JPWO2006104094A1 - Aqueous polyurethane resin composition and method for producing the same - Google Patents

Abstract

[PROBLEMS] To develop a method of using a polyamine in an aqueous polyurethane resin composition so that the gelation time is extended even at room temperature curing than in the case of using a diol compound, and the strength and water resistance and solvent resistance are excellent. Develop polyurethane resin paints or adhesives that provide excellent physical properties. As a component (A), (a) a diisocyanate compound, (b) a compound having a terminal hydroxyl group, a carbon-carbon unsaturated bond and an adjacent carbonyl group, (c) a fatty acid having an active hydrogen group, and (d ) A resin reacted with a polyol compound, an aqueous polyamine resin containing an amine residue by a urea reaction and a Michael addition reaction after neutralization, and a polyisocyanate compound dispersible in the component (A) as the component (B) An aqueous polyurethane resin composition, comprising:

Description

The present invention relates to an aqueous polyurethane resin composition and a method for producing the same.
By using a polyamine compound in a specific embodiment, the gelation time can be extended, and even at room temperature curing, high strength and excellent water resistance, solvent resistance, etc. can be expressed. It relates to paints and adhesives.

Polyurethane resin compositions are widely used as paints, adhesives, various molding materials for industrial materials, etc., but because the application fields are very wide, improvements in various performances and physical properties are always required. Improvement and development of catalysts and functions continue.
In the polyurethane resin composition as a composition for paints and adhesives, an aqueous (aqueous) composition that does not use an organic solvent is preferable from the viewpoint of environmental friendliness and workability, and economically because no organic solvent is used. In an advantageous aqueous polyurethane resin composition, effective use of a polyamine as a chain extender has long been used in order to obtain various physical properties such as water resistance and solvent resistance equivalent to those of an organic solvent-based composition. Widely used (see, for example, Patent Document 1).

  And in the use of polyamines in aqueous paints or adhesive compositions, using Michael addition reaction with α, β-unsaturated carbonyl compounds, the reaction with isocyanate groups is controlled by changing primary amines to secondary amines. It is also known to use an unsaturated oligoester as an α, β-unsaturated carbonyl compound, extending the service life (pot life), quick-drying and good in water resistance (Patent Document 2) ), A coating (Patent Document 3) that provides high film strength with radiation fast curing using a hydroxy group-containing prepolymer having an α, β-ethylenically unsaturated double bond and a diamine, etc. There is also known a pressure-sensitive adhesive that is non-aqueous but has a high removability by a urethane urea resin using Michael addition by polyamine (Patent Document 4).

JP 7-268208 A (summary) Japanese Patent Laid-Open No. 10-81746 (summary, paragraphs 0003 and 0004) JP 11-315130 A (Summary, paragraph 0014) JP 2001-192636 A (summary, paragraph 0071)

  The present invention uses a Michael addition reaction with an α, β-unsaturated carbonyl compound in the use of a polyamine in an aqueous paint or adhesive composition as described in paragraph 0003, thereby converting a primary amine to a secondary amine. In order to control the reaction with the isocyanate group, the improvement method of the polyurethane resin composition is developed, and the gelation time is extended even at room temperature curing than when the diol compound is used, resulting in high strength, water resistance and resistance. It is an object of the present invention to develop a polyurethane resin paint or an adhesive that provides excellent physical properties such as solvent properties.

The inventors of the present invention aim at solving the above-mentioned problems by using a Michael addition reaction with an α, β-unsaturated carbonyl compound when using a polyamine in an aqueous polyurethane resin composition. In order to develop a polyurethane resin composition improvement method that controls the reaction with isocyanate groups by changing amines to secondary amines, the selection of raw materials such as polyamines and α, β-unsaturated carbonyl compounds or Michael addition The reaction conditions, polymerization conditions, water-solubilization of the composition, composition ratio, etc. were considered from various viewpoints and experimented repeatedly.
In those processes, a compound having a terminal hydroxyl group, a carbon-carbon unsaturated bond and an adjacent carbonyl group is selected, and the compound is pre-incorporated into the polyurethane prepolymer before the reaction with the polyamine, and the water dispersibility is increased. Recognizing that it is effective to incorporate fatty acids having active hydrogen groups into the prepolymer in order to increase it, reacting them with diisocyanate compounds and polyol compounds to produce urethane prepolymers, and neutralizing with tertiary amines The present invention was newly created and constructed by processing, then adding a polyamine, performing a urea reaction and a Michael addition reaction, and performing a crosslinking reaction with a polyfunctional polyisocyanate curing agent.

