JP6478694B2 - Aqueous dispersion of polyurethane urea-acrylic composite resin - Google Patents

Description

  The present invention relates to an aqueous dispersion of a polyurethaneurea-acrylic composite resin.

Water-based polyurethane resins are conventionally useful materials as adhesives, coatings, paints, modifiers, binders and the like, and are used in a wide range of applications. As such a water-based polyurethane resin, a method of containing an anionic, cationic, non-ionic or other hydrophilic group in a urethane resin skeleton to self-emulsify and disperse can be used to make the particle diameter finer, and also to be effective. It is known to be excellent, but further improvement in water resistance and solvent resistance is desired.
As a solution, methods of blending isocyanate type, epoxy type, aziridine type, carbodiimide type and metal chelate type crosslinking agent are known, but the stability after compounding is poor, and in order to obtain the crosslinking property, Heat treatment is required. In general, for the production of aqueous polyurethane resin, a hydrophilic group-containing urethane prepolymer is synthesized in an organic solvent, and in the case of an anionic or cationic resin, a polyvalent amine compound (e.g. It is produced by polymerizing with C), but this method requires desolvation. It is very uneconomical to remove the solvent due to great energy and complicated operation, and it is difficult to completely remove the used organic solvent from the obtained aqueous polyurethane resin.
Various methods have been proposed that utilize self-crosslinking between a hydrazide group and a carbonyl group as a countermeasure for crosslinking at normal temperature and having good emulsion stability (Patent Documents 1 to 4). Specifically, a mixture of a carbonyl group- or hydrazide group-containing crosslinking agent or resin that reacts with a water-based polyurethane resin having a hydrazide group or a carbonyl group introduced therein is disclosed.

Unexamined-Japanese-Patent No. 02-238015 gazette JP, 2011-149011, A Japanese Patent Application Laid-Open No. 01-3017762 JP-A-11-50002

  In view of the above, the inventors of the present invention have shown cross-linking properties higher than those of the prior art, and studied to carry out the synthesis without using a surfactant or an organic solvent. The crosslinking property of the carbonyl group-containing alcohol is weak, and the reaction product of diepoxide and ketocarboxylic acid is not preferable because significant coloration is observed at the time of synthesis of the reaction product. In the method described in Patent Document 2, the carbonyl group-containing acrylic polymer is emulsion-polymerized in an aqueous urethane, but the crosslinking effect is weak because the urethane skeleton and the carbonyl group-containing acrylic polymer do not crosslink. In addition, since a surfactant is required during the emulsion polymerization of the acrylic polymer, the water resistance is poor. In the method described in Patent Document 3, the hydrazide-terminated urethane crosslinks with the carbonyl group-containing acrylic polymer, but the molecular weight of the hydrazide-terminated urethane is limited, and the introduced amount of the hydrazide group is also limited. From the above, there is a limit to its crosslinking properties. In addition, an organic solvent must be used at the time of synthesis of the urethane prepolymer, and a surfactant is required for the emulsion polymerization of the carbonyl group-containing acrylic polymer. In the method described in Patent Document 4, a carbonyl group-containing acrylic polymer is copolymerized in the unsaturated bond-introduced urethane portion, but what is substantially disclosed is one using an OH-terminated prepolymer Since the urethane molecular weight is a low molecular weight, the properties of the urethane are lost. Further, an organic solvent must be used at the time of synthesis of the urethane prepolymer, and an emulsifier is required for the emulsion polymerization of the carbonyl group-containing acrylic polymer.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, the NCO-terminated urethane prepolymer (A) and the ethylenically unsaturated monomer (B) having a specific structure were emulsified in water at a specific ratio. The aqueous dispersion of polyurethaneurea-acrylic composite resin (X) is obtained by dispersing and then chain-extending with a polyhydric amine compound (C) and further polymerizing (A) and (B). It has been found that it can be solved and the present invention has been completed.

That is, the present invention relates to the inventions listed below.
(1) Emulsify and disperse (A) and (B) at least (A) / (B) = 95/5 to 40/60 (weight ratio) in water, and then chain extension with a polyvalent amine compound (C) And an aqueous dispersion of polyurethaneurea composite resin (X) obtained by polymerizing (A) and (B).
(A) A polyol component containing an active hydrogen group-containing anionic salt forming group-containing compound (A1) and an unsaturated polyester polyol (A2) having at least two or more hydroxyl groups, and a polyisocyanate component (A3) NCO-terminated urethane prepolymer obtained
(B) Ethylenic selected from at least one selected from acrolein, diacetone (meth) acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, and acetoacetoxy ethyl methacrylate (B1) Unsaturated monomer
(2) The NCO-terminated urethane prepolymer (A) is obtained by reacting an isocyanate group and an active hydrogen group by (isocyanate group: active hydrogen group =) 1.5 to 3.0: 1 (molar equivalent ratio), (1) An aqueous dispersion of the polyurethaneurea composite resin (X) described above.
(3) The ionic salt forming group of the active hydrogen group-containing anionic salt forming group-containing compound (A1) is a carboxyl group, and the acid value of the NCO-terminated urethane prepolymer (A) is 7 to 50 mg KOH / g, Aqueous dispersion of polyurethane urea composite resin (X) as described in (1) or (2).
(4) Furthermore, at least 2 of the hydrazide group is contained in an amount of 0.3 to 1.3 moles with respect to 1 mole of the carbonyl group of the ethylenically unsaturated monomer (B1) contained in the polyurethaneurea composite resin (X). The aqueous dispersion of polyurethane urea composite resin (X) in any one of (1)-(3) obtained by mixing the hydrazide compound (D) which has a hydrazide group of more than this.
(5) An aqueous dispersion of polyurethaneurea composite resin (X) according to any one of (1) to (4), which is produced substantially without solvent and without using a surfactant.
(6) A step of emulsifying and dispersing (A) and (B) in water at least (A) / (B) = 95/5 to 40/60 (weight ratio), and chaining with polyvalent amine compound (C) The manufacturing method of the water dispersion of polyurethane urea composite resin (X) including the process of extending | stretching and the process of polymerizing (A) and (B).
(A) A polyol component containing an active hydrogen group-containing anionic salt forming group-containing compound (A1) and an unsaturated polyester polyol (A2) having at least two or more hydroxyl groups, and a polyisocyanate component (A3) NCO-terminated urethane prepolymer obtained
(B) Ethylenic selected from at least one selected from acrolein, diacetone (meth) acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, and acetoacetoxy ethyl methacrylate (B1) Unsaturated monomer

