JPH10273587A - Aqueous polyurethane emulsion composition, and water-based emulsion coating material and adhesive prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give a water-based adhesive and a water-based coating material having good adhesion and close adhesion to various substrates, especially nonpolar substrates by mixing an aqueous polyurethane emulsion with an aqueous resin emulsion obtained from an unsaturated monomer. SOLUTION: An aqueous polyurethane emulsion is mixed with an aqueous resin emulsion obtained from an unsaturated monomer in a ratio of 95/5 to 5/95 by weight of solids. The aqueous polyurethane emulsion is obtained by reacting an organic diisocyanate with a polymer polyol selected among polyester polyols, polyether polyols and polycarbonate polyols, a chain extender, a carboxylic-acid-containing low-molecular polyol and a neutralizing agent. The aqueous resin emulsion obtained from the unsaturated monomer is an isoprene latex or a product obtained by the carboxyl modification thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin emulsion composition obtained from an aqueous polyurethane emulsion and an unsaturated monomer, and an aqueous adhesive having good adhesion and adhesion to various materials, especially to a nonpolar substrate. And water-based paints.

[0002]

2. Description of the Related Art In recent years, in the field of adhesives, paints, etc., organic solvents have been the mainstream, but from the viewpoints of air pollution prevention, regulations of the Fire Service Law, occupational hygiene, etc., water-based adhesives have been adopted. Is starting to be. This water-based adhesive, as a resin for paint,
There have been proposed polyester-based and polyether-based polyurethane resins containing a hydrophilic polar group such as a carboxylate. For example, JP-A-4-68022 discloses an aqueous dispersion of a polyurethane resin obtained from a hydroxyl-containing polyalkylene oxide and a polyisocyanate. JP-A-5-117358 discloses that the molecular weight is 15,
A water-based polyurethane resin composition obtained from 2,000 to 10,000 polyester diols having hydroxyl groups at both ends and an isocyanate monomer having at least one isocyanate group is shown. Japanese Patent Publication No. 5-86829 discloses an aqueous polyurethane resin-based adhesive containing a hydroxyl group-containing hydrogenated polybutadiene. JP-A-6-65552 discloses an aqueous adhesive containing an aqueous polyurethane emulsion and rubber latex.

[0003]

However, various problems have been pointed out with the conventional aqueous polyurethane emulsion in actual use. For example, the aqueous polyurethane emulsion described in JP-A-4-68022 has a problem in water resistance and the like because it is based on polyether. The water-based polyurethane resin described in JP-A-5-117358 has good adhesion and adhesion to so-called polar substrates such as polyethylene terephthalate and nylon, but does not have satisfactory adhesion to non-polar substrates. Was. In the aqueous polyurethane-based adhesive disclosed in Japanese Patent Publication No. 5-86829, the ratio of the linear unit to the side chain unit of the introduced hydroxyl group-containing hydrogenated polybutadiene is extremely uneven, so that the crystallinity of the polyolefin portion is high. Is getting too big. Therefore, the obtained adhesive does not have good adhesiveness and adhesion to the substrate. Also, conventional hydroxyl group-containing polyolefins such as hydroxyl group-containing polybutadiene have more than two functional groups, and thus it was difficult to obtain the desired polyurethane resin itself. -The water-based adhesive disclosed in JP-A-6-65552 is inferior in workability since a primer component is required.

The present invention sufficiently satisfies the adhesiveness and adhesion to various substrates such as aqueous polyurethane emulsion compositions and all kinds of plastics including general-purpose polyolefins, and has excellent stability over time and durability. It is an object to provide a water-based adhesive and a water-based paint.

[0005]

That is, the present invention provides the following (1) to (4). (1) An aqueous polyurethane-based emulsion composition characterized by satisfying the following conditions (A) to (C). (A) an aqueous polyurethane emulsion composition is obtained by mixing an aqueous polyurethane emulsion (a) and an aqueous resin emulsion (b) obtained from an unsaturated monomer, and
(A) / (b) is 95/5 to 5/95 in terms of solid content weight ratio. (B) The aqueous polyurethane emulsion (a) is obtained by reacting at least the following (a) to (e). (A) Organic diisocyanate. (B) A polymer polyol selected from at least one or more of polyester polyols, polyether polyols, and polycarbonate polyols. (C) a chain extender. (D) Carboxylic acid-containing low molecular polyol. (E) Neutralizer. (C) The aqueous resin emulsion (b) is at least one selected from the following. Isoprene latex, chloroprene emulsion,
Styrene-butadiene emulsion, nitrile-butadiene emulsion, butadiene emulsion, vinyl chloride emulsion, vinylpyridine-styrene-
Butadiene emulsion, polybutene emulsion, polyethylene emulsion, vinyl acetate emulsion, ethylene-vinyl acetate emulsion, vinylidene chloride emulsion, methyl methacrylate-butadiene emulsion, and those obtained by carboxyl-modifying these latexes