More specifically, as a preferred embodiment, the diisocyanate compound is an aliphatic diisocyanate compound, and the compound having a terminal hydroxyl group and having an intercarbon unsaturated bond and an adjacent carbonyl group has a molar ratio of 50% or more with respect to the diisocyanate compound. It is a (meth) acrylate compound, the fatty acid having an active hydrogen group is dimethylol fatty acid, the polyol compound is a polyester diol (including polycarbonate diol) or a polyether diol having a number average molecular weight of 800 to 6,000, and a urea reaction And the amine residue obtained by Michael addition reaction is a primary and / or secondary amino residue and is contained in the resin solid content in an amount of 0.2 to 3.0 mmol / g, and the active component molar ratio of [NCO] / [NH] is An aqueous polyurethane resin composition configured to be 1.5 to 6.0 .
Additionally, the aqueous polyurethane resin composition is a two-component coating composition or a two-component adhesive composition, and the coating composition is a two-component assembly material of a water-based polyamine resin and a polyisocyanate as a curing catalyst, An aqueous polyurethane resin coating composition in which two components are mixed when used as a coating.

  As a method for producing the aqueous polyurethane resin composition of the present invention, a diisocyanate compound having a molar ratio of 50% or more, a compound having a terminal hydroxyl group, a carbon-carbon unsaturated bond and an adjacent carbonyl group, and an active hydrogen group are used. Is reacted with a fatty acid-containing polyol compound and a polyol compound to form a terminal isocyanate prepolymer, neutralized with a tertiary amine, dispersed in an aqueous solution containing a primary amine compound, urea reaction with an isocyanate residue, and carbon A polyisocyanate cure that can be dispersed in the water-based polyamine resin component by producing a water-based polyamine resin containing primary and / or secondary amine residues by performing a Michael addition reaction between a compound having an intersaturated bond and an adjacent carbonyl group. It can manufacture by becoming a composition with an agent component.

  By the way, in patent document 2 which is a prior art described in paragraph 0003, an unsaturated oligoester is used as an α, β-unsaturated carbonyl compound when polyamine is used for improving the physical properties of a coating composition such as a paint. Using a Michael addition (Michael addition) reaction, the primary amine is changed to a secondary amine to control the reaction with the isocyanate group, but an unsaturated oligoester or the like and an aliphatic diamine are reacted in advance. In addition, in Patent Document 3, it is a radiation curable paint using a hydroxy group-containing prepolymer having an α, β-ethylenically unsaturated double bond, a diamine, etc. In the present invention, (a) the diisocyanate compound has (b) a terminal hydroxyl group and an intercarbon unsaturated bond and an adjacent carbonyl. (C) a prepolymer obtained by reacting a fatty acid having an active hydrogen group and (d) a polyol compound, a polyamine was reacted after neutralization to form an amine residue by urea reaction and Michael addition reaction. Since it is a water-based polyurethane resin, it can be said that the present invention is basically an invention that basically differs in configuration from the prior art inventions in Patent Documents 2 and 3, although only a part thereof is approximated.

  The present invention created as described above is clearly described as a whole. The present invention is composed of the following invention unit groups, and the invention of [1] is the basic invention, and the following The invention embodies or embodies the basic invention. (The invention group as a whole is collectively referred to as “the present invention”.)

[1] As the component (A), (a) a diisocyanate compound (b) a compound having a terminal hydroxyl group, a carbon-carbon unsaturated bond and an adjacent carbonyl group, (c) a fatty acid having an active hydrogen group, and (d) A resin obtained by reacting a polyol compound, an aqueous polyamine resin containing an amine residue by a urea reaction and a Michael addition reaction after neutralization, and a polyisocyanate compound dispersible in the component (A) as the component (B) An aqueous polyurethane resin composition characterized by containing.
[2] (a) The diisocyanate compound is an aliphatic diisocyanate compound, and (b) a compound having a terminal hydroxyl group and having a carbon-carbon unsaturated bond and an adjacent carbonyl group has a molar ratio of 50% or more with respect to (a). A (meth) acrylate compound having a terminal hydroxyl group, (c) a fatty acid having an active hydrogen group is dimethylol fatty acid, and (d) a polyester diol having a number average molecular weight of 800 to 6,000 (polycarbonate diol). Or amine diols by urea reaction and Michael addition reaction are primary and / or secondary amino residues, and 0.2 to 3.0 mmol / g in the resin solid content, Aqueous polyurethane resin according to [1], wherein the active ingredient molar ratio of NCO] / [NH] is 1.5 to 6.0 Composition.
[3] The aqueous polyurethane resin composition, wherein the aqueous polyurethane resin composition in [1] or [2] is a two-component paint composition or a two-component adhesive composition.
[4] The coating composition is a two-component assembly material of a water-based polyamine resin as component (A) and a polyisocyanate as a curing agent for component (B), and the two components are mixed when used as a coating material. The aqueous polyurethane resin coating composition according to [3], wherein
[5] As the component (A), (a) a compound having a terminal hydroxyl group and a carbon-carbon unsaturated bond and an adjacent carbonyl group in the diisocyanate compound (b) and (a) in a molar ratio of 50% or more. And (c) a fatty acid having an active hydrogen group and (d) a polyol compound are reacted to form a terminal isocyanate prepolymer, neutralized with a tertiary amine, and dispersed in an aqueous solution having a primary amine compound. A water-based polyamine resin containing a primary and / or secondary amine residue is produced by a urea reaction with an isocyanate residue and a Michael addition reaction with a compound having an unsaturated bond between carbon and an adjacent carbonyl group, and then (A) A method for producing an aqueous polyurethane resin composition according to [1] or [2], wherein the composition is a composition with a polyisocyanate compound of component (B) dispersible in the component .