  According to the present invention, an aqueous dispersion of a polyurethaneurea-acrylic composite resin having good emulsion stability and good water resistance and solvent resistance of the obtained coating substantially without using an organic solvent and surfactant Can provide a body.

  The aqueous dispersion of the polyurethaneurea-acrylic composite resin (X) of the present invention comprises at least (A) and (B) emulsified and dispersed in water, followed by chain extension with the polyvalent amine compound (C), and (A) And (B) by polymerization.

  The NCO-terminated urethane prepolymer (A) of the present invention comprises a polyol component containing an active hydrogen group-containing anionic salt forming group-containing compound (A1) and an unsaturated polyester polyol (A2) having at least two or more hydroxyl groups. And polyisocyanate component (A3).

  In the present invention, the active hydrogen group-containing anionic salt forming group-containing compound (A1) refers to a compound having one or more active hydrogen groups and an ionic salt forming group. In the present invention, the active hydrogen group is not particularly limited as long as it is a functional group having an active hydrogen atom reactive with an NCO group, and examples thereof include a hydroxyl group, an amino group and a thiol group.

  In the present invention, the active hydrogen group-containing anionic salt-forming group-containing compound (A1) and the corresponding salt-forming agent are not particularly restricted but, for example, compounds having a salt-forming carboxylic acid or sulfonic acid group and the corresponding Salt forming agents and corresponding salt forming agents etc. may be mentioned. For example, hydroxy acids, amino sulfonic acids, hydroxy sulfonic acids, amino carboxylic acids, polyvalent hydroxy acids and the like can be mentioned. The hydroxy acid is not particularly limited, and examples thereof include glycolic acid, malic acid, dimethylol propionic acid, and dimethylol butanoic acid. The aminocarboxylic acid is not particularly limited, and examples thereof include glycine, aminobenzoic acid and alanine. The aminosulfonic acid is not particularly limited, and examples thereof include aminoethylsulfonic acid and (aminoethyl) aminoethanesulfonic acid. The hydroxysulfonic acid is not particularly limited, and examples thereof include 2-hydroxyethanesulfonic acid, an ester of dimethyl sodium 5-sulfoisophthalate and a polyhydric alcohol, and the like. Among these, hydroxy acids and hydroxy sulfonic acids are preferable, and dimethylol propionic acid, dimethylol butanoic acid, and an esterified product of dimethyl sodium 5-sulfoisophthalate and a polyhydric alcohol are more preferable. The corresponding salt-forming agent is not particularly limited, and examples thereof include monovalent metal hydroxides and tertiary amine compounds. The monovalent metal hydroxide is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide and calcium hydroxide. The tertiary amine compound is not particularly limited, and examples thereof include monovalent metal hydroxides, ammonia, trimethylamine and triethylamine. Among these, tertiary amine compounds are preferable, and triethylamine is more preferable.

  In the present invention, the unsaturated polyester polyol (A2) having at least two or more hydroxyl groups has at least two or more hydroxyl groups obtained by condensation reaction of i) unsaturated dibasic acid and polyhydric alcohol. A compound, ii) a compound having at least two or more hydroxyl groups obtained by condensation reaction of an unsaturated dibasic acid, a saturated polybasic acid and a polyhydric alcohol, iii) an ethylenic acid containing two or more hydroxyl groups Compound having at least two or more hydroxyl groups obtained by condensation reaction of saturated monomer and saturated polybasic acid, and iv) Ethylenically unsaturated monomer containing two or more hydroxyl groups, polyhydric alcohol And compounds having at least two or more hydroxyl groups obtained by condensation reaction of saturated polybasic acids. Among these, i) and ii) are preferable from the viewpoint of versatility of raw materials and expression of desired performance.

  Examples of the unsaturated dibasic acid include itaconic acid, itaconic acid anhydride, maleic acid, maleic acid anhydride, citraconic acid, chloromaleic acid, fumaric acid, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl maleate, and dibutyl acid. Examples thereof include unsaturated carboxylic acids such as maleate, dimethyl itaconate and diethyl itaconate, and alkyl esters thereof.

