JPH11279236A - Water-based resin and ink produced by using the resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a water-based resin essentially without using a solvent- removal process and obtain an ink containing the resin and useful for film or paper. SOLUTION: A polyurethane is produced in an unsaturated monomer (in place of an organic solvent) essentially containing an unsaturated monomer having at least two hydroxyl groups and one unsaturated group in one molecule and the produced polyurethane is dispersed in water in the presence of an unsaturated monomer having active hydrogen. The water-based resin is produced by polymerizing an aqueous dispersion of the polyurethane dispersed in the unsaturated monomer solution. The objective ink is produced by using the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin comprising a radical polymer of urethane and an unsaturated monomer, and an ink using the resin. The aqueous resin obtained by the present invention provides a coating film having excellent weather resistance, solvent resistance, and adhesion, is useful in the fields of paints, inks, adhesives, and particularly inks, and can be used widely. It is.

[0002]

2. Description of the Related Art Urethane resins have excellent adhesiveness to substrates, abrasion resistance, impact resistance, and solvent resistance.
It is widely used in paper, plastics, films, metals, textiles, etc. as inks, adhesives, and various coating agents. Conventionally, aqueous urethane resins such as emulsions, colloidal dispersions, and water-soluble urethane resins have been developed mainly by synthesis with acetone, methyl ethyl ketone, n-methylpyrrolidone, an aromatic organic solvent and the like, and after a solvent removal process (Progress in). Organic C
coatings, 9, 281, 1981). Although these aqueous urethane resins are superior to conventional oil-based urethane resins in use and handling, a step of removing the solvent is required in the production thereof. Therefore, problems such as the time and cost required for the solvent removal step, reuse of the organic solvent, and incineration disposal have newly arisen.

[0003] Urethane resins have properties not found in other resins as described above, but are still insufficient from the point of versatility of use as paints, inks, and adhesives, for example, weather resistance and alkali resistance. In terms of heat resistance, it is inferior to other resins. As a method for compensating for these drawbacks, a composite with another resin has been attempted. For example, JP-A-60-550
As disclosed in Japanese Unexamined Patent Application Publication No. 64-164, and Japanese Patent Application Laid-Open No. 5-117611, there is a blend of a urethane resin and an acrylic resin. However, in this system, there are problems such as stability over time due to blending of both emulsions and phase separation at the time of film formation because both resins are not chemically bonded. JP-A-6-8
No. 0930 discloses emulsion polymerization of acrylic in the presence of an aqueous urethane resin. This method is an excellent method for compounding a urethane resin and an acrylic resin, and although improvement in physical properties can be expected, an organic solvent is used when synthesizing the urethane resin, and the aqueous solution is obtained by removing the solvent as described above. There are environmental pollution, health and safety issues. As means for solving these problems, for example, Japanese Unexamined Patent Publication No.
Japanese Patent Publication No. 138211 discloses a method of synthesizing a polyurethane in an acrylic monomer to form a composite. In this method, an unsaturated monomer having no active hydrogen is generally required, and if a normal unsaturated monomer having active hydrogen is used, a reaction between the isocyanate and the unsaturated monomer occurs. There is a disadvantage that it is difficult to increase the molecular weight of the urethane resin. In addition, this method has the drawbacks that the ratio of the urethane resin is reduced because the viscosity is significantly increased in the chain extension reaction, that a special stirring device is required, and that the aqueous dispersion is difficult due to the high viscosity.

[0004]

As described above, in the prior art, the step of removing the solvent is always required in the production of the aqueous urethane resin, and the time and cost required for the step are problematic. At the same time, weather resistance, a disadvantage of urethane resin,
A water-based urethane composite resin with improved alkali resistance could not be easily obtained. For these reasons, there has been a strong demand for an aqueous urethane resin which does not essentially require solvent removal in the production process and which overcomes the drawbacks of conventional urethane resins in the fields of paints, inks and adhesives.

The present invention provides an aqueous resin comprising an aqueous urethane composite resin which is excellent in weather resistance and alkali resistance, which are disadvantages of conventional urethane resins, without using an organic solvent in the production thereof, and using the resin. It is to provide the ink that was used.

[0006]

Means for Solving the Problems The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, they have no problems in environment, health and safety, and have excellent weather resistance and alkali resistance. An aqueous resin composed of a urethane composite resin and an ink using the resin have been completed.