  In the present invention, in the use of a polyamine in an aqueous polyurethane resin composition, a primary amine is changed to a secondary amine using a Michael addition reaction with an α, β-unsaturated carbonyl compound having a terminal hydroxyl group, and an isocyanate group is converted into a secondary amine. By controlling the reaction, the gelation time is extended and the appearance is better than when using a diol compound even at room temperature curing, and it is possible to form a coating with high strength and excellent water resistance and solvent resistance. It can be used as a useful and excellent polyurethane resin paint or adhesive.

  Although the present invention has been described in accordance with the basic configuration of the present invention as means for solving the problems, the embodiments of the invention of the present invention group described above will be described in detail below. .

1. Raw Material of Aqueous Polyurethane Resin Composition (1) Diisocyanate Compound As the diisocyanate component used in the present invention, an organic diisocyanate compound is used, and a normal one as a raw material of polyurethane resin is used, and is not particularly defined. . In order to avoid yellowing of the coating film due to ultraviolet rays, aliphatic or alicyclic diisocyanates are preferred over aromatic diisocyanates.
Specifically, allophanate-modified polyisocyanate obtained from hexamethylene diisocyanate and monool having 1 to 6 carbon atoms, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methyl Examples include aliphatic diisocyanates such as pentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, and isophorone diisocyanate. , Cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethylxylylene diisocyanate, etc. Sulfonate are exemplified. These diisocyanates are used individually by 1 type or in mixture of 2 or more types.
Furthermore, these adduct modified products, carbodiimide modified products, allophanate modified products, burette modified products, uretdione modified products, uretoimine modified products, isocyanurate modified products, and the like can also be used.

(2) Compound having a terminal hydroxyl group and having an unsaturated bond between carbon and an adjacent carbonyl group Since this compound has a hydroxyl group at the terminal, it is bonded to the terminal of the urethane prepolymer by the hydroxyl group, and the carbon-carbon double bond A diamine or triamine is Michael added to form a prepolymer end.
A carbonyl group is a broad term including a C═O group derived from a carboxyl group. The terminal hydroxyl group does not mean —OH in the carboxyl group.
A typical example of the compound is a terminal-hydroxy (meth) acrylate compound as an α, β-unsaturated carbonyl compound having a terminal hydroxyl group.
Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di (meth) acrylate, 2-hydroxy -3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, and the like, such as acrylic glycidyl ether, allyl glycidyl ether, glycidyl (meth) And a glycidyl group-containing compounds such as acrylates, are also exemplified compounds obtained by addition reaction of (meth) acrylic acid.

(3) Fatty acid having an active hydrogen group This fatty acid has an active hydrogen group. For example, active hydrogen groups at both ends react with isocyanate groups and are incorporated into the main chain of the prepolymer, and free carboxyl groups are hydrophilic. Therefore, it acts to increase the water dispersibility of the prepolymer.
Examples of the fatty acid compound having an active hydrogen group include dimethylolpropionic acid and dimethylolbutanoic acid having two terminal hydroxyl groups, other reaction products of polyamine and acid anhydride, dimethylolpropionic acid and dimethylol. Also included are lactone adducts using butanoic acid as an initiator.
As the fatty acid, dimethylolpropionic acid and dimethylolbutanoic acid are preferable.

(4) Polyol compound The polyol compound in the present invention includes a diol compound and a triol compound. As the polyol component used in the present invention, a polyester polyol (including polycarbonate diol) or a polyether polyol is used. Are used as usual raw materials for polyurethane resins, and are not particularly defined.
Those having a number average molecular weight of 800 to 6,000 are preferred, and representative examples include polypropylene ethylene polyol (PPG), polytetramethylene ether glycol (PTG), polytetramethylene glycol (PTMG) and the like.