(2) The aqueous polyurethane emulsion composition according to the above (1), which satisfies the following conditions (A) to (C). (A) An aqueous polyurethane emulsion composition is obtained by mixing an aqueous polyurethane emulsion (a) and an aqueous resin emulsion (b) from an unsaturated monomer, and (a) /
(B) is 95/5 to 5/95 in terms of solid content weight ratio. (B) The aqueous polyurethane emulsion (a) is obtained by reacting at least the following (a) to (e). (A) An organic diisocyanate selected from at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. (B) Polyester diol in which the acid component is aromatic dicarboxylic acid / aliphatic dicarboxylic acid = 35/65 to 65/35 (weight ratio), polyether diol having an ethylene oxide unit of 50 mol% or less, 1,6- A polymer polyol selected from at least one or more of polycarbonate diols using hexanediol. (C) a chain extender having 15 or less carbon atoms. (D) A low molecular weight carboxylic acid-containing polyol selected from at least one selected from 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. (E) Neutralizer. (C) The aqueous resin emulsion (b) uses isoprene latex.

(3) An aqueous emulsion paint characterized by using the aqueous polyurethane emulsion composition according to (1) and / or (2).

(4) An aqueous emulsion adhesive characterized by using the aqueous polyurethane emulsion composition according to (1) and / or (2).

[0009]

DETAILED DESCRIPTION OF THE INVENTION The organic diisocyanate (a) used in the aqueous polyurethane emulsion (a) in the present invention is toluene diisocyanate (hereinafter referred to as TDI), diphenylmethane diisocyanate (hereinafter MD).
I), diphenyldimethylmethane diisocyanate, dibenzyl diisocyanate, naphthylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, aromatic diisocyanate such as tetramethyl xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methyl Pentane-1,5-
Aliphatic such as diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexaethylene-1,6-diisocyanate, and 2,4,4-trimethylhexaethylene-1,6-diisocyanate Diisocyanate, isophorone diisocyanate (hereinafter referred to as IPDI), cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate (hereinafter H ₆
Referred to as XDI), referred to as hydrogenated diphenylmethane diisocyanate (hereinafter H ₁₂ MDI), there are alicyclic diisocyanates such as hydrogenated trimethyl xylylene diisocyanate. These organic diisocyanates can be used alone or as a mixture.
Furthermore, modified products such as modified adducts, modified carbodiimides, modified allophanates, modified burettes, modified uretdione, modified uretoimines, modified isocyanurates, and the like can also be used.

In these organic polyisocyanates, TD
_{I, MDI, IPDI, H 6} XDI, H 12 MDI are preferred.

The polymer polyol (b) used in the aqueous polyurethane emulsion (a) in the present invention is selected from at least one or more of polyester polyols, polyether polyols and polycarbonate polyols having a number average molecular weight of 500 to 10,000. Things.

The polyester polyols include phthalic acid, isophthalic acid (hereinafter referred to as iPA), terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Curtaconic acid, azelaic acid (hereinafter A
ZA), sebacic acid, succinic acid, adipic acid,
Sebacic acid, azelaic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, One or more kinds of polycarboxylic acids or anhydrides such as hemimelitic acid, trimellitic acid, pyromellitic acid and benzophenonetetracarboxylic acid, and ethylene glycol (hereinafter referred to as EG), diethylene glycol, dipropylene glycol, 1,2-propane Diol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol (hereinafter 1,6-HD) ), 3-methyl-1,5-pentanediol, 1,
8-octanediol, 1,9-nonanediol, neopentyl glycol (hereinafter referred to as NPG), diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol It is obtained from a dehydration condensation reaction of A with ethylene oxide or propylene oxide adduct, one or more of low molecular diols such as trimethylolpropane, glycerin, hexanetriol, and quadrol, and low molecular triols. Further, there are lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (so-called lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone.

In these polyester polyols, the acid component is aromatic dicarboxylic acid / aliphatic dicarboxylic acid = 35
/ 65-65 / 35 (weight ratio) is preferable, and a polyester diol using a low molecular weight polyol having 8 or less carbon atoms is more preferable.