[0007] In order to overcome the problems in the conventional aqueous urethane resin production method, instead of a usual organic solvent,
1) The urethanization reaction was carried out using unsaturated monomers having no active hydrogen as a solvent for synthesizing urethane, and the reactivity was analyzed. As a result, the reaction proceeded in the same manner as in an organic solvent.
2) When an urethanation reaction is performed in an unsaturated monomer containing at least two hydroxyl groups and an unsaturated monomer having one unsaturated group in the same molecule, the unsaturated monomer having the hydroxyl group is obtained. Is incorporated into the urethane to obtain a urethane having an unsaturated group, and it becomes possible to form a polymer of the urethane and the unsaturated monomer through a chemical bond. 3) The presence of a urea bond in the urethane resin Otherwise, the increase in the viscosity of the urethane unsaturated monomer solution is considerably suppressed. 4) It is confirmed that a stable aqueous dispersion can be easily obtained when the aqueous dispersion is performed in the presence of the active hydrogen-containing unsaturated monomer. I found it. Finally, the radical polymerization of the unsaturated monomers has led to the discovery of an aqueous urethane composite resin having excellent weather resistance, alkali resistance and heat resistance, which are the drawbacks of conventional urethane resins.
The ink containing the aqueous resin is particularly useful in terms of physical properties and cost.

[0008] That is, the first invention is to provide a) a polyol and an unsaturated monomer having as an essential component an unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule. First step of reacting an organic polyisocyanate to obtain an unsaturated monomer solution (A) of polyurethane having a number average molecular weight of 30,000 or less b) In the presence of (A) an unsaturated monomer having active hydrogen Second step of dispersing in water to obtain an aqueous dispersion (B) of a polyurethane solution c) An aqueous resin obtained from the third step of radically polymerizing (B).

A second invention is the aqueous resin according to the first invention, wherein the unsaturated monomer in the first step contains an aromatic unsaturated monomer. A third invention is the aqueous resin according to the first invention, wherein the polyurethane contains polyethylene glycol as an essential component in the first step. A fourth invention is that the unsaturated monomer having active hydrogen in the second step is an unsaturated monomer selected from acrylic acid, methacrylic acid, 2-hydroxyethylacrylic acid, and 2-hydroxyethylmethacrylic acid. The aqueous resin according to the first aspect of the present invention is characterized in that:

In a fifth aspect, the polyurethane content in the resin solid content of the aqueous resin obtained in the third step is 5 to 9%.
5% by weight of the aqueous resin of the first invention. A sixth invention is an ink containing the aqueous resin according to any one of the first invention to the fifth invention.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the production of an aqueous urethane composite resin, an unsaturated monomer essentially comprising an unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule in the first step In the reaction between the polyol and the organic polyisocyanate, the polyol is dissolved and dispersed in the unsaturated monomer in advance, and then the polyisocyanate is added.
It is preferable to make it drop. As a method of dissolving and dispersing the polyol in the unsaturated monomer, an operation of dissolving and dispersing the polyol at room temperature as it is, or an operation of heating and stirring can be used. The heating is preferably performed at a lower temperature to prevent unnecessary polymerization of the unsaturated monomer, or under a purge with dry air and / or in the presence of a trace amount of a polymerization inhibitor. The urethanization reaction is carried out in the presence of a catalyst in the range of 50 to 1
It is preferably performed at 00 ° C. for 1 to 20 hours. The end point of the reaction is determined by NCO% measurement and disappearance of NCO peak by IR measurement.

The polyol used in the first step preferably has two or more hydroxyl groups in one molecule. For example, low molecular weight polyols include dihydric alcohols such as ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopentyl glycol;
Examples include trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and sorbitol.

[0013] Examples of higher molecular weight polyols include polyether polyols, polyester polyols, acrylic polyols, epoxy polyols and the like. Examples of the polyether polyol include polyethylene glycol, polyoxypropylene glycol, poly (ethylene / propylene) glycol, polytetramethylene glycol, and the like. Polyester polyols are obtained from the polycondensation of diols and dibasic acids. As diols, in addition to the above-mentioned ethylene glycol and diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and as dibasic acids, adipic acid, azelaic acid, sebacic acid, and isophthalic acid Acid and terephthalic acid. In addition, there are lactone ring-opening polymer polyols such as polycaprolactone and poly β-methyl-δ-valerolactone, and polycarbonate diol. Examples of the acrylic polyol include a copolymer of a monomer having a hydroxyl group. Examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, and dihydroxy acrylate, and examples of the epoxy polyol include an amine-modified epoxy resin. Other examples include polybutadiene diol and castor oil.