  As saturated polybasic acids, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, succinic acid anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like, and dimethyl esters thereof Aliphatic dicarboxylic acids and their alkyl esters, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc. Alicyclic dicarboxylic acids and their alkyl esters, orthophthalic acid, phthalic anhydride and isophthalic acid And aromatic dicarboxylic acids such as terephthalic acid and terephthalic acid dimethyl ester and alkyl esters thereof; and saturated polybasic acids and alkyl esters thereof such as trimellitic acid, trimellitic acid anhydride and pyromellitic acid anhydride.

The ethylenically unsaturated monomer containing two or more hydroxyl groups is not particularly limited, and examples thereof include those having (meth) acryloyl group, vinyl group, vinyl ether group, allyl group and allyl ether group. Among these, (meth) acryloyl group and allyl group are preferable from the viewpoint of reactivity and discoloration prevention property of a film, and examples thereof include glycerin mono (meth) acrylate and glycerin monoallyl ether.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 2-methyl-1,4-propanediol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neodymium, and the like. Pentyl glycol, 1,5-pentanediol, 1,6-hexanediol, tetraethylene glycol, 3-methyl-1,5 pentanediol, 2-ethyl-1,3 hexanediol, 2-butyl-2-ethyl-1 3, 3-propanediol, cyclohexane-1,4 dimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, spiro glycols, bisphenol A, bisphenol B, bisphenol S, hydrogenated bisphenol A, dibromo bisphenol A, glycerin, trimethylolethane , To Trimethylol propane, polyhydric alcohols such as pentaerythritol.

  In the present invention, the polyol component may contain another polyol (A4) other than (A1) and (A2). The other polyol (A4) is not particularly limited. For example, the polyhydric alcohol and the polyether polyol are not particularly limited. For example, an alkylene derivative of a polyhydric alcohol, polytetramethylene glycol, polythioether polyol and the like Can be mentioned. The polyester polyol and the polyether ester polyol are not particularly limited, and examples thereof include polyhydric alcohols, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, polyether polyols, esters from polyhydric carboxylic acid esters, castor oil polyols, Polycaprolactone polyol etc. are mentioned. The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene polyol, polyisoprene polyol, and hydrogenated polyols thereof. Of these, polyether polyols and polyester polyols are preferred. These can be used alone or in combination of two or more.

  In the present invention, the number average molecular weight of the polyol component is not particularly limited, but is preferably 50 to 10000, more preferably 500 to 5000, from the viewpoint of emulsifiability and emulsion stability.

  In the present invention, the content of (A2) in the polyol component is, from the viewpoint of crosslinking properties, preferably the number of unsaturated bond moles in (A2) / (A) 1000 parts by weight = 0.1 to 3.5. More preferably, 0.2 to 2.5 is more preferable.

  In the present invention, the polyisocyanate component (A3) is not particularly limited, and examples thereof include organic polyisocyanates such as aromatic, aliphatic, alicyclic and aromatic fats. Among them, organic polyisocyanates such as aliphatic, alicyclic and aromatic fats can be easily controlled because the reaction with emulsified water can be easily controlled, and aggregates do not occur at the time of reaction with the polyhydric amine compound (C). The above-mentioned large amount modified products (dimers, trimers, etc.), or a biuret modified product produced by the reaction of the above-mentioned organic polyisocyanate with water is preferable. Organic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate [bis (isocyanonatomethyl) cyclohexane], hexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, xylylene diisocyanate, etc., modified products thereof Is more preferred. Further, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate are more preferable. These can be used alone or in combination of two or more.

  In the present invention, the acid value of the NCO-terminated urethane prepolymer (A) is not particularly limited, but is preferably 7 to 50 mg KOH / g, and more preferably 10 to 30 mg KOH / g. If it is 7 to 50 mg KOH / g, even if the carbonyl group-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomer are mixed, the particle size of the emulsion particle of the NCO group-terminated urethane prepolymer becomes fine, Water-based urethane urea resin chain-extended with the polyvalent amine compound (C), and then, the emulsion particles after polymerization of the carbonyl group-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers are also fine and emulsion stable. It is preferable because it is excellent in the properties. When the acid value is 50 mgKOH / g or less, the viscosity of the prepolymer is suitable, production with no solvent becomes easy, and the water resistance is also good.

  In the present invention, the ratio (molar equivalent ratio) of isocyanate group to hydroxyl group used to obtain an NCO-terminated urethane prepolymer is not particularly limited as long as (isocyanate group: hydroxyl group =) 1.1 or more. The viscosity is preferably 1.5 to 1.0: 1, and more preferably 1.6 to 2.2: 1 because the viscosity of the emulsion is low and a stable emulsion can be obtained. If it is 1.5 molar equivalent or more, the viscosity of the prepolymer is low, and the production of a solvent-free, self-crosslinking aqueous polyurethaneurea-acrylic composite resin composition becomes easy. It is possible to reduce the amount of low viscosity acrylate monomer which may cause the particle diameter of the emulsion to be coarse and the emulsion stability to be reduced, the amount of polyurethaneurea does not decrease, and the flexibility, flexibility, adhesiveness, etc. are good. Become. Below 3.0 molar equivalents, the amount of urea bond does not become too high, and the flexibility, the flexibility, the adhesiveness, etc. become good. In addition, the particle size of the emulsion is fine, and the emulsion stability is also good.