More specifically, polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, malonic acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, kurtaconic acid, Azelaic acid, 1,4-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylmuconic acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, other dibasic 1 type or 2 types or more, such as an acid, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3 Methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol It can be obtained by polycondensation reaction of A with adducts such as ethylene oxide and propylene oxide, bis (β-hydroxyethyl) benzene, xylylene glycol, other diols, or polyols such as glycerin, trimethylolpropane and pentaerythritol. Polyester polyol is used.
Furthermore, lactone-based polyester polyols obtained by ring-opening polymerization of monomers such as cyclic esters (lactones) such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone are also mentioned. A polyester amide polyol obtained by changing a part of the low molecular polyol to a low molecular amine such as hexamethylene diamine, isophorone diamine or monoethanolamine, or a low molecular amino alcohol can also be used.

  As the polyether polyol, two or more active hydrogen groups such as the above diols and polyols, or amines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine are used. Preferably, a compound having 2 to 3 compounds is used as an initiator, alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, alkyl or aryl glycidyl ethers such as methyl glycidyl ether and phenyl glycidyl ether, and cyclic ethers such as tetrahydrofuran A polyether polyol obtained by addition polymerization of one kind or two or more kinds of monomers is used.

  As the polycarbonate polyol, a polycarbonate polyol obtained by the reaction of the low molecular diols or low molecular triols described in paragraph 0017 with ethylene carbonate, diethyl carbonate, diphenyl carbonate or the like is used. A polyol obtained by transesterification between a polycarbonate polyol and a polyester polyol can also be suitably used.

  In addition, copolyols obtained from polyether polyols and dicarboxylic acids, and polyether ester polyols obtained by reaction of polyesters and polycarbonates with epoxides and cyclic ethers can also be used, and polybutadiene having two or more hydroxyl groups, Polyolefin polyols such as hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene may also be used.

(5) Diamine or polyamine compound The diamine or polyamine compound is used as a chain extender for the prepolymer,
Rather than using a diol compound as a chain extender, it is more easily crosslinked, which is advantageous in terms of physical properties such as water resistance, solvent resistance and stain resistance.
Use of diamines or triamine compounds instead of diols as reactive agents that react with diisocyanate compounds prevents the formation of prepolymers due to the high reactivity of these amine compounds, so these amine compounds are used as chain extenders for prepolymers. To do.
Specific examples of these amine compounds, ethylenediamine diamine (EDA), isophorone diamine (IPDA) is illustrated in the _{polyamine, H 2 N- (C 2 H} 4 NH) n -C 2 H 4 NH 2 (n = 1-8), diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like are exemplified.

(6) Curing catalyst and curing agent Resinization catalyst (urethanization catalyst) as a curing catalyst (polymerization catalyst) for urethane reaction is used as necessary, and is a metal catalyst such as dibutyltin dilaurate or zinc naphthenate or triethylenediamine. Ordinary curing catalysts such as amine catalysts such as N-methylmorpholine are used, and the reaction rate can be increased and the reaction temperature can be lowered.
As a curing agent for curing a polyurethane resin, one molecule derived from hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) is used as one liquid in a two-component system (two-component composition) in the present invention. A trimer or adduct having 3 or more NCO groups is used. Specific examples include urethane-modified products, urea-modified products, allophanate-modified products, burette-modified products, uretdione-modified products, and isocyanurate-modified products of organic diisocyanates.
In the isocyanurate modified type curing agent derived from hexamethylene diisocyanate (HDI), it is preferable that the molar ratio of NCO of the curing agent / NH of the main component is 2.5 to 4.5.

(7) Other auxiliaries In the present invention, in addition to the polyamine compound described in paragraph 0018, a chain extender in a usual polyaddition reaction may be used as necessary.
As the chain extender, an ordinary low-molecular compound having two or more active hydrogen groups is used. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neo Pentyl glycol, diethanolamine, triethanolamine, HDI isocyanurate modified, diisocyanate allophanate modified, and the like are used.
In order to enhance physical properties and add various physical properties, various additives such as flame retardants, plasticizers, antioxidants, ultraviolet absorbers, dyes, pigments, fillers, internal mold release agents, reinforcement Materials, matting agents, conductivity imparting agents, charge control agents, antistatic agents, lubricants, and other processing aids can be used.

2. Aqueous polyurethane resin composition
(1) Main agent and curing agent The aqueous polyurethane resin composition in the present invention is basically composed of a main agent and a curing agent.
The main component is (A) component: (a) a diisocyanate compound (b) a compound having a terminal hydroxyl group, a carbon-carbon unsaturated bond and an adjacent carbonyl group, (c) a fatty acid having an active hydrogen group, and (d) a polyol. A resin obtained by reacting a compound, which is an aqueous polyamine resin containing an amine residue by a urea reaction and a Michael addition reaction after neutralization.
A hardening | curing agent is a polyisocyanate compound represented by the above-mentioned HDI trimer which can be disperse | distributed to (A) component as (B) component.
The composition ratio is preferably used in the range where the active component molar ratio of [NCO] / [NH] is 1.5 to 6.0 in the component (B) / (A).