These polyols can be used alone or in combination. In order to balance the adhesion to the object to be coated, the paintability, the physical properties of the coating film, and the like, it is generally necessary to use two or more kinds having different chemical structures in combination or to appropriately select the molecular weight thereof. In addition, it is necessary to select a polyol from the viewpoint of solubility in unsaturated monomers having no active hydrogen and urethanization reaction. For example, when a polyester polyol or polyether polyol which is a versatile polyol is used, its molecular weight is 5,0.
If it is more than 00, a high temperature is required for dissolution, or the urethane-forming reaction becomes difficult due to thickening. Even if the polyol has two or more active hydrogens, it becomes a branched structure, so that the problem of thickening is likely to occur. When polyethylene glycol is used alone or in combination with other diols, the diol can be easily made water-soluble, and a stable dispersion or hydrosol can be obtained.

When a polyol having an ionizable group such as a carboxyl group or a sulfone group is used as the diol component, a self-emulsifiable polyurethane can be obtained. As the carboxyl group-containing polyol, dimethylol propionic acid, 2,2-dimethylol acetic acid, 2,2-
Dimethylol butyric acid, 2,2-dimethylolpentanoic acid,
Examples include dimethylolalkanoic acid such as dihydroxypropionic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. Particularly, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferred from the viewpoint of reactivity and solubility.

Examples of the unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule used in the first step include 1) disclosed in, for example, JP-A-56-127618. Reaction product of glycidol and acrylic acid as described above, 2) reaction product of triol, diisocyanate and 2-hydroxymethacrylate, 3) glycerin monomethacrylate derivative (for example, GMGA-70x,
Kyoeisha Chemical, molecular weight 218). By using these unsaturated monomers, it becomes possible to introduce an unsaturated group into the urethane main chain, and it becomes possible to form a complex through a chemical bond with a polymer of the unsaturated monomer. The composite resin thus obtained is excellent in compatibility and storage stability.

The other monomer is preferably an unsaturated monomer having no active hydrogen and copolymerizable with the above-mentioned unsaturated monomer having at least two hydroxyl groups and unsaturated groups in the same molecule. . Specific examples include unsaturated monomers containing no carboxyl group, hydroxyl group, methylol group, silanol group, primary or secondary amino group, and the like. For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl methacrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters; unsaturated monomers having an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether; acrylamide, N-butoxymethyl (meth) acrylamide, N-methylacrylamide, N, N- Dimethylacrylamide, N-isop Unsaturated monomers having an amide group such as pyracrylamide; (meth) having a tertiary amino group such as N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate Acrylic acid; N-vinylpyrrolidone, N-vinylimidazole,
Nitrogen-containing unsaturated monomers such as N-vinylcarbazole; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; styrene, α-methylstyrene, methacrylic acid Aromatic unsaturated monomers such as phenyl; silicon-containing unsaturated monomers such as vinyltriethoxysilane and γ-methacryloyloxypropyltrimethoxysilane; octafluoropentyl (meth) acrylate;
There are monomers having one unsaturated group such as a fluorine-containing unsaturated monomer such as perfluorocyclohexyl (meth) acrylate and an unsaturated monomer having an isocyanate group blocked. Examples of the unsaturated monomer having no active hydrogen and having two unsaturated groups include divinylbenzene and polyethylene glycol di (meth) acrylate.

In selecting an unsaturated monomer having no active hydrogen, it is desirable to dissolve the polyol and the polyisocyanate well. However, it is also possible to select a system which does not completely dissolve as the reaction proceeds. It is. If the solubility is poor, a monomer having high solubility in urethane resin such as vinylpyrrolidone, or a monomer relatively soluble in urethane such as aromatic unsaturated monomer is used. It is preferred to use.

As the organic polyisocyanate, there are aromatic, aliphatic and alicyclic polyisocyanates. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate , Isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4, 4'-
Buphenylene diisocyanate, 3,3'-dichloro-
4,4'-biphenylenediisocyanate, 1,5-naphthalenediisocyanate, 1,5-tetrahydronaphthalenediisocyanate, and the like can be used alone or in a mixture.

The catalyst used for the reaction between the isocyanate and the hydroxyl group includes dibutyl tin dilaurate, tin octoate, dibutyl tin di (2-ethylhexoate),
Lead 2-ethylhexoate, 2-ethylhexyl titanate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, stannous chloride, Stannic chloride,
Iron chloride.

In the reaction in an unsaturated monomer, the solution viscosity generally becomes higher than that in a solvent system, so it is important to keep the molecular weight of the polyurethane within a specific range. When the number average molecular weight of the polyurethane is 30,000 or more, the viscosity is remarkably increased or the reaction takes a long time. When the ratio of the polyurethane to the sum of the weight of the polyurethane and the weight of the unsaturated monomer as the solvent is 95% by weight or more, it is difficult to obtain weather resistance and the like characteristic of the unsaturated monomer. It is difficult to exhibit characteristics such as adhesion to a substrate, abrasion resistance, solvent resistance, and rebound resilience. These unsaturated monomers having active hydrogen account for 1% by weight of the total unsaturated monomers as a solvent.
~ 30% by weight is preferred. If it is less than 1% by weight, water dispersibility is not good, and if it is more than 30% by weight, aggregates are liable to be generated during polymerization.

