust the viscosity. Resin (Showa High Polymer Co., Ltd., trade name: CKM-2400, softening point 15
82 parts by weight (solid content 41 parts by weight) of 0% and 50% by weight methyl ethyl ketone solution) was added and mixed to obtain a transparent urethane polymer solution. Then, 320 parts by weight of water was added to the urethane polymer solution with vigorous stirring at room temperature,
Immediately thereafter, 13 parts by weight of a 20% by weight ethylenediamine aqueous solution (2.6 parts by weight of solid content) was added, and the mixture was further stirred for 1 hour at room temperature.
A wt% urethane-based aqueous composition was obtained.

(Example 5) Solid content 4 obtained in Example 1
0% by weight of a urethane-based aqueous composition, an acrylic emulsion (manufactured by Asahi Kasei, trade name: Polytron U-15
4, solid content 60% by weight) 99.9 parts by weight (solid content 59.
9 parts by weight) was added and mixed to obtain a urethane-based aqueous composition having a solid content of 43% by weight.

(Comparative Example 1) In place of the novolac type alkylphenol resin of Example 1, a novolac type alkylphenol resin (manufactured by Hitachi Chemical Co., Ltd., trade name: Hitanol 15) was used.
01, softening point 95 ° C., 50 wt% methyl ethyl ketone solution) 90 parts by weight (solid content 45 parts by weight) was used in the same manner as in Example 1 to obtain a urethane-based aqueous composition having a solid content of 40% by weight. .

Comparative Example 2 Instead of the novolac type alkylphenol resin of Example 1, xylene resin (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: Nikanol HP-70, softening point 80) was used.
A urethane-based aqueous composition having a solid content of 40% by weight was obtained in the same manner as in Example 1, except that 90 parts by weight of a 50% by weight methyl ethyl ketone solution (45 parts by weight of solid content) was used.

(Example 6) Solid content 4 obtained in Example 1
A urethane-based aqueous composition of 0% by weight was further added with an aziridine-based crosslinking agent (trade name: Chemitite DZ-2 manufactured by Nippon Shokubai Co., Ltd.).
2E, aqueous dispersion: solid content 25% by weight) 24 parts by weight (solid content 6 parts by weight) were added and mixed to obtain a urethane-based aqueous composition having a solid content of 39% by weight.

(Example 7) Solid content 4 obtained in Example 4
0% by weight of the urethane-based aqueous composition, 10.8 parts by weight (solid content: 5% by weight) of a carbodiimide-based crosslinking agent (manufactured by Union Carbide, trade name: Yucarlink XL-25SE, water dispersion: solid content: 50% by weight) 0.4 parts by weight) was added and mixed to obtain a urethane-based aqueous composition having a solid content of 40% by weight.

Comparative Example 3 Solid content 4 obtained in Comparative Example 1
A urethane-based aqueous composition of 0% by weight was further added with an aziridine-based crosslinking agent (trade name: Chemitite DZ-2 manufactured by Nippon Shokubai Co., Ltd.).
2E, aqueous dispersion: solid content 25% by weight) 24 parts by weight (solid content 6 parts by weight) were added and mixed to obtain a urethane-based aqueous composition having a solid content of 39% by weight.

In order to evaluate the performance of the urethane-based aqueous compositions obtained in the above Examples and Comparative Examples, the normal adhesive strength and
The 0 ° C peel adhesion was tested by the method shown below. The test results are shown in Tables 1 and 2.

(1) Normal-state adhesive strength: The urethane-based aqueous composition thus obtained was applied at a coating amount of 100 g / m ² on canvas and a coating amount of 4 on cold-rolled steel sheets (25 mm × 125 mm × 2 mm).
Each layer was coated with a brush at 0 g / m ² and dried in a hot air drying oven at 80 ° C. for 4 minutes, the coated surfaces were stuck together, and roll-pressed at a pressure of 60 kg / 25 mm to prepare a laminate. After curing the laminate at 23 ° C. for 1 week, at 23 ° C., a tensile speed of 50 mm / min was applied for 9 minutes.
A 0 degree peel test was performed.

(2) Peeling adhesive strength at 80 ° C .: The same laminated body as used in the normal adhesive strength test was heated in an atmosphere of 80 ° C. for 5 minutes, and in an atmosphere of 80 ° C., 50 mm / min.
A 90-degree peel test was performed at a pulling speed of.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

Since the aqueous composition of the present invention is constituted as described above, it has high normal state adhesive properties and maintains high quality even under severe use environment such as high temperature and high pressure, and is excellent. It shows the workability.

Claims (2)

[Claims] 1. A urethane polymer and / or urethane prepolymer having a self-emulsifying property and a softening point of 130 to 20.
A water-based composition, characterized in that a mixture comprising a tackifying resin at 0 ° C. is dispersed in water. 2. An aqueous composition obtained by further adding a compound having two or more functional groups reactive with a carboxyl group of a urethane polymer and / or a urethane prepolymer to the aqueous composition according to claim 1. Composition.