(2) Aspect as a composition The aqueous polyurethane resin composition of the present invention is a two-component system composed of the curing agent of the component (A) and the component (B) as the main components as described above. Is a two-component composition material such as a two-component paint composition or a two-component adhesive composition. When used as a paint, the two components are mixed and three-dimensional by a polyfunctional NCO compound as a curing agent. Hardened.
In general, the meaning of the composition for coating is not necessarily unambiguous, so in the present invention, it is not a composition in which all components are mixed in advance, but a composition as a two-component assembled material.

3. Method for producing aqueous polyurethane resin composition
(1) Production method of the composition The aqueous polyurethane resin composition of the present invention is produced by (a) a diisocyanate compound that forms the main chain of the urethane prepolymer, and (b) a component for Michael addition, And a compound having a terminal hydroxyl group, an unsaturated bond between carbon atoms and an adjacent carbonyl group, and a component for imparting water dispersibility (c) having an active hydrogen group. (D) A polyol compound is reacted to form a terminal isocyanate prepolymer, followed by neutralization of the carboxyl group of the fatty acid with a tertiary amine to form a chain extension. It is dispersed in an aqueous solution containing a primary amine compound as a polyamine to form an aqueous solution, and a urea reaction with an isocyanate residue and an unsaturated bond between carbon atoms and an adjacent carbonyl group are formed. A water-based polyamine resin containing primary and / or secondary amine residues by a Michael addition reaction with a compound having a composition with a curing agent component such as an HDI trimer that is then dispersible in the water-based polyamine resin component; It is done by doing.

(2) Chemical reaction and polymer structure in the production method of the composition In order to clarify the constitution and production method of the aqueous polyurethane resin composition of the present invention,
The chemical reaction and polymerization reaction and the prepolymer structure and polymer structure in the production method of the composition are specifically described below in terms of the production system.
i) Production of prepolymer
Aliphatic diisocyanate OCN-A-NCO, polyester (or polyether) diol HO-B-OH, dimethylol fatty acid HOCH ₂ R (COOH) CH ₂ OH, and 2-hydroxyethyl acrylate are reacted to form a prepolymer. ((U) in the following represents a urethane bond.)

_{OCN-A- (U) -B- (} U) -A- (U) -CH 2 R (COOH) CH 2 - (U) -A- (U) -C 2 H 5 -COO-CH = CH 2

ii) Neutralization treatment By the neutralization treatment with the tertiary amine NR ₃ , the —COOH group is neutralized to be water-dispersible.

OCN-A- (U) -B- ( U) -A- (U) -CH 2 R (COO - NH + R 3) CH 2 - (U) -A- (U) -C 2 H 5 -COO -CH = CH ₂

iii) Reaction of polyamine Polyamine NH ₂ —X—NH ₂ is added to react with the OCN group at the end of the prepolymer to introduce a polyamine group at the end, and —COO at the other end of the polyamine and the prepolymer A polyamine group is introduced by Michael addition reaction with —CH═CH ₂ group to form a polyamine dispersion.

~NH-CO-NH-X- NH-CO-NH~ ····· ( _{backbone) ····· ~-C 2 H 5} -COO-CH 2 CH 2 -NH-X-NH 2

iv) Addition of multifunctional curing agent The multifunctional curing agent Y (NCO) _n (n ≧ 3) is added to react with the terminal primary amine group to form a primary amine reactant.

~NH-CO-NH-X- NH-CO-NH~ ····· ( _{backbone) ····· ~-C 2 H 5} -COO-CH 2 CH 2 -NH-X-NH-CO -NH-Y- (NCO) _n-1

v) Urea reaction of secondary amine groups Over time, secondary amine groups formed by the introduction of polyamine groups react with NCO of the curing agent to form secondary amine reactants.

~NH-CO- (U) -X- ( U) -CO-NH~ ····· ( _{backbone) ····· ~-C 2 H 5} -COO-CH 2 CH 2 - (U) -X- (U) -CO- (U) -Y- (NCO) _n-1

vi) Reaction of NCO of Curing Agent with Water Over time, NCO in the curing agent and water of the aqueous dispersion undergo a urea reaction to form a water-reacted urea highly crosslinked body.