  In the present invention, the average molecular weight of the NCO-terminated urethane prepolymer is preferably 5000 or less, more preferably 4000 or less, from the viewpoint of emulsifiability and emulsion stability. The average molecular weight as referred to herein is a theoretical value calculated from the number average molecular weight of the feed material.

  In the present invention, the ethylenically unsaturated monomer (B) contains a carbonyl group-containing ethylenically unsaturated monomer (B1). The carbonyl group-containing ethylenic unsaturated monomer (B1) is not particularly limited as long as it is an unsaturated monomer having at least one carbonyl group, and examples thereof include acrolein, diacetone (meth) acrylamide, and formylstyrene. And vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, acetoacetoxyethyl methacrylate and the like. Among these, diacetone (meth) acrylamide is preferable from the viewpoint of reactivity and availability. When a water-soluble unsaturated monomer such as diacetone (meth) acrylamide is used, it is possible to start the polymerization after mixing with the emulsion before the start of the polymerization or to perform the polymerization while adding an aqueous solution.

  In the present invention, the ethylenically unsaturated monomer (B) may contain another ethylenically unsaturated monomer (B2) other than (B1). The other ethylenically unsaturated monomer (B2) is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (for example) Alkyl or cycloalkyl (meth) acrylates such as (meth) acrylates, lauryl (meth) acrylates, (iso) stearyl (meth) acrylates, cyclohexyl (meth) acrylates, etc .; polymerization having an isobornyl group such as isobornyl (meth) acrylates Unsaturated compounds, polymerizable unsaturated compounds having an adamantyl group such as adamantyl (meth) acrylate, vinyl aromatic compounds such as styrene, polymerizable unsaturated compounds having an alkoxysilyl group such as vinyltrimethoxysilane and vinyltriethoxysilane A compound, a polymerizable unsaturated compound having a fluorinated alkyl group such as perfluorobutylethyl (meth) acrylate, a polymerizable unsaturated compound having a photopolymerizable functional group such as a maleimide group; a vinyl compound such as N-vinylpyrrolidone Compounds having a carboxyl group such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc., allyl (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylpropane tri (meth ) Acrylates, neopentyl glyco-di (meth) acrylates, 1,6-hexanediol di (meth) acrylates, pentaerythritol di (meth) acrylates, dipentaerythritol hexa (meth) Acrylates-Toglycero-di (meth) acrylates, triallyliso Anure - compounds with polyvalent ethylenically unsaturated group such as bets and the like. In addition, polymerizable unsaturated compounds such as (meth) acrylate having hydroxyl group such as 2-hydroxyethyl (meth) acrylate having hydroxyl group, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate are also available. Use under conditions that do not react with the NCO group of (A) is also possible. In addition, at least one or more ethylenic properties in one molecule such as a polymerizable unsaturated compound having a sulfonic acid group such as a (meth) acrylate having a polyoxyethylene chain whose molecular terminal is an alkoxy group, a styrene sulfonic acid sodium salt, etc. The compound etc. which have an unsaturated group are mentioned. These can be used alone or in combination of two or more depending on the performance desired for the aqueous resin dispersion to be obtained. In addition, low viscosity (meth) acrylate having no active hydrogen atom such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate The compound can be used as a viscosity reducing agent at the time of urethane prepolymer reaction.

  In the present invention, the content (mass ratio) ratio of (B1) and (B2) in the above-mentioned ethylenically unsaturated monomer (B) is (B1): (B2) from the viewpoint of polymerization reactivity and crosslinking characteristics. ) = 100: 0 to 1300 are preferable, and 100: 100 to 700 are more preferable.

  In the present invention, the content (mol) of the carbonyl group-containing ethylenically unsaturated monomer (B1) in 1000 g of the polyurethaneurea-acrylic composite resin (X) is preferably 0.1 to 1.5 mol, More preferably, it is 1.0 mole. If the amount is 0.1 mol or more, the crosslinking effect is good, and if the amount is 1.5 mol or less, the crosslinking effect does not reach a ceiling and the water resistance does not decrease. In addition, the particle size of the emulsion is fine, there is no significant thickening, and the emulsion stability is also good.

  In the present invention, when emulsifying and dispersing (A) and (B) in water, the weight ratio of (A) and (B) is (A) / (B) = 95/5 to 40/60, 95 / 5 to 70/30 is preferable. If it is 95/5 or less, the polymerizability of the ethylenically unsaturated monomer (B) becomes good, and the content of the carbonyl group ethylenically unsaturated monomer (B1) becomes sufficient, and the crosslinking effect becomes good. . If it is 40/60 or more, the amount of polyurethaneurea is sufficient, and the flexibility, the flexibility, the adhesiveness, etc. become good. In addition, the particle size of the obtained emulsion is fine even without the surfactant, and the emulsion stability is also good.

  In the present invention, when (A) and (B) are emulsified and dispersed in water, substantially no emulsifier such as nonionic surfactant, anionic surfactant and cationic surfactant is contained. preferable. By not using a surfactant, excellent water resistance and solvent resistance can be obtained. Here, "not substantially contained" means 0.50% by weight or less based on the total weight of (A) and (B), but it is preferable not to contain at all.