The unsaturated monomer having an active hydrogen used in the second step includes unsaturated monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid and crotonic acid; 2-hydroxyethyl (meth And (meth) acrylic acid esters having a hydroxyl group such as acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl acrylate; N-methylol (meth) acrylamide; These unsaturated monomers having active hydrogen can be added before or during aqueous dispersion. This will lower the solution viscosity and if the polyurethane ends have NCO groups, some of the unsaturated monomers will react with the ends, and can be combined with other unsaturated monomers through chemical bonding in a later step. become. Among unsaturated monomers having active hydrogen, acrylic acid, methacrylic acid, 2-hydroxyethylacrylic acid, and 2-hydroxyethylmethacrylic acid are particularly preferable in terms of decreasing the viscosity.

In the second step, the method for dispersing the unsaturated monomer solution of polyurethane in water is as follows: 1) a method in which a diol component containing a carboxyl group is used as a diol component, and neutralization with a base; 2) an alkyl having a tertiary amino group. Prepolymerization with dialkanolamine and quaternization 3)
A method of prepolymerizing with an alkyl dialkanolamine having a tertiary amino group, neutralizing with an acid, and forming an amine salt,
4) A method in which a polyol having high water solubility, for example, polyethylene glycol is used as a urethane component. Further, in the present invention, it is preferable not to use a surfactant, but the stability of the aqueous dispersion of the unsaturated monomer solution of the polyurethane or the polymerization of a composite resin dispersion obtained by radical polymerization of the dispersion. A small amount of a surfactant may be used in combination for the purpose of improving stability.

The basic compound used for aqueous conversion includes sodium hydroxide, potassium hydroxide, ammonia,
Methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N
-Methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine and the like; , Used in mixing. When neutralizing the unsaturated monomer solution of the polyurethane, it is necessary to appropriately select a neutral compound because the compatibility with the solution and the stability after dispersion in water may differ depending on the type of the basic compound. In neutralizing a compound having a carboxyl group such as dimethylolalkanoic acid, the amount is preferably 0.6 to 1.2 equivalents per equivalent of the carboxyl group.

Examples of the surfactant include a fatty acid salt, an alkyl sulfate salt, an alkylbenzene sulfonate,
Anionic surfactants such as naphthalene sulfonate and alkyl sulfosuccinate; polyoxyethylene alkyl ether, polyoxyethylene alkyl ester,
There are nonionic surfactants such as polyoxyethylene alkylphenyl ether and polyoxyethylene alkylphenyl ester. It is also possible to use a reactive activator in combination to suppress a decrease in water resistance.

In the aqueous dispersion, the total amount of the polyurethane and the unsaturated monomer is preferably within a range of 70% by weight or less based on the total amount. If it is more than 70% by weight, aggregates are easily formed, and it is difficult to obtain a uniform polymer. As a method for dispersing the unsaturated monomer solution of polyurethane in water, it is possible to disperse the aqueous solution using a usual stirrer. In order to obtain a stable aqueous dispersion, forcible dispersion under a high shearing force using a homomixer, a homogenizer, or a microfluidizer (manufactured by Mizuho Industry Co., Ltd.) is preferable.

In the third step, a known radical polymerization method is preferred for obtaining a composite resin dispersion by radical polymerization of the aqueous dispersion. As the polymerization initiator, both a water-soluble initiator and an oil-soluble initiator can be used. When using the oil-soluble initiator, it is preferable to dissolve it in advance in the unsaturated monomer solution of the polyurethane. These polymerization initiators are suitably used in the range of 0.05 to 5% with respect to the unsaturated monomer. The temperature is preferably from 40 to 100C, and 80C or less is sufficient for a redox initiator. Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile and azobisisobutylvaleronitrile, benzoyl peroxide, isobutyryl peroxide, octanoyl peroxide, cumylperoxyoctate, and t-butylperoxy-. 2-
Organic peroxides such as ethylhexanoate, t-butylperoxyacetate, lauryl peroxide, di-t-butylperoxide, di-2-ethylhexylperoxyzine carbonate, potassium persulfate, ammonium persulfate, hydrogen peroxide And the like. Organic or inorganic peroxide compounds can also be used as redox initiators in combination with reducing agents. Examples of the reducing agent used include L-ascorbic acid, L-sorbic acid, sodium metabisulfite,
Ferric sulfate, ferric chloride, Rongalit and the like.