Examples of the polyether polyols include the aforementioned low-molecular polyols, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugar alcohols such as sucrose, glucose, fructose, ethylenediamine, propylenediamine, toluenediamine, and metadiamine. A compound having two or more active hydrogen groups such as phenylenediamine, diphenylmethanediamine, xylylenediamine, etc. as an initiator, ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), butylene oxide,
It can be obtained by addition polymerization from a single product or a mixture of alkyl glycidyl ethers such as amylene oxide and methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and cyclic ether monomers such as tetrahydrofuran by a known method.

In these polyether polyols, E
A polyether diol having an O unit of 50 mol% or less is preferable.

As the polycarbonate polyol, one of the above-mentioned low molecular weight polyols of the polyester polyol source is used.
It can be obtained from a dealcoholation reaction, a glycol removal reaction, or a phenol reaction of any one or more kinds with a dialkyl carbonate, dialkylene carbonate, or diphenyl carbonate. Further, a copolymer with the above-mentioned polyester polyol or polyether polyol can also be used.

Among these polycarbonate polyols, a polycarbonate diol using 1,6-HD is preferable, and 1,6-H in the starting polyol is more preferable.
Those having D of 50 mol% or more are preferred.

The above-mentioned polymer polyols include urea resins, acrylic resins, melamine resins, epoxy resins,
As long as it contains two or more active hydrogen groups, such as polyester resin and polyvinyl alcohol, it can be used as a high molecular polyol.

Examples of the chain extender (c) used in the aqueous polyurethane emulsion (a) of the present invention include water having a molecular weight of 18 to 500, urea, low molecular polyol, low molecular polyamine and low molecular amino alcohol. These may be used alone or in combination of two or more.

The low-molecular polyol as a chain extender includes the low-molecular polyol of the above-mentioned polyester polyol source.

Examples of the low molecular weight polyamine include ethylenediamine, hexamethylenediamine, isophoronediamine (hereinafter referred to as IPDA), mensendiamine, diphenylmethanediamine, diaminodiphenylsulfone, xylenediamine, piperazine, hydrogenated xylylenediamine, and hydrogenated diphenylmethanediamine. (Hereinafter H ₁₂ M
DA) or a mixture of two or more of these.

Examples of the amino alcohol include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-phenyldipropanolamine and the like.

Among these chain extenders, those having 15 or less carbon atoms are preferred.

The low-molecular-weight carboxylic acid-containing polyol (d) used in the aqueous polyurethane emulsion (a) in the present invention includes 2,2-dimethylolpropionic acid (hereinafter referred to as DMPA), 2,2-dimethylolbutane Examples thereof include acids (hereinafter referred to as DMBA), carboxylic acid-containing polyols such as 2,2-dimethylolvaleric acid, and adducts of iminodiacetic acid and glycidol. These may be used as a chain extender as they are, or may be introduced into a polyol.

In these carboxylic acid-containing low molecular weight polyols, it is preferable to use at least one of DMPA and DMBA.

The neutralizing agent (e) used in the aqueous polyurethane emulsion (a) in the present invention includes ammonia, ethylamine, trimethylamine, triethyl
Amine, triisopropylamine, tributylamine,
Organic amines such as triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, Examples include alkali metals such as lithium, potassium, and sodium, and inorganic alkalis such as sodium hydroxide and potassium hydroxide.However, in order to improve weather resistance and water resistance after drying, volatile compounds that are easily dissociated by heat are used. Are preferable, and ammonia, trimethylamine and triethylamine are preferable. These neutralizing agents may be used alone or in combination of two or more.

The above-mentioned hydrophilic polar group is finally present in the polyurethane resin in the form of a salt. However, it may be neutralized before introduction into the resin, or the polar group may be added to the resin. And then neutralized.

The aqueous polyurethane emulsion (a) of the present invention may have another hydrophilic polar group. For example, anionic polar groups such as sulfonate groups, phosphate groups, phosphinate groups, phosphonate groups, and the like,
Cationic polar groups such as tertiary amino groups and quaternary ammonium bases; amphoteric polar groups such as carboxylbetaine groups, sulfobetaine groups, and phosphobetaine groups; nonionic polar groups such as oxyethylene groups; Is mentioned.

The amount of the carboxylate to be introduced into the aqueous polyurethane emulsion (a) is 0.1 to 3.
0 mmol / g, preferably 0.2 to 2.9 m
mol / g. When the amount of the carboxylate introduced is less than the above lower limit, the polyurethane resin does not disperse well in water. If it exceeds the upper limit, the water resistance of the dried polyurethane resin is insufficient.

The polyurethane resin composition of the present invention comprises:
A reaction terminator can be used if necessary. Examples of the reaction terminator include monoalcohols, monoamines, aminoalcohols, and mixtures thereof, and monoisocyanates such as phenyl isocyanate, butyl isocyanate, and cyclohexyl isocyanate can also be used as the reaction terminator.