  The polyhydric amine compound (C) in the present invention is not particularly limited, and examples thereof include hydrazides and polyamines. The hydrazides are not particularly limited, and examples thereof include hydrazine and adipic acid hydrazide. Examples of the polyamines include, but are not limited to, ethylene diamine, propylene diamine, hexylene diamine, isophorone diamine, xylylene diamine, piperazine, diphenylmethane diamine, ethyl tolylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, and tetraethylene tetramine. Ethylene pentamine and the like can be mentioned. These can be used alone or in combination of two or more.

  In the present invention, to polymerize (A) and (B) means to polymerize the ethylenically unsaturated monomer contained in (A) and (B). When polymerizing (A) and (B), it is preferable to use a polymerization initiator. The polymerization initiator is not particularly limited, and examples thereof include oil-soluble and water-soluble polymerization initiators. The oil-soluble polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as benzoyl peroxide, and azobisisobutyronitrile. The water-soluble polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as cumene hydroperoxide and tert-butyl peroxide, azo compounds such as azobis (2-methylpropionnitrile), and potassium persulfate And persulfates such as ammonium persulfate and sodium persulfate. These can be used alone or in combination of two or more. In addition, the above-mentioned polymerization initiator can be used in combination with a reducing agent such as sugar, sodium formaldehyde sulfoxylate, sodium sulfite or the like, if necessary. The amount of the polymerization initiator used is preferably in the range of 0.01 to 1% by weight, particularly 0.02 to 0.5% by weight based on the amount of the polyurethaneurea-acrylic composite resin (X) to be obtained.

  It is also a preferable embodiment to mix a hydrazide compound (D) having at least two or more hydrazide groups in the polyurethane urea-acrylic composite resin of the present invention. By mixing (D), polyurethaneurea-acrylic composite resin (X) water dispersion can be obtained which dramatically improves the water resistance and solvent resistance due to the crosslinking property and is also excellent in emulsion stability. .

In the present invention, the hydrazide compound (D) having at least two or more hydrazide groups is not particularly limited as long as it is a compound having two or more hydrazide groups in one molecule, and examples thereof include oxalic acid dihydrazide and malonic acid dihydrazide. , Adipic acid dihydrazide, azelaic acid dihydrazide, succinic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, carbohydrazide, dodecane Examples include geohydrazide and isophthalic acid dihydrazide. Also, polyurethane prepolymer having -NHNH ₂ group at the molecular end, which is obtained by reacting a compound having two or more hydrazide groups in one molecule or hydrazine with a polyurethane prepolymer having a molecular terminal free isocyanate group is also obtained. It can be used. These can be used alone or in combination of two or more.

  The mixing amount of the hydrazide compound (D) having two or more hydrazide groups in the present invention is not particularly limited, and, for example, 1 mole of the carbonyl group contained in (X) in the polyurethaneurea-acrylic composite resin On the other hand, 0.3 to 1.3 mol of a hydrazide group is preferable, and 0.5 to 1.0 mol is more preferable. If it is 0.3 mol or more, crosslinking will be sufficient and water resistance and chemical resistance will be good. If it is 1.3 mol or less, water resistance and chemical resistance become good, and the unreacted hydrazide compound does not bleed out.

  As a method for producing an aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention, at least (A) / (B) = 95/5 to 40/60 (weight ratio) (A) and The process of emulsifying and dispersing (B) in water, the process of chain extension with a polyhydric amine compound (C), and the process of polymerizing (A) and (B) are included.

  It does not specifically limit as a stirring apparatus in the process of carrying out emulsification dispersion | distribution of this invention in water. If it is a low viscosity NCO-terminated prepolymer, a conventional stirring apparatus can be preferably used without requiring high shear force, and if it is a high viscosity NCO-terminated prepolymer, a disperser having high energy shearing ability, for example, a high pressure homogenizer And in-line rotor-stator type mixers are preferably used.

  In the present invention, in order to obtain the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin, although not particularly limited, it is preferable not to use the organic solvent substantially. By not using an organic solvent, an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin can be economically obtained. Here, "not substantially contained" means 0.5 wt% or less based on the total of the weight of (A) and (B), but it is preferable not to include at all.

  The temperature of the NCO-terminated urethane prepolymer used in the step of emulsifying and dispersing in water of the present invention is not particularly limited, but is preferably 80 ° C. or less, and more preferably 60 ° C. or less.

  Although it does not specifically limit as a process to chain-extend with a polyhydric amine compound (C) in this invention, It is preferable to chain-extend while adding the aqueous solution of a polyhydric amine compound (C) gradually.

  The addition method of the polymerization initiator in the step of polymerizing (A) and (B) in the present invention is not particularly limited, and may be added to the pre-emulsification prepolymer, but in the water-soluble initiator, It is preferred to add as an aqueous solution.

  The polymerization temperature in the step of polymerizing (A) and (B) in the present invention is not particularly limited, but is, for example, preferably 80 ° C. or less, more preferably 60 ° C. or less. When the temperature exceeds 80 ° C., the emulsion aggregates. In addition, addition of an initiator and a reducing agent is required to gradually add a dilute aqueous solution so that the emulsion does not aggregate.

  The weight of the non-volatile component in the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention is economical and stable when the value measured according to JIS K 6828 is 15 to 60%. It is preferable from the viewpoint.