With respect to the method of polymerizing the unsaturated monomer, a method in which the entire amount is charged, the entire amount is dripped, or a part is charged and the rest is dropped is possible. In the polymerization of unsaturated monomers, a known chain transfer agent for the purpose of adjusting the molecular weight,
For example, octyl mercaptan, lauryl mercaptan,
It is also possible to use 2-mercaptoethanol, tercharddecyl mercaptan, thioglycolic acid, and the like.

The aqueous resin of the present invention is particularly useful for inks, but can also be used for paints and adhesives. For inks, the aqueous resin is contained in an amount of 3% by weight or more based on the solid content of the ink.
Desirably, the content is 80% by weight. If it is 3% by weight or less, the adhesiveness to the film is poor, and if it is 80% by weight or more, the coloring and hiding properties are poor.

The ink of the present invention may optionally contain other resins, for example, acrylic resin, polyester resin, amino resin, polyurethane resin, epoxy resin, etc.
In addition, it is possible to appropriately add a dispersing aid, an antifoaming agent, a thickener, a surfactant, an ultraviolet absorber, a light stabilizer, and an organic solvent according to the use. Further, depending on the purpose, a crosslinking agent can be added to improve water resistance, film strength and chemical resistance. Examples of the crosslinking agent include a blocked isocyanate compound, an oxazoline compound, a carbodiimide compound, an aziridine compound, and an epoxy compound. The ink containing the aqueous urethane composite resin thus obtained can be widely applied to films and papers.

[0031]

EXAMPLES The present invention will be described in detail below with reference to examples based on resins obtained in production examples, but the present invention is not limited to these examples. In the following production examples and examples,
Unless otherwise specified, “parts” means parts by weight.

[0032]

Production Example 1 A 4-neck 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and 21.9 parts of glycerin monomethacrylate (molecular weight: 218), butyl 15 parts of acrylate,
8 parts of methyl methacrylate, number average molecular weight about 2,000
(Hydroxyl value 56) polytetramethylene glycol 22
1.4 parts, 27.7 parts of polyethylene glycol having a number average molecular weight of 2,000 (hydroxyl value: 56) and 25.4 parts of dimethylolpropionic acid were charged, and the temperature was raised to 60 ° C. Under stirring, 83.8 parts of isophorone diisocyanate and 0.08 part of dibutyltin dilaurate were added, and the temperature was raised to 80 ° C.
Let react for 3 hours, polyurethane number average molecular weight about 7,500
Was obtained.

The polyurethane monomer solution was cooled to 30 ° C., and 2 parts of acrylic acid were added. Ammonia water15.
0 parts and 600 parts of distilled water were added to obtain a dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and 0.3 parts of potassium persulfate was added to carry out an acrylic polymerization reaction for 4 hours. Furthermore,
0.1 part of potassium persulfate was added and the reaction was continued for 2 hours to obtain an aqueous urethane composite resin dispersion (A).

[0034]

Production Example 2 A four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and 10.3 parts of glycerin monomethacrylate (molecular weight: 218), butyl 20 parts of acrylate,
30 parts of methyl methacrylate, number average molecular weight about 1,50
0 (hydroxyl value 75.6) polypropylene glycol 1
81.0 parts, number average molecular weight about 2,000 (hydroxyl value 5
33.3 parts of the polyethylene glycol of 6) and 24.7 parts of dimethylolbutanoic acid were charged and heated to 60 ° C.
Under stirring, 83.9 parts of diphenylmethane diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted for 6 hours to obtain a polyurethane monomer solution having a number average molecular weight of 16,500.

The polyurethane monomer solution was cooled to 30 ° C., and 10 parts of 2-hydroxyethyl acrylate and 6.7 parts of acrylic acid were added. 17.8 parts of aqueous ammonia,
600 parts of distilled water was added to obtain an aqueous dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and potassium persulfate 1.1 was added.
An acrylic polymerization reaction was performed for 4 hours. Further, 0.3 part of potassium persulfate was added and the reaction was continued for 2 hours to obtain an aqueous urethane composite resin dispersion (B).