Specific monoalcohols include methanol, ethanol, propanol, isopropanol,
2-ethylhexanol and the like. Monoamines include primary amines such as ethylamine, propylamine and butylamine, and secondary amines such as diethylamine and dibutylamine.
There are secondary amines. Examples of the amino alcohol include monoethanolamine and diethanolamine.

The method for producing the polyurethane resin used in the present invention includes a one-shot method in which an active hydrogen compound is reacted in an atmosphere having an excess of active hydrogen, and a method in which an active hydrogen compound and an organic diisocyanate are reacted in an excess of NCO groups to synthesize an NCO-terminated prepolymer. In advance, it can be synthesized by a known method such as a prepolymer method in which an active hydrogen compound is reacted. Also, after reacting the polyurethane resin in an organic solvent compatible with water, add water, and then remove the organic solvent or synthesize the resin without using a solvent and forcibly disperse or dissolve in water. Can also be obtained by the method

In the case of the one-shot method, active hydrogen / NCO
Is from 0.5 to less than 1, preferably from 0.8 to 1.
It is less than 1. When it is less than 0.5, the molecular weight of the polyurethane resin is too small, resulting in a lack of durability. In the case of one or more, gelation is likely to occur when synthesizing the resin.

In the case of the prepolymer method, the ratio of active hydrogen / NCO at the time of prepolymer synthesis is from 1.1 to 5.0, preferably from 1.5 to 4.0. If less than 1.1,
The molecular weight of the prepolymer becomes too large, making it difficult to proceed to the subsequent reaction steps. If it exceeds 5.0, the adhesiveness will be poor.

When an organic solvent is used, usable organic solvents include toluene, xylene, swazol (an aromatic hydrocarbon solvent manufactured by Cosmo Oil Co., Ltd.) and Solvesso (an aromatic hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.). Aromatic solvents such as hydrogen solvents), ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate; Glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate; Air such as tetrahydrofuran and dioxane Le-based solvents. One or more of the above solvents can be used.

As a reaction catalyst for synthesizing an isocyanate group-terminated prepolymer or a polyurethane resin used in the present invention, a known so-called urethanization catalyst can be used. Specific examples include organic metal compounds such as dioctyltin dilaurate, organic amines such as triethylenediamine, and salts thereof. The reaction temperature at the time of urethanization is 10 to 100 ° C, preferably 30 to 80 ° C.

The number average molecular weight of the polyurethane resin thus obtained is preferably 5,000 or more, and more preferably 10,000 or more. When the number average molecular weight of the polyurethane resin is less than 5,000, durability becomes poor.

The aqueous resin emulsion (b) from the unsaturated monomer in the present invention includes isoprene-based emulsion, chloroprene-based emulsion, styrene-butadiene-based emulsion, nitrile-butadiene-based emulsion, butadiene-based emulsion, and vinyl chloride-based emulsion. , Vinylpyridine-styrene-butadiene emulsion, polybutene emulsion, polyethylene emulsion, vinyl acetate emulsion, ethylene-
At least one selected from vinyl acetate emulsions, vinylidene chloride emulsions, methyl methacrylate-butadiene emulsions, and carboxyl-modified latexes thereof.

Specific examples of the aqueous resin emulsion that can be used in the present invention include the following. Isoprene latex: Claprene LIR-700 (manufactured by Kuraray) Chloroprene latex: Denka chloroprene LA-50, LT-50 (manufactured by Denki Kagaku Kogyo) Styrene-butadiene latex: JSR 0561, 2108 (manufactured by Nippon Synthetic Rubber) Nipol LX119 (manufactured by Nippon Zeon) ) Nitrile-butadiene latex: Nipol 1551, 1577 (manufactured by Nippon Zeon) Butadiene latex: JSR 0700 (manufactured by Nippon Synthetic Rubber) Nipol LX111 (manufactured by Nippon Zeon) Vinyl chloride latex: Zeon 151, 351, 576 (manufactured by Zeon) Vinylpyridine -Styrene-butadiene latex: Nipol 2518FS (manufactured by Nippon Zeon) JSR 0650 (manufactured by Nippon Synthetic Rubber) Polybutene latex: HV-100, 300 (Nisseki Polyethylene latex: Sunstar polish E-162, E-362 (manufactured by Sunstar Giken) Vinyl acetate latex: Sumikaflex S-500, S-510 (manufactured by Sumitomo Chemical) Ethylene-vinyl acetate latex: EVA Dick EV-15, 260 (manufactured by Dainippon Ink and Chemicals) Vinylidene chloride latex: Saran latex 103S (manufactured by Asahi Dow) Methyl methacrylate-butadiene latex Closrene 2M-33A, 2M-36 (manufactured by Takeda Pharmaceutical) Carboxyl-modified styrene-butadiene Latex: JSR 0668, 0691, 0591 (manufactured by Nippon Synthetic Rubber) Carboxyl-modified nitrile-butadiene latex: Closlen NA-10, 11 (manufactured by Takeda Pharmaceutical) Carboxyl-modified methyl methacrylate-bu Tadiene latex crosslen 2M-30, 2M-38 (manufactured by Takeda Pharmaceutical)