  The viscosity of the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention is BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 20 ° C. from the viewpoint of emulsion stability and usability. It is preferable that the value measured according to JISZ8803 is 5 to 3000 (20 ° C. mPa · s).

  The particle diameter of (X) in the aqueous dispersion of (X) in the polyurethane urea-acrylic composite resin of the present invention is 50% as measured by Microtrac UPA-UZ 152 (manufactured by Nikkiso Co., Ltd.) from the viewpoint of emulsion stability. The value calculated using the average value as the particle diameter is preferably 0.6 μm or less.

  The emulsion stability of (X) in the polyurethaneurea-acrylic composite resin of the present invention is preferably such that there is no viscosity change or sedimentation in the method described in the examples.

  The water resistance of the cured product of the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention is preferably 150% or less, more preferably 50% or less, in the method described in the examples. Further, it is preferable that the amount of swelling and tackiness is small, and whitening and decrease in strength are also small.

  The MEK resistance of the cured product of the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention is preferably 300% or less, more preferably 200% or less in the method described in the examples. In addition, it is preferable that there is less swelling and tack and less decrease in strength.

  In the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention, a filler, a flame retardant, an antifoaming agent, an antifungal agent, an antirust agent, and a stability are possible within the range not inhibiting the effect of the present invention Additives can be included such as agents, plasticizers, thickeners, mildewproofing agents, and other aqueous dispersion resins.

  Hereinafter, the aqueous dispersion of (X) in the polyurethaneurea-acrylic composite resin of the present invention will be described in detail based on Examples and Comparative Examples. The present invention is not limited to these examples. In the present specification, “parts” and “%” represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.