[0036]

Production Example 3 A four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and 7.7 parts of glycerin monomethacrylate (molecular weight: 218), ethyl Acrylate 50 parts, butyl acrylate 80 parts, methyl methacrylate 30
Parts, 105.4 parts of polytetramethylene glycol having a number average molecular weight of about 1,500 (hydroxyl number 75.6), 20.0 parts of polyethylene glycol having a number average molecular weight of about 2,000 (hydroxyl number 56), dimethylolbutanoic acid 14.8 parts were charged and the temperature was raised to 60 ° C. Under stirring, 52.0 parts of diphenylmethane diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted for 8 hours to obtain a polyurethane monomer solution having a number average molecular weight of 21,500.

The polyurethane monomer solution was cooled to 30 ° C., and 20 parts of 2-hydroxyethyl acrylate, 20 parts of acrylic acid and 4 parts of azobisisobutyronitrile were added. 38.2 parts of triethylamine and 600 parts of distilled water were added to obtain an aqueous dispersion of a polyurethane monomer solution.
Next, while introducing nitrogen gas into the flask, the aqueous dispersion
The temperature was raised to 5 ° C., and the acrylic polymerization reaction was performed for 6 hours to obtain an aqueous urethane composite resin dispersion (C).

[0038]

Production Example 4 A 4-neck 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and glycidol / methacrylic acid = 1 /
5.8 parts of 1 reactant (molecular weight: 160), 50 parts of ethyl acrylate, 100 parts of butyl acrylate, 35 parts of methyl methacrylate, 97.0 parts of polytetramethylene glycol having a number average molecular weight of about 1,000 (hydroxyl value: 111),
20.0 parts of polyethylene glycol having a number average molecular weight of about 1,000 (hydroxyl value: 111), dimethylolbutanoic acid 1
8.5 parts were charged and heated to 60 ° C. Under stirring, 59.7 parts of isophorone diisocyanate and 0.05 part of dibutyltin dilaurate were added, the temperature was raised to 80 ° C., and the mixture was reacted for 5 hours to obtain a polyurethane monomer solution having a number average molecular weight of 25,200.

The polyurethane monomer solution was cooled to 30 ° C., and 20 parts of 2-hydroxyethyl methacrylate was added.
15 parts of methacrylic acid were added. Triethylamine30.
2 parts and 600 parts of distilled water were added to obtain an aqueous dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and 3 parts of potassium persulfate was added to carry out an acrylic polymerization reaction for 4 hours. Further, 1 part of potassium persulfate was added and the reaction was continued for 2 hours to obtain an aqueous urethane composite resin dispersion (D).

[0040]

Production Example 5 A 4-neck 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and glycidol / methacrylic acid = 1 /
0.5 part of 1 reactant (molecular weight 160), 90 parts of butyl acrylate, 72 parts of methyl methacrylate, styrene 10
0 parts, 40 parts of 2-ethylhexyl acrylate, 10.4 parts of polypropylene glycol having a number average molecular weight of about 1,000 (hydroxyl value: 111), and a number average molecular weight of about 1,000
2 parts of polyethylene glycol (hydroxyl value 111) and 1.5 parts of dimethylolbutanoic acid were charged and heated to 60 ° C. Under stirring, 5.6 parts of isophorone diisocyanate,
0.01 part of dibutyltin dilaurate was added, the temperature was raised to 80 ° C., and the mixture was reacted for 5 hours to obtain a polyurethane monomer solution having a number average molecular weight of 28,800.

The polyurethane monomer solution was cooled to 30 ° C., and 30 parts of 2-hydroxyethyl methacrylate were added.
Acrylic acid 38 parts, azobisisobutyronitrile 7.6
Parts were added. 54.4 parts of triethylamine, 60 distilled water
0 parts were added to obtain an aqueous dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and an acrylic polymerization reaction was performed for 6 hours.
An aqueous urethane composite resin dispersion (E) was obtained.

[0042]

Production Example 6 A 4-neck 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and glycidol / methacrylic acid = 1 /
1 reaction product (molecular weight 160) 5.7 parts, ethyl acrylate 50 parts, butyl acrylate 100 parts, methyl methacrylate 35 parts, polytetramethylene glycol 106.7 having a number average molecular weight of about 1,000 (hydroxyl value 111)
Parts, polyethylene glycol having a number average molecular weight of about 1,000 (hydroxyl value 111), dimethylolbutanoic acid 2
0.3 part was charged and the temperature was raised to 60 ° C. Under stirring, 65.3 parts of isophorone diisoanate and 0.05 part of dibutyltin dilaurate were added, the temperature was raised to 80 ° C., and the mixture was reacted for 12 hours to obtain a polyurethane monomer solution having a number average molecular weight of 31,100.