The aqueous resin emulsion (b) used in the present invention includes isoprene-based emulsion, chloroprene-based emulsion, nitrile-butadiene-based emulsion, butadiene-based emulsion, vinylpyridine-styrene-butadiene-based emulsion, polybutene-based emulsion, and polyethylene-based emulsion. And at least one selected from methyl methacrylate-butadiene emulsions and carboxyl-modified emulsions thereof, and more preferably those containing isoprene-based latex and carboxyl-modified latex thereof.

The water-based resin emulsion obtained from the unsaturated monomer may be used in combination with other known water-based resin emulsions such as acrylic emulsions and natural rubber latex. Further, the aqueous polyurethane-based emulsion composition of the present invention may be mixed with another aqueous resin such as an aqueous acrylic resin, polyvinyl alcohol, an aqueous polyester resin, and an aqueous polyolefin resin.

The mixing ratio of the aqueous polyurethane emulsion (a) and the aqueous resin emulsion (b) in the aqueous polyurethane emulsion composition of the present invention is (a) / (b) = 95/5 to 5 in terms of solid content. / 95. When the amount of the aqueous polyurethane emulsion is less than 5% by weight, the adhesion to a non-polar substrate such as a polyolefin becomes poor.
When the aqueous resin emulsion is less than 5% by weight,
Poor adhesion to polar substrates such as polyester and nylon.

The aqueous adhesive of the present invention can be obtained by blending additives and auxiliaries commonly used in aqueous adhesive systems with the aqueous polyurethane emulsion composition of the present invention, if necessary. For example, pigments, solvents, anti-blocking agents, dispersion stabilizers, viscosity modifiers, leveling agents, anti-gelling agents,
Light stabilizer, antioxidant, ultraviolet absorber, heat resistance improver,
Inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing materials, catalysts and the like. The compounding method is obtained by a known method such as stirring and dispersion. If necessary, a curing agent such as Aquanate-100 (a water-dispersible polyisocyanate manufactured by Nippon Polyurethane Industry) may be blended immediately before use.

The aqueous coating composition of the present invention is obtained by blending the aqueous polyurethane-based emulsion composition of the present invention with additives and auxiliaries commonly used in aqueous coating systems, if necessary. For example, pigments, solvents, antiblocking agents, dispersion stabilizers, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antioxidants, UV absorbers, heat resistance improvers, inorganic and organic fillers, plastics Agents, lubricants, antistatic agents, reinforcing materials,
Catalyst. The compounding method is obtained by a known method such as stirring and dispersion. If necessary, a curing agent such as Aquanate-100 (a water-dispersible polyisocyanate manufactured by Nippon Polyurethane Industry) may be blended immediately before use.

[0045]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Unless otherwise specified, "parts" and "%" in the examples mean "parts by weight" and "% by weight", respectively.

[Synthesis of Aqueous Polyurethane Emulsion] Synthesis Example 1 A poly (oxytetramethylene) diol having a number average molecular weight of 2,000 (hereinafter PTG-) was placed in a reactor equipped with a stirrer, a thermometer, a nitrogen sealed tube, and a cooler. 2000)
44 parts, 126 parts of IPDI, and 0.03 part of dibutyltin dilaurate (hereinafter referred to as DBTDL) were charged.
The reaction was performed at 80 ° C. for 2 hours. Then, the reaction solution was heated to 50 ° C
After cooling, 23.5 parts of DMPA, 17.7 parts of triethylamine (hereinafter referred to as TEA) and 194 parts of acetone were added and reacted for 3 hours. Further, 216 parts of acetone was added to the reaction solution, and the mixture was cooled to 30 ° C.
A mixed liquid consisting of 33.5 parts of A, 2.67 parts of monoethanolamine (hereinafter referred to as MEA), 103 parts of isopropyl alcohol (hereinafter referred to as IPA), and 778 parts of water was added, and the mixture was stirred at high speed. Acetone and IPA from liquid
Was distilled off to obtain an aqueous polyurethane emulsion PU-1 having a solid content of 40% and a viscosity of 100 cP / 25 ° C.