~NH-CO- (U) -X- ( U) -CO-NH~ ····· ( _{backbone) ····· ~-C 2 H 5} -COO-CH 2 CH 2 - (U) -X- (U) -CO- (U) -Y-((U)) _nx

  In the following, the present invention will be described in more detail by comparing the comparative examples with examples, to clarify the configuration of the present invention, and to demonstrate the rationality of each requirement of the configuration of the present invention.

[Synthesis of aqueous polyamine resin]
(A) a diisocyanate compound having (b) a molar ratio of 50% or more with respect to (a), a compound having a terminal hydroxyl group and having an intercarbon unsaturated bond and an adjacent carbonyl group; and (c) a terminal hydroxyl group. Two fatty acids and (d) a polyol compound are reacted to form a terminal isocyanate prepolymer, neutralized with a tertiary amine, dispersed in an aqueous solution having a primary amine compound, and an isocyanate residue. A water-based polyamine resin containing primary and / or secondary amine residues is produced by the urea reaction and the Michael addition reaction between the compound having an unsaturated bond between carbon atoms and an adjacent carbonyl group.

(Production example of polyurethane emulsion)
In a reactor having a capacity of 3,000 ml equipped with a stirrer, thermometer, nitrogen seal tube and condenser, 141.8 g of polyol A (polytetramethylene glycol Mn = 2,000 f = 2), 9.2 g of methylolpropionic acid (DMPA), 15.9 g of 2-hydroxyethyl acrylate (HEA) and 63.8 g of dipropylene glycol dimethyl ether (DMDPG) were charged and dissolved by heating at 90 ° C. for 10 minutes. After cooling to 60 ° C., 120.3 g of isocyanate A (HDI isopropanol-modified allophanate compound: NCO = 19.1%) and 0.04 g of dioctyltin dilaurate (DOTDL) were charged and reacted at 80 ° C. for 2 hours to contain a carboxyl group An isocyanate group-terminated prepolymer solution was obtained. The isocyanate content of this prepolymer solution was 3.40%, and the amount of carboxylic acid introduced into the prepolymer was 0.75 mmol / g.
Next, 6.9 g of triethylamine (TEA) was charged to neutralize the carboxyl group, and then 482 g of water and 10.4 g of diethyltriamine (DETA) were charged while stirring, and the chain extension reaction between water and amine was carried out at 30 ° C. I went for 12 hours. When the presence of isocyanate groups was no longer confirmed by FT-IR, an aqueous polyurethane emulsion PU-1 was obtained. The solid content of PU-1 was 32.5%, the pH was 9.5, and the viscosity at 25 ° C. was 40 mPa · s.

[Production of aqueous polyurethane resin composition]
To 100 parts of the aqueous polyamine resin dispersion A produced in the above synthesis example, a water / isocyanate curing agent (polyisocyanate A; methoxypolyethylene glycol modified of 3-methylpentanediol modified allophanate compound of HDI: NCO = 16.4 %) = 50/50 (mass%) 40 parts is blended, and the mixture B is stirred and dispersed at 2,000 rpm for 30 seconds and mixed by manual stirring to obtain aqueous polyamine resin compositions described in Tables 1-4. .

[Evaluation of liquid mixture]
(Gel time)
The time when the hardener HDI trimer was dispersed in the aqueous polyamine resin and gelled to become unusable as a paint was measured. The longer the times listed in Tables 1 to 4, the better the paint.
(Thickening)
The thickening at the time of addition of the curing agent was visually observed. The lower the thickening, the more suitable it is for use as a paint. In Table 1, it is evaluated as “◯: no thickening Δ: there is a little thickening, but it can be used as a paint ×: the thickening is large”. Was described.

[Performance evaluation as a coating film]
The mixed solution was applied to an aluminum plate to a thickness of 200 μm with an applicator and dried at room temperature for 7 days.
(Appearance of coating film)
After coating and visually observing the appearance of the coating film after drying for 7 days at room temperature, in Tables 1 to 4, depending on the glossiness of the coating film and the presence or absence of repelling, “○: Good Δ: Almost good” The evaluation of the appearance of the coating film was described as “The coating film was not glossy, had repelling, and was defective”.
(water resistant)
After coating, an immersion test in water at 50 ° C. for 3 hours was performed. After the test, the coating film was observed visually and by touch. According to Tables 1 to 4, “○: Good △” : Almost good ×: The coating film is whitened and sticky and has no water resistance ”.
(Methanol and MEK rubbing test / solvent resistance test)
Methanol and MEK rubbing tests were performed on the dried coating film. Absorbent cotton dipped lightly in methanol or MEK (methyl ethyl ketone) was reciprocated on the coating film, and the number of reciprocations until the coating film was scratched or peeled off was measured.