Example 1
Charge 600 parts of unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 43 parts of dimethylol propionic acid, 357 parts of isophorone diisocyanate, and react at a temperature of 90 ° C for 60 minutes. Thus, a urethane prepolymer having an isocyanate group content of 6.7% and a carboxyl group acid value of 18 mgKOH / g was obtained. 100 parts of methyl methacrylate and 50 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., 32.5 parts of triethylamine is mixed, and then 2000 parts of emulsified water (20 ° C.) are charged to obtain Homomixer (Plymix Co., Ltd. The mixture was emulsified with a homomixer MARKII). Next, an aqueous solution prepared by diluting 43 parts of ethylene diamine in 170 parts of water was charged to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 2 parts of tert-butyl peroxide in 50 parts of water was charged, and then an aqueous solution prepared by diluting 2 parts of sodium sulfite in 50 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 2)
Charge 600 parts of unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 43 parts of dimethylol propionic acid, 357 parts of isophorone diisocyanate, and react at a temperature of 90 ° C for 60 minutes. Thus, a urethane prepolymer having an isocyanate group content of 6.7% and a carboxyl group acid value of 18 mgKOH / g was obtained. 200 parts of methyl methacrylate and 100 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., 32.5 parts of triethylamine is mixed, and then 2000 parts of emulsified water (20 ° C.) are charged. The mixture was emulsified with a homomixer MARKII). Next, an aqueous solution prepared by diluting 43 parts of ethylene diamine in 170 parts of water was charged to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 2 parts of tert-butyl peroxide in 50 parts of water was charged, and then an aqueous solution prepared by diluting 2 parts of sodium sulfite in 50 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 3)
266 parts of unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 355 parts of polyester polyol (number average molecular weight 2000) consisting of 3-methyl-1,5-pentanediol and adipic acid 47 parts of dimethylol propionic acid and 332 parts of isophorone diisocyanate were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 6.2% and a carboxyl group acid value of 19.9 mg KOH / g. 100 parts of methyl methacrylate and 100 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., 36 parts of triethylamine is mixed, 2000 parts of emulsified water (20 ° C.) are charged, and homomixer (Plymix Co., Ltd. The mixture was emulsified with a homomixer MARKII). Next, an aqueous solution prepared by diluting 43 parts of ethylene diamine in 170 parts of water was charged to increase the molecular weight. The obtained emulsion is cooled to 30 ° C., and an aqueous solution prepared by diluting 1.5 parts of tert-butyl peroxide in 50 parts of water is charged, and then an aqueous solution prepared by diluting 1.5 parts of sodium sulfite in 50 parts of water is charged and polymerization is initiated did. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 4)
216 parts unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 415 parts difunctional propylene glycol (number average molecular weight 2000), 46.4 parts dimethylol propionic acid, 323 parts isophorone diisocyanate And reacted for 60 minutes at a temperature of 90.degree. C. to obtain a urethane prepolymer having an isocyanate group content of 6.1% and a carboxyl group acid value of 19.6 mg KOH / g. 100 parts of 1,6-hexanediol diacrylate and 100 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, and after cooling to 60 ° C., 35 parts of triethylamine is mixed and then 1800 parts of emulsified water (20 ° C.) is charged The mixture was mixed and emulsified with a homomixer (homomixer MARKII manufactured by Primix). Next, an aqueous solution prepared by diluting 41 parts of ethylene diamine with 200 parts of water was charged to obtain high molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 2 parts of tert-butyl peroxide in 50 parts of water was charged, and then an aqueous solution prepared by diluting 2 parts of sodium sulfite in 50 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 5)
Unsaturated polyester polyol consisting of 1,6-hexanediol, fumaric acid and adipic acid (number average molecular weight 2000 maleic anhydride / adipic acid = 1/1 molar ratio) 3313 parts, bifunctional propylene glycol (number average molecular weight 2000) 331 Parts, 44.4 parts of dimethylol propionic acid and 294 parts of isophorone diisocyanate are charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.5% and a carboxyl group acid value of 18.6 mg KOH / g. The 100 parts of 2-ethylhexyl acrylate and 100 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., 34 parts of triethylamine is mixed, and then 1800 parts of emulsified water (20 ° C.) The mixture was mixed and emulsified in a homomixer MARKII manufactured by Primix. Next, an aqueous solution prepared by diluting 36 parts of ethylene diamine in 200 parts of water was charged to obtain high molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 2 parts of tert-butyl peroxide in 50 parts of water was charged, and then an aqueous solution prepared by diluting 2 parts of sodium sulfite in 50 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 6)
Unsaturated polyester polyol (number average molecular weight 2000) composed of 1,6-hexanediol and maleic anhydride 331 parts, bifunctional propylene glycol (number average molecular weight 2000) 331 parts, dimethylol propionic acid 44.4 parts, isophorone diisocyanate Then, 294 parts were charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.5% and a carboxyl group acid value of 18.6 mg KOH / g. After mixing and dissolving 200 parts of methyl methacrylate and 100 parts of diacetone acrylamide in the obtained urethane prepolymer and cooling to 60 ° C., 34 parts of triethylamine is mixed, and then 1800 parts of emulsified water (20 ° C.) is charged to prepare a homomixer (Plymix Co., Ltd. The mixture was emulsified with a homomixer MARKII). Next, an aqueous solution prepared by diluting 36 parts of ethylene diamine in 200 parts of water was charged to obtain high molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 2 parts of tert-butyl peroxide in 50 parts of water was charged, and then an aqueous solution prepared by diluting 2 parts of sodium sulfite in 50 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 7)
222 parts unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 366 parts bifunctional propylene glycol (number average molecular weight 2000), 47.8 parts dimethylol propionic acid, 4,4 ' -374 parts of dicyclohexylmethane diisocyanate was charged and reacted at a temperature of 90 ° C for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 5.9% and a carboxyl group acid value of 20.0 mgKOH / g. After mixing and dissolving 500 parts of methyl methacrylate and 100 parts of diacetone acrylamide in the obtained urethane prepolymer and cooling to 60 ° C., 36 parts of triethylamine is mixed and then 2200 parts of emulsified water (20 ° C.) are charged to prepare a homomixer (Plymix Co., Ltd. The mixture was emulsified with a homomixer MARKII). Next, an aqueous solution prepared by diluting 40 parts of ethylene diamine with 200 parts of water was charged to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 4 parts of tert-butyl peroxide with 100 parts of water was charged, and then an aqueous solution prepared by diluting 4 parts of sodium sulfite with 100 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Example 8)
222 parts unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 366 parts bifunctional propylene glycol (number average molecular weight 2000), 47.8 parts dimethylol propionic acid, 4,4 ' 524 parts of dicyclohexylmethane diisocyanate was charged and reacted at a temperature of 90 ° C. for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 9.2% and a carboxyl group acid value of 17.4 mg KOH / g. 100 parts of methyl methacrylate and 50 parts of diacetone acrylamide are mixed and dissolved in the obtained urethane prepolymer, cooled to 60 ° C., 36 parts of triethylamine is mixed, 2800 parts of emulsified water (20 ° C.) are charged, and homomixer (Plymix Co., Ltd. The mixture was emulsified with a homomixer MARKII). Next, an aqueous solution prepared by diluting 40 parts of ethylene diamine with 200 parts of water was charged to increase the molecular weight. After cooling the obtained emulsion to 30 ° C., an aqueous solution prepared by diluting 4 parts of tert-butyl peroxide with 100 parts of water was charged, and then an aqueous solution prepared by diluting 4 parts of sodium sulfite with 100 parts of water was charged and polymerization was initiated. The mixture was then reacted at a temperature of 50 ° C. for 30 minutes to obtain an aqueous dispersion of (X) in a polyurethaneurea-acrylic composite resin.

(Comparative example 1)
305 parts of unsaturated polyester polyol (number average molecular weight 1250) consisting of 1,6-hexanediol and maleic anhydride, 314 parts of bifunctional polypropylene glycol (number average molecular weight 2000), 46.9 parts of dimethylol propionic acid, 334 parts of isophorone diisocyanate And reacted at a temperature of 90.degree. C. for 60 minutes to obtain a urethane prepolymer having an isocyanate group content of 6.3% and a carboxyl group acid value of 19.6 mg KOH / g. The obtained urethane prepolymer was cooled down to 60 ° C., 35 parts of triethylamine was mixed, 1500 parts of emulsified water (20 ° C.) was charged, and mixed and emulsified with a homomixer (homomixer MARKII manufactured by Primix, Inc.). Next, an aqueous solution in which 35 parts of ethylene diamine was diluted in 170 parts of water was charged to increase the molecular weight.

(Examples 9 to 16)
The aqueous dispersion of (X) in the polyurethaneurea composite resin shown in Examples 1 to 9 was mixed with the adipic acid hydrazide in the amount shown in Table 1 and sufficiently dissolved.