Synthesis Example 2 The same reactor as in Synthesis Example 1 was charged in a reactor having a number average molecular weight of 2,000.
0 poly (oxypropylene) glycol (hereinafter PPG)
-2000 referred to as) 345 parts of the H ₆ XDI 77.
8 parts and 0.03 part of DBTDL were charged and reacted at 80 ° C. for 2 hours. Next, the reaction solution was cooled to 50 ° C., and 11.7 parts of DMPA, 8.85 parts of TEA, and 177 parts of acetone were added, and the mixture was reacted for 3 hours. Further, 175 parts of acetone was added to the reaction solution and cooled to 30 ° C.
A mixed solution consisting of 13.4 parts of IPDA, 1.07 parts of MEA, 87.9 parts of IPA, and 1039 parts of water was added, and the mixture was stirred at a high speed. An aqueous polyurethane emulsion PU-2 having a viscosity of 30% and a viscosity of 1000 cP / 25 ° C. was obtained.

Synthesis Example 3 In a reactor similar to that of Synthesis Example 1, a number average molecular weight of 1,000 was added.
175 parts of poly (hexamethylene carbonate) diol (hereinafter abbreviated as PCD-1000)
9.11 parts, 138 parts of H ₁₂ MDI, and IPDI 3
8.9 parts, 0.02 part of DBTDL are charged, and 2 at 80 ° C.
Allowed to react for hours. Next, after cooling the reaction solution to 50 ° C., 35.2 parts of DMPA, 26.6 parts of TEA, and 143 parts of acetone were added, and the mixture was reacted for 3 hours. Further, 176 parts of acetone was added to the reaction solution, and the mixture was cooled to 30 ° C., and 26.8 parts of H ₁₂ MDA, 2.14 parts of MEA, and I
A mixed solution consisting of 79.7 parts of PA and 637 parts of water was added, and the mixture was stirred at high speed. Acetone and IPA were distilled off from this solution to obtain an aqueous polyurethane emulsion PU- having a solid content of 30% and a viscosity of 3000 cP / 25 ° C. 3 was obtained.

Synthesis Example 4 The same reactor as in Synthesis Example 1 was charged with a number average molecular weight of 2,000.
0, iPA / AZA = 1/1 (weight ratio), NPG / E
G = 9/1 (weight ratio) polyester diol (hereinafter referred to as P) obtained from mixed carboxylic acid and mixed low molecular weight polyol.
343 parts, NPG 36.
5 parts, 26.2 parts of DMBA, 119 parts of TDI, 208 parts of acetone, and 0.03 part of DBTDL were charged.
The reaction was performed at 0 ° C. for 10 hours. Next, TEA was added to the reaction solution.
And 17.7 parts of acetone and 301 parts of acetone.
08 parts was added and the mixture was stirred at a high speed, and acetone was distilled off from the liquid to obtain an aqueous polyurethane emulsion PU-4 having a solid content of 30% and a viscosity of 1000 cP / 25 ° C.

Synthesis Example 5 In a reactor similar to that of Synthesis Example 1, 3 PTG-2000 was added.
45 parts, NPG 18.2 parts, DMBA 26.2 parts,
125 parts of MDI and 0.03 parts of 202 parts of acetone were charged and reacted at 50 ° C. for 10 hours. Next, 17.7 parts of TEA and 293 parts of acetone were added to the reaction solution, and 1183 parts of water was added thereto, followed by high-speed stirring. Acetone was distilled off from this solution to give a solid content of 30% and a viscosity of 3500 cP / 2.
An aqueous polyurethane emulsion PU-5 at 5 ° C was obtained.
Table 1 shows Synthesis Examples 1 to 5.

[0051]

[Table 1]

In Table 1, PTG-2000: polytetramethylene glycol having a number average molecular weight of 2,000 PPG-2000: number average molecular weight of 2,000 polypropylene glycol PCD-1000: poly (hexamethylene carbonate) having a number average molecular weight of 1,000 Diol PES-2000: iPA / AZA = 1/1, NPG /
EG = 1/1 (weight ratio) mixed carboxylic acid and mixed low molecular weight diol, number average molecular weight 2,000 polyester diol obtained IPDI: isophorone diisocyanate H ₆ XDI: hydrogenated xylylene diisocyanate H ₁₂ MDI: 4, 4 ′ - dicyclohexylmethane diisocyanate TDI: toluene diisocyanate MDI: 4,4'-diphenylmethane diisocyanate DBTDL: dibutyltin dilaurate DMPA: dimethylolpropionic acid DMBA: dimethylolbutanoic acid TEA: triethylamine NPG: neopentyl glycol IPDA: isophorone diamine H ₁₂ MDA: 4,4'-dicyclohexylmethanediamine MEA: monoethanolamine

[Preparation of Aqueous Polyurethane Emulsion Composition] Example 1 Claprene LIR-7 prepared in PU-1 at pH = 8
00 was blended so that PU-1 / LIR-700 = 70/30 (in terms of solid content). The obtained aqueous polyurethane emulsion composition is designated as E-1.