The performance results of the water-based polyamine resin composition are listed in Tables 1 to 4. The symbols in the table are as follows.
Polyol A; polytetramethylene glycol Mn = 2,000 f = 2
Polyol B: Polycarbonate polyol Mn = 2,000 f = 2
Polyol C; polyester polyol based on phthalic acid Mn = 2,000 f = 2
Isocyanate A; isopropanol-modified allophanate compound of HDI (NCO = 19.1%)
Isocyanate B; isophorone diisocyanate (NCO = 37.8%)
DMPA; dimethylolpropionic acid
HEA; 2-hydroxyethyl acrylate
EDA; ethylenediamine
DETA; diethylenetriamine TETA; triethylenetetramine TEPA; tetraethylenepentamine
Polyisocyanate A; methoxypolyethylene glycol modified form of 3-methylpentanediol modified allophanate compound of HDI (NCO = 16.4%)
Polyisocyanate B; methoxypolyethylene glycol modified form of 3-dimethylpentanediol modified allophanate compound of HDI (NCO = 18.3%)
PU-2 to 9 are water-based polyurethane emulsions manufactured according to the method of the water-based polyurethane emulsion PU-1 described in Paragraph 0031 and having the performance described in Tables 1 to 4.

[Examples of physical properties as adhesives and comparative examples]
Evaluation of the aqueous polyamine resin composition produced in Paragraph 0032 as an adhesive is as follows.
(Adhesion performance test)
Adhesive piece preparation procedure: (1) Rubber buffing Rubber: Natural rubber (2) Primer is applied to two rubber surfaces (dried at 60 ° C for 3 min) Primer: Trichloroisocyanuric acid (2.5% acetone solution) (3) Apply the compounded liquid on the primer (dry at 60 ° C. for 6 min) (4) Laminate two sheets and press at 5 MPa / 20 sec pressure Compounded liquid: Main ingredient = Aqueous polyamine dispersion Curing agent = Polyisocyanate B blending = 50/50 hardener and water stirred at 2,000 rpm for 20 seconds, blending 20 parts with 100 parts of main agent (test item)
Adhesive strength (N / cm); initial adhesive strength = adhesive strength immediately after bonding Final adhesive strength = adhesive strength after 24 hours of bonding Measurement condition = peeling speed 5 cm / min
Hydrolysis resistance (N / cm): Adhesive strength after standing at 70 ° C./95% RH for 7 days Heat resistance: At 70 ° C., the test piece was subjected to a load of 4.9 N / cm for 1 hour and then peeled off The presence or absence of was observed visually.
The results of the adhesion performance test are listed in Table 5. In the table, “R value of liquid mixture” is
The molar ratio of NCO to NH active ingredient (NCO / NH).

[Consideration of results of Examples and Comparative Examples]
By comparing each of the above Examples and Comparative Examples, the present invention utilizes a Michael addition reaction with an α, β-unsaturated carbonyl compound having a terminal hydroxyl group in the use of a polyamine in an aqueous polyurethane resin composition. In contrast to the comparative example, which is a conventional example, by changing the primary amine to a secondary amine to control the reaction with the isocyanate group, the gelation time is extended, and there is no thickening when adding a curing agent. It has been clarified that it is possible to produce a polyurethane resin paint or an adhesive that can form a coating having an excellent coating appearance, such as coating film appearance and coating stickiness, and high strength and water resistance and solvent resistance. Yes.
Specifically, in Examples 1 to 4, diethylenetriamine and ethylenediamine are used together with an α, β-unsaturated carbonyl compound having a terminal hydroxyl group, and in either case, good physical properties are exhibited. In Examples 5 and 6, TETA and TEPA having a carbon chain longer than that of DETA are used as polyamines, and it can be seen that methanol solvent resistance is further improved.
In Comparative Examples 1 and 3, diethylenetriamine is used. In Comparative Example 3, active hydrogen derived from the amino group of the monomer is present. In Comparative Example 2, ethylenediamine is used. Since a saturated carbonyl compound is not used, the central requirement of the present invention is lacking, and the physical property improving action by active hydrogen of polyamine is not seen, and various physical properties in each table are inferior.
From the above data results and discussion, it can be said that the rationality and significance of the constituent elements of the present invention are demonstrated, and it is clear that the present invention has a remarkable superiority as compared with the prior art.

Industrial application fields

In the present invention, in the use of the polyamine in the aqueous polyurethane resin composition, the gelation time is extended, the appearance is good, the strength is high, the water resistance and the solvent resistance, etc., compared with the case where the diol compound is used even at room temperature curing. And can be used as an industrially useful and excellent polyurethane resin paint or adhesive.