(How to make a test piece)
The aqueous dispersion of (X) in the obtained polyurethaneurea-acrylic composite resin is charged into a Teflon (registered trademark) -coated petri dish to have a film thickness of 200 μm, and dried at 20 ° C. for 3 days to prepare a test piece did.

(Evaluation method)
Urethane prepolymer temperature: The temperature immediately before emulsification was measured.
Weight of nonvolatile content: Measured according to JIS K 6828.
Viscosity: Measured at 20 ° C. using a B8M viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to JIS Z8803.
Particle size: Measured by Microtrac UPA-UZ152 (manufactured by Nikkiso Co., Ltd.), and the 50% average value was calculated as the particle size.

(Emulsification stability)
The emulsion stability was confirmed by storing for 30 days in a 40 ° C. thermostat.

(water resistant)
An evaluation sample was produced by cutting the test film into a predetermined size (2 cm × 4 cm). Tap water was used as a test solution. The test piece was immersed in a test solution at 20 ° C. for 4 hours, and the weight increase rate with respect to the initial weight was determined by the following equation.
Weight increase rate = (weight after immersion-initial weight) / initial weight x 100

(MEK resistance)
An evaluation sample was produced by cutting the test film into a predetermined size (2 cm × 4 cm). MEK was used as a test solution. The test piece was immersed in a test solution at 20 ° C. for 4 hours, and the weight increase rate with respect to the initial weight was determined by the following equation.
Weight increase rate = (weight after immersion-initial weight) / initial weight x 100

<Evaluation result>
As can be seen from Examples 1 to 16, the aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention is a coating having good emulsion stability and obtained substantially without using an organic solvent and a surfactant. It can be seen that the water resistance and solvent resistance of the above are also good.

On the other hand, when the polymerization step was not performed without B as in Comparative Example 1, the swelling of the MEK resistance was large and poor.

The aqueous dispersion of the polyurethaneurea-acrylic composite resin of the present invention is remarkably excellent in water resistance and solvent resistance due to the excellent crosslinking property by blending the hydrazide compound with the carbonyl group-containing aqueous polyurethaneurea-acrylic composite resin composition. The emulsion stability is also excellent. In addition, the water resistance and solvent resistance are further improved by not using a surfactant, and further, even without using an organic solvent, the particle diameter is fine and the storage stability is excellent, and the self-crosslinkable water-based urethane is excellent. Since a urea resin composition can be produced and no organic solvent is used, the productivity is also excellent. Due to such properties, it is widely and suitably used in fields where conventional water-based polyurethane resins are used, adhesives, coatings, paints, modifiers, binders and the like.

Claims (6)

After emulsifying and dispersing (A) and (B) at least (A) / (B) = 95/5 to 40/60 (weight ratio) in water, chain elongation is carried out with the polyhydric amine compound (C),
Further obtained by polymerizing (A) and (B),
Aqueous dispersion of polyurethane urea composite resin (X).
(A) A polyol component containing an active hydrogen group-containing anionic salt forming group-containing compound (A1) and an unsaturated polyester polyol (A2) having at least two or more hydroxyl groups, and a polyisocyanate component (A3) The obtained NCO-terminated urethane prepolymer (B) acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl ethyl ketone, vinyl butyl ketone, and acetoacetoxyethyl methacrylate Ethylenically unsaturated monomer containing (B1)   The NCO-terminated urethane prepolymer (A) is obtained by reacting an isocyanate group and an active hydrogen group by (isocyanate group: active hydrogen group =) 1.5 to 3.0: 1 (molar equivalent ratio) An aqueous dispersion of polyurethane urea composite resin (X) according to claim 1.   The ionic salt forming group of the active hydrogen group-containing anionic salt forming group-containing compound (A1) is a carboxyl group, and the acid value of the NCO-terminated urethane prepolymer (A) is 7 to 50 mg KOH / g. Or the water dispersion of polyurethane urea composite resin (X) of 2 statement. Furthermore, at least an amount such that the hydrazide group is 0.3 to 1.3 mol with respect to 1 mol of the carbonyl group of the ethylenically unsaturated monomer (B1) contained in the polyurethane urea composite resin (X 2 ) Obtained by mixing a hydrazide compound (D) having two or more hydrazide groups,
The aqueous dispersion of polyurethane urea composite resin (X) in any one of Claims 1-3.   The aqueous dispersion of polyurethaneurea composite resin (X) according to any one of claims 1 to 4, which is produced substantially without solvent and without using a surfactant. Emulsifying and dispersing (A) and (B) at least (A) / (B) = 95/5 to 40/60 (weight ratio) in water,
Chain extension with a polyvalent amine compound (C),
Including the step of polymerizing (A) and (B),
The manufacturing method of the water dispersion of polyurethane urea complex resin (X).
(A) A polyol component containing an active hydrogen group-containing anionic salt forming group-containing compound (A1) and an unsaturated polyester polyol (A2) having at least two or more hydroxyl groups, and a polyisocyanate component (A3) The obtained NCO-terminated urethane prepolymer (B) acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl ethyl ketone, vinyl butyl ketone, and acetoacetoxyethyl methacrylate Ethylenically unsaturated monomer containing (B1)