Examples 2 to 20, Comparative Examples 1 to 4 Water-based polyurethane emulsion compositions E-2 to 24 were obtained in the same manner as in Example 1 at the ratios shown in Tables 2 to 4.

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

In Tables 2 to 4, the symbols of the aqueous resin emulsion (b) are as follows. (A): Kuraprene LIR-700 (Kuraray isoprene system) (B): Denka chloroprene LA-50 (Chloroprene system manufactured by Denki Kagaku Kogyo) (C): JSR 0561 (Styrene-butadiene system manufactured by Japan Synthetic Rubber) (D) : Nipol 1551 (Nitrile-butadiene system manufactured by Zeon Corporation of Japan) (E): JSR 0700 (butadiene system of Japan Synthetic Rubber) (F): Zeon 151 (vinyl chloride system of Zeon Japan) (G): Nipol 2518FS (manufactured by Zeon Japan) (H): HV-100 (Polybutene system manufactured by Nisseki Resin Chemical) (I): Sunstar Polyethylene E-162 (Polyethylene system manufactured by Sunstar Giken) (J): Sumikaflex S -500 (Vinyl acetate based by Sumitomo Chemical) (K): Evadic EV- 60 (manufactured by Dainippon Ink and Chemicals, ethylene - vinyl acetate) (L): Saran Latex 103S (manufactured by Asahi Dow vinylidene chloride) (M): Kurosuren 2M-33A (manufactured by Takeda Chemical Industries
(N): JSR 0668 (Nippon Synthetic Rubber Carboxyl-Modified Styrene-Butadiene System) (O): Closlene NA-10 (Takeda Pharmaceutical Co., Ltd., Carboxyl-Modified Nitrile-Butadiene System) (P): Closrene 2M -30 (Carboxy-modified methyl methacrylate-butadiene system manufactured by Takeda Pharmaceutical Co., Ltd.)

[Formation of Coating Film] Example 21 To E-1 prepared in Example 1, 20 parts of Aquanate 100 (self-emulsifying polyisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.) based on the total solid content, and Kyowanol M 15 parts of a film-forming auxiliary (manufactured by Kyowa Hakko Kogyo Co., Ltd.) was blended with respect to the total solid content to prepare a clear paint. Using this paint, a dry coating film 30 ~ on a polypropylene plate with a bar coater.
After coating to 40 μm, the coating was dried at 80 ° C. for 20 minutes and allowed to stand at room temperature for 5 hours to obtain a coating sample.

Example 22, Comparative Examples 5 and 6 Instead of E-1, E-2, 21, and 22 were used in the proportions shown in Table 5 to prepare clear paints. Coating samples were obtained from these paints in the same manner as in Example 21.

The adhesion and flexibility of the coating films in Examples 21 and 22 and Comparative Examples 5 and 6 were evaluated. Adhesion is JIS
It measured according to the crosscut tape method of K-5400. Flexibility was evaluated by a hot and cold repetition test. Cross-cut tape method: Cut 100 mm squares into 100 squares with a cutter knife using a cutter guide, apply pressure to the coating with cellophane tape, then peel off instantaneously, peeling off the coating I saw 10: No peeling of the coating film is observed. 8: Peeling of the coating film is 0 to 5%. 6: Peeling of the coating film is 5 to 15%. 4: Peeling of the coating film is 15 to 35%. 35-65% 0: Peeling of coating film is 65% or more Repeated heating / cooling method: coating film at -20 ° C for 1 hour, 50 ° C for 1 hour
Evaluation of the appearance of the coating film after 10 cycles in the time cycle ○: No crack was observed in the coating film ×: Cracking occurred in the coating film
Shown in

[0062]

[Table 5]

[Preparation of Adhesive] Example 23 To E-3 prepared in Example 3, 20 parts of Aquanate 100 based on the total solid content and 15 parts of Kyowanol M based on the total solid content were blended. The adhesive was prepared.