The polyurethane monomer solution was cooled to 30 ° C., and 20 parts of 2-hydroxyethyl methacrylate were added.
15 parts of methacrylic acid were added. Triethylamine 31.
Five parts and 600 parts of distilled water were added to obtain an aqueous dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and 3 parts of potassium persulfate was added to carry out an acrylic polymerization reaction for 4 hours. Further, 1 part of potassium persulfate was added and the reaction was continued for 2 hours to obtain an aqueous urethane composite resin dispersion (F).

[0044]

Production Example 7 A four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and 150 parts of butyl acrylate, 100 parts of methyl methacrylate, and 2-ethylhexyl were used. 20 parts of acrylate, number average molecular weight about 1,500 (hydroxyl value 7
5.6) 57.6 parts of polytetramethylene glycol,
12.4 parts of polyethylene glycol having a number average molecular weight of 1,000 (hydroxyl value: 111) and 7.4 parts of dimethylolpropionic acid were charged, and the temperature was raised to 60 ° C. Under stirring, 22.6 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate were added, the temperature was raised to 80 ° C., and the mixture was reacted for 15 hours to obtain a polyurethane monomer solution having a number average molecular weight of 18,500.

The polyurethane monomer solution was cooled to 30 ° C., and 10 parts of 2-hydroxyethyl methacrylate was added.
20 parts of methacrylic acid were added. Triethylamine 29
And 600 parts of distilled water, to obtain an aqueous dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and potassium persulfate 4
An acrylic polymerization reaction was performed for 4 hours. Further, 2 parts of potassium persulfate was added and the reaction was continued for 2 hours to obtain an aqueous urethane composite resin dispersion (G).

[0046]

[Production Example 8] A 4-neck 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry air, and 16.5 parts of glycerin monomethacrylate (molecular weight: 218) was added. 30 parts of acrylate,
30 parts of methyl methacrylate, 7 parts of 2-ethylhexyl acrylate, a number average molecular weight of about 2,000 (hydroxyl value 5
161.0 parts of polypropylene glycol of 6), 33.3 parts of polyethylene glycol having a number average molecular weight of 2,000 (hydroxyl value 56) and 30.8 parts of dimethylolbutanoic acid were charged, and the temperature was raised to 60 ° C. Under stirring, 91.6 parts of diphenylmethane diisocyanate was added, the temperature was raised to 80 ° C., and the mixture was reacted for 10 hours to obtain a polyurethane monomer solution having a number average molecular weight of 16,400.

21 parts of triethylamine and 600 parts of distilled water were added to obtain an aqueous dispersion of a polyurethane monomer solution. Next, the temperature of the aqueous dispersion was raised to 75 ° C. while introducing nitrogen gas into the flask, and 1 part of potassium persulfate was added to carry out an acrylic polymerization reaction for 4 hours. Furthermore, potassium persulfate was added to 0.4
The reaction was continued for additional 2 hours to obtain an aqueous urethane composite resin dispersion (H).

[0048]

Production Example 9 A four-necked 2000 ml flask equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer was replaced with dry nitrogen, and 600 parts of methyl ethyl ketone, a number average molecular weight of about 2,000 (hydroxyl group) was obtained. 556 parts of polytetramethylene glycol having a valence of 56) and a number average molecular weight of about 1,000
32 parts of polyethylene glycol (hydroxyl value 111) 29.6 parts of dimethylolpropionic acid were charged, and the temperature was raised to 60 ° C. Under stirring, isophorone diisocyanate 8
6.4 parts and 0.1 part of dibutyltin dilaurate were added and 80
Temperature, and allowed to react for 4 hours to obtain a number average molecular weight of 9,800.
Of polyurethane was obtained.

The polyurethane was cooled to 30 ° C., 15 parts of ammonia water and 660 parts of distilled water were added, and the solvent was removed to obtain an aqueous urethane resin (I).

Using the aqueous urethane composite resins and aqueous urethane resins obtained in Production Examples 1 to 9, samples shown in the following Examples were obtained and evaluated.

Example 1 A coating liquid was prepared by adding 10% of butyl cellosolve as a film forming aid to the aqueous urethane composite resin (A). Next, the coating liquid for the adjustment was applied to a thickness of 0.5 mm on a slate plate to which black lacquer was applied, and was formed into a film by a drier at 60 ° C to obtain a sample. The sample was irradiated for 500 hours with a Du-cycle type weather meter, and its gloss was measured. The gloss retention was calculated from the difference from the initial gloss. The aqueous resins used in Examples and Comparative Examples are described below. Example 2 Aqueous urethane composite resin (B) Example 3 Aqueous urethane composite resin (C) Example 4 Aqueous urethane composite resin (D) Example 5 Aqueous urethane composite resin (E) Comparative Example 1 Aqueous urethane composite resin (F) Comparative Example 2 Aqueous urethane composite resin (G) Comparative Example 3 Aqueous urethane composite resin (H) Comparative Example 4 Aqueous urethane resin (I)