More specifically, polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, malonic acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, kurtaconic acid, Azelaic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylmuconic acid, α, β-diethylsuccinic acid, maleic acid, fumaric acid, other dibasic and one or more such acids, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3 - butanediol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol By polycondensation reaction of bisphenol A adducts such as ethylene oxide and propylene oxide, bis (β-hydroxyethyl) benzene, xylylene glycol, other diols, or polyols such as glycerin, trimethylolpropane, pentaerythritol The resulting polyester polyol is used.
Furthermore, lactone-based polyester polyols obtained by ring-opening polymerization of monomers such as cyclic esters (lactones) such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, alkyl-substituted δ-valerolactone, and the like are also included. A polyester amide polyol obtained by changing a part of the low molecular polyol to low molecular amines such as hexamethylene diamine, isophorone diamine, and monoethanol amine, or a low molecular amino alcohol can also be used.

(Production example of polyurethane emulsion)
In a reactor having a capacity of 3,000 ml equipped with a stirrer, thermometer, nitrogen seal tube and condenser, 141.8 g of polyol A (polytetramethylene glycol Mn = 2,000 f = 2), 9.2 g of methylolpropionic acid (DMPA), 15.9 g of 2-hydroxyethyl acrylate (HEA) and 63.8 g of dipropylene glycol dimethyl ether (DMDPG) were charged and dissolved by heating at 90 ° C. for 10 minutes. After cooling to 60 ° C., 120.3 g of isocyanate A (HDI isopropanol-modified allophanate compound: NCO = 19.1%) and 0.04 g of dioctyltin dilaurate (DOTDL) were charged and reacted at 80 ° C. for 2 hours to contain a carboxyl group to obtain a diisocyanate over preparative group-terminated prepolymer solution. The isocyanate content of this prepolymer solution was 3.40%, and the amount of carboxylic acid introduced into the prepolymer was 0.75 mmol / g.
Next, 6.9 g of triethylamine (TEA) was charged to neutralize the carboxyl group, and then 482 g of water and 10.4 g of diethyltriamine (DETA) were charged while stirring, and the chain extension reaction between water and amine was carried out at 30 ° C. I went for 12 hours. When the presence of isocyanate groups was no longer confirmed by FT-IR, an aqueous polyurethane emulsion PU-1 was obtained. The solid content of PU-1 was 32.5%, the pH was 9.5, and the viscosity at 25 ° C. was 40 mPa · s.

Claims (5)

As component (A), (a) a diisocyanate compound, (b) a compound having a terminal hydroxyl group, an intercarbon unsaturated bond and an adjacent carbonyl group, (c) a fatty acid having an active hydrogen group, and (d) a polyol compound. It is a reacted resin, and contains a water-based polyamine resin containing an amine residue by a urea reaction and a Michael addition reaction after neutralization, and a polyisocyanate compound dispersible in the component (A) as the component (B). An aqueous polyurethane resin composition characterized by the above. (A) The diisocyanate compound is an aliphatic diisocyanate compound, and (b) a terminal hydroxyl group having a terminal hydroxyl group and having a carbon-carbon unsaturated bond and an adjacent carbonyl group is a molar ratio of 50% or more with respect to (a). A (meth) acrylate compound having (c) a fatty acid having an active hydrogen group is a dimethylol fatty acid, and (d) a polyester diol having a number average molecular weight of 800 to 6,000 (including polycarbonate diol). Or a polyether diol, wherein the amine residue by urea reaction and Michael addition reaction is a primary and / or secondary amino residue and is contained in an amount of 0.2 to 3.0 mmol / g in the resin solid content, [NCO] / The aqueous polyurethane according to claim 1, wherein the molar ratio of the active component of [NH] is 1.5 to 6.0. Fat composition. An aqueous polyurethane resin composition, wherein the aqueous polyurethane resin composition according to claim 1 or 2 is a two-component paint composition or a two-component adhesive composition. The coating composition is a two-component assembly material of (A) component water-based polyamine resin and (B) component polyisocyanate as a curing agent, and the two components are mixed when used as a coating material. The aqueous polyurethane resin coating composition according to claim 3. As the component (A), (a) a diisocyanate compound having a molar ratio of 50% or more with respect to (b) (a), a compound having a terminal hydroxyl group and having an intercarbon unsaturated bond and an adjacent carbonyl group (c) ) A fatty acid having an active hydrogen group and (d) a polyol compound are reacted to form a terminal isocyanate prepolymer, neutralized with a tertiary amine, dispersed in an aqueous solution having a primary amine compound, and an isocyanate residue. A water-based polyamine resin containing primary and / or secondary amine residues is produced by a urea reaction with a group and a Michael addition reaction with a compound having an unsaturated bond between carbon and an adjacent carbonyl group, and then dispersed in the component (A) The aqueous polyurethane resin composition according to claim 1 or 2, wherein the composition is a composition with a polyisocyanate compound as a possible component (B). Law.