Examples 24 and 25, Comparative Examples 7 and 8 E-4, 5, 23 and 24 were used in place of E-3 and blended at the ratios shown in Table 3 to prepare adhesives.

[Adhesion Test] The prepared adhesive was applied to a bar coater No. At 6, coating was performed on both sides with the following film combinations so that the coating amount was 2 g per square meter dry. (1) Corona treated CPP film / Corona treated CPP film (2) Corona treated PET film / Corona treated PET film (3) Corona treated PET film / Corona treated CPP film (4) Corona treated CPP film / Corona treated nylon film Adhesive Is applied to the adherend, and after taking an open time of 80 ° C. × 5 seconds, immediately bonding, and after bonding, 50 ° C.
It was left still for 24 hours. Then, it is cut to a width of 15 mm, a tensile speed: 50 mm / min, and a measurement atmosphere: 25
A T-type peel test was performed at 50 ° C. × 50% RH. Table 6 shows the results of the adhesion test.

[0066]

[Table 6]

In Table 6, CPP: unstretched polypropylene PET: polyethylene terephthalate Measurement unit: gf / 15 mm Film material breakage occurs in the CPP film

[0068]

As described above, according to the present invention, the adhesiveness and adhesion to various substrates such as polyolefin-containing aqueous polyurethane resin compositions and all plastics including general-purpose polyolefins can be sufficiently satisfied. It has become possible to provide a water-based adhesive and a water-based paint having excellent durability.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 30, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

In the case of the one-shot method, NCO group / activity
The ratio of hydrogen groups is from 0.5 to less than 1, preferably
0.8 to less than 1. When it is less than 0.5, the molecular weight of the polyurethane resin is too small, resulting in a lack of durability.
In the case of one or more, gelation is likely to occur when synthesizing the resin.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

In the case of the prepolymer method, the ratio of NCO groups / active hydrogen groups at the time of prepolymer synthesis is from 1.1 to 5.0, preferably from 1.5 to 4.0. If it is less than 1.1, the molecular weight of the prepolymer becomes too large, making it difficult to proceed to the subsequent reaction step. If it exceeds 5.0, the adhesiveness will be poor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 175/04 C09J 175/04

Claims (4)

[Claims] 1. An aqueous polyurethane emulsion composition which satisfies the following conditions (A) to (C). (A) An aqueous polyurethane emulsion composition is prepared by mixing an aqueous polyurethane emulsion (a) and an aqueous resin emulsion (b) obtained from an unsaturated monomer, and (a) / (b) is a solid content weight ratio. 95 / 5-5 /
95. (B) The aqueous polyurethane emulsion (a) is obtained by reacting at least the following (a) to (e). (A) Organic diisocyanate. (B) a polymer polyol selected from at least one selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols. (C) a chain extender. (D) Carboxylic acid-containing low molecular polyol. (E) Neutralizer. (C) The aqueous resin emulsion (b) is at least one selected from the following. Isoprene emulsion, chloroprene emulsion, styrene-butadiene emulsion, nitrile-butadiene emulsion, butadiene emulsion, vinyl chloride emulsion, vinylpyridine-styrene-butadiene emulsion, polybutene emulsion, polyethylene emulsion, vinyl acetate emulsion Ethylene-vinyl acetate emulsion, vinylidene chloride emulsion, methyl methacrylate-butadiene emulsion, and carboxyl-modified latex of these 2. The aqueous polyurethane emulsion composition according to claim 1, wherein the following conditions (A) to (C) are satisfied. (A) An aqueous polyurethane emulsion composition is obtained by mixing an aqueous polyurethane emulsion (a) and an aqueous resin emulsion (b) from an unsaturated monomer, and (a) /
(B) is 95/5 to 5/95 in terms of solid content weight ratio. (B) The aqueous polyurethane emulsion (a) is obtained by reacting at least the following (a) to (e). (A) An organic diisocyanate selected from at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. (B) a polyester diol in which the acid component is aromatic dicarboxylic acid / aliphatic dicarboxylic acid = 35/65 to 65/35 (weight ratio); a polyether diol having an ethylene oxide unit of 50 mol% or less; Polycarbonate diol using hexanediol. A polymer polyol selected from at least one or more of the following. (C) a chain extender having 15 or less carbon atoms. (D) A carboxylic acid-containing low-molecular-weight polyol selected from at least one selected from 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. (E) Neutralizer. (C) The aqueous resin emulsion (b) uses isoprene latex. 3. An aqueous emulsion paint comprising the aqueous polyurethane-based emulsion composition according to claim 1 and / or 2. 4. An aqueous emulsion adhesive comprising the aqueous polyurethane-based emulsion composition according to claim 1 and / or 2.