[0052]

Example 6 50 parts of an aqueous urethane composite resin (A), 20 parts of a phthalocyanine blue pigment (Lionol Blue KLH manufactured by Toyo Ink Mfg. Co., Ltd.), 0.1 part of an antifoaming agent, and 2 parts of water
9.9 parts were stirred with a homomixer at 7,000 rpm for 20 minutes to obtain a pigment dispersion. The pigment dispersion was adjusted with a mixed solvent of water / isopropyl alcohol = 1/1 in Zahn Cup # 4 so as to be 19 seconds, and treated OPP film ("Pyren P2161" manufactured by Toyobo Co., Ltd.), treated PET film ("Ester E5 100" manufactured by Toyobo Co., Ltd.) using a # 7 bar coater. Then 6
Dried in a drying oven at 0 ° C for 1 minute,
This was used as a sample for color development evaluation.

The aqueous resins used in Examples and Comparative Examples are described below. Example 7 Aqueous urethane composite resin (B) Example 8 Aqueous urethane composite resin (C) Example 9 Aqueous urethane composite resin (D) Example 10 Aqueous urethane composite resin (E) Comparative Example 5 Aqueous urethane composite resin (F) Comparative Example 6 Aqueous urethane composite resin (G) Comparative Example 7 Aqueous urethane composite resin (H) Comparative Example 8 Aqueous urethane resin (I)

The methods for evaluating the samples obtained in Examples 1 to 10 and Comparative Examples 1 to 8 are described below. The results are shown in Tables 1 and 2.

A) Evaluation of weather resistance The gloss retention of Examples 1 to 5 and Comparative Examples 1 to 4 was examined. ◎ Gloss retention is 80% or more ○ ６０ 60 to 80% △ 〃 40 to 60% × 〃 40% or less

B) Evaluation of Adhesion to OPP and PET Films The samples obtained in Examples 6 to 10 and Comparative Examples 5 to 8 were subjected to a tape peeling test to examine the adhesion. ◎ Does not peel at all. ○ Almost no peeling. △ Peel a little. X: It peels considerably.

C) Evaluation of color development The color development of the samples obtained in Examples 6 to 10 and Comparative Examples 5 to 8 was visually and comprehensively determined from density, gloss and transparency. ◎ Very good ○ Good △ Normal × Poor

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

The present invention is an aqueous resin excellent in cost because no step using an organic solvent is required. In the production process, since the urethanization reaction is performed in an unsaturated monomer having at least two hydroxyl groups, the main chain of the urethane resin and the unsaturated monomer may be directly chemically bonded. It is possible to have a resin form different from that of the blend system. Urethane resin composited with such an unsaturated monomer has good compatibility at the time of film formation, and adhesion to a substrate, which is an advantage of urethane, abrasion resistance, solvent resistance,
It is possible to improve physical properties such as weather resistance, alkali resistance, and heat resistance, which are disadvantages of urethane resins, without impairing impact resistance. According to this method, it has become possible to provide a very practical aqueous resin and an ink using the resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 11/00 C09D 11/00 // C08G 18/00 C08G 18/00 B (72) Inventor Tsukasa Otsuki Futoshi Kyobashi, Chuo-ku, Tokyo Chome 3-13 Toyo Inki Manufacturing Co., Ltd.

Claims (6)

[Claims] A) reacting a polyol with an organic polyisocyanate in an unsaturated monomer having an unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule as an essential component; A) a first step of obtaining a polyurethane unsaturated monomer solution (A) having a number average molecular weight of 30,000 or less b) dispersing (A) in water in the presence of an unsaturated monomer having active hydrogen; C) Aqueous resin obtained from the third step of radically polymerizing (B). 2. The aqueous resin according to claim 1, wherein in the first step, the unsaturated monomer contains an aromatic unsaturated monomer. 3. The aqueous resin according to claim 1, wherein in the first step, the polyurethane contains polyethylene glycol as an essential component. 4. The method according to claim 1, wherein the unsaturated monomer having active hydrogen in the second step is an unsaturated monomer selected from acrylic acid, methacrylic acid, 2-hydroxyethylacrylic acid and 2-hydroxyethylmethacrylic acid. The aqueous resin according to claim 1, wherein 5. The aqueous resin according to claim 1, wherein the polyurethane content in the resin solid content of the aqueous resin obtained in the third step is 5 to 95% by weight. 6. An ink comprising the aqueous resin according to any one of claims 1 to 5.