JP5457039B2 - Curable composition for water-based soft-feel coatings with improved coating flexibility and resistance balance - Google Patents

Description

  The present invention provides (A) a carboxyl group and / or sulfonic acid group-containing polyol or salt portion in the molecule, a polycarbonate diol portion represented by a specific structural formula, a polyisocyanate compound portion and other copolymers. An aqueous dispersion of a polyurethane containing a portion of a possible polyol monomer at a specific mass ratio and not having an OH group at the molecular end; and (B) a portion of a polyol or salt thereof containing a carboxyl group and / or a sulfonic acid group in the molecule And a polycarbonate diol portion represented by a specific structural formula, a polyisocyanate compound portion and other copolymerizable polyol monomer portions in a specific mass ratio, and a polyurethane having a molecular terminal that is an OH group. The aqueous dispersion is blended at a weight ratio such that (A) and (B) are in a specific range, and (C) A water-dispersed curing agent of polyisocyanate containing at least two isocyanate groups in (B) a blend ratio of OH groups in the molecule and (C) NCO groups in the molecule (NCO groups / OH groups) The present invention relates to a curable composition for water-based soft-feel paints formulated so that the molar ratio is within a specific range.

Conventionally, polyurethane resins are used in a wide range of areas such as synthetic leather, artificial leather, adhesives, furniture paints, and automobile paints. Polyether polyols and polyester polyols are used as polyol components that react with isocyanates. Has been. However, in recent years, demands for chemical resistance such as heat resistance, weather resistance, abrasion resistance, and the like, and resistance to hydrolysis, oil resistance, acid resistance, alkali resistance, chemical resistance, etc. have increased. In addition, a soft touch is required. As a usual means for solving the strength and chemical resistance of the resin, it is common to introduce a crosslinked structure into the polymer chain.
As this means, a method of introducing a trifunctional monomer part into the polymer main chain or a method described in Patent Documents 1 and 2 below can be considered. However, according to these means, the coating film of the paint becomes hard. Therefore, it was insufficient to achieve both a high level of demand for resistance and a soft feel.
In addition, in order to improve the performance of the polyol itself and to make it compatible with a soft feel, a polycarbonate polyol of a type in which two or more kinds of diol monomers are copolymerized has been used. Therefore, there has been a demand for further improvement in resistance, and improvement in the performance balance between soft feeling and coating film resistance has been desired.

JP 2008-303284 A JP2008-303285A

  The present invention makes it possible to form a coating film that is excellent in chemical resistance such as acid resistance, alkali resistance, and alcohol resistance, and also in abrasion resistance without impairing the softness of the coating film, that is, the soft feeling of the touch. An object of the present invention is to provide a water-based curable composition for paint.

As a result of intensive studies, the present inventors have
(A) Carboxyl group and / or sulfonic acid group-containing polyol or salt portion thereof, polycarbonate diol portion represented by a specific structural formula, polyisocyanate compound portion and other copolymerizable polyol monomers In a specific mass ratio and the molecular terminal of which is not an OH group, an aqueous dispersion of polyurethane, (B) a carboxyl group and / or sulfonic acid group-containing polyol or salt thereof in the molecule, and a specific part An aqueous dispersion of a polyurethane containing a polycarbonate diol part represented by the structural formula, a polyisocyanate compound part and other copolymerizable polyol monomer parts in a specific mass ratio and having molecular ends that are OH groups , (A) and (B) are blended in a specific weight ratio, and (C) A water-dispersed curing agent of polyisocyanate containing at least two isocyanate groups is mixed with a blend ratio of (B) OH groups in the molecule and (C) NCO groups in the molecule (molar ratio of NCO groups / OH groups). It was found that the intended purpose can be achieved by blending the composition so that the amount is within a specific range, and the present invention has been achieved.

That is, the present invention
(1) It contains the following (A), (B) and (C) as essential components, and (A) / (B) = 0.2 to 5 (however, the mass ratio of nonvolatile content), and (B) Curing for water-based paints, characterized in that the ratio of the OH group contained in the molecule to the NCO group contained in the molecule (C) is NCO / OH = 2.5 to 0.9 (mole ratio of functional groups) Sex composition:
(A) An aqueous dispersion of a polyurethane having a carboxyl group and / or a sulfonic acid group-containing polyol or a salt thereof in the molecule, a polycarbonate skeleton, and a molecular end group that is not a hydroxyl group, Before the emulsion dispersion in water, the content of the monomer part of the carboxyl group and / or sulfonic acid group-containing polyol or salt thereof copolymerized with the NCO end group-containing urethane prepolymer is 1% by mass to 25% by mass, polycarbonate diol The content of the polyisocyanate compound monomer is 5% by mass to 94% by mass, the content of the polyisocyanate compound monomer is 5% by mass to 94% by mass, and the content of the other copolymerizable monomer is 0% by mass to 10% by mass. %, An aqueous dispersion of the above polyurethane,
(B) an aqueous dispersion of a polyurethane having a carboxyl group and / or a sulfonic acid group-containing polyol or a salt thereof in the molecule, a polycarbonate skeleton, and a molecular end group being a hydroxyl group, Before emulsifying and dispersing in water, the content of the monomer part of the carboxyl group and / or sulfonic acid group-containing polyol or salt thereof copolymerized with the OH terminal group-containing urethane polymer is 0.5% by mass to 25% by mass, The content of the polycarbonate diol part is 20% by mass to 99% by mass, the content of the polyisocyanate compound monomer part is 0.5% by mass to 79.5% by mass, and the content of the other copolymerizable monomer part is An aqueous dispersion of the polyurethane, which is 0% by mass to 10% by mass,
(C) A water-dispersed curing agent of a polyisocyanate compound containing at least two isocyanate groups in the molecule.
(2) The structure of the polycarbonate diol used in each of (A) and (B) described in (1) includes two or more types of repeating units selected from the following formulas (1) to (4), and is a number average The curable composition for water-based paints according to (1), wherein the molecular weight is 500 to 4000, and the terminal group is a hydroxyl group.

(3) The polycarbonate diol is one or more aliphatic polycarbonate diols selected from the following (a), (b) and (c), and these polycarbonate diols (a), (b) and (c) ) Is composed of two types of repeating units selected from the following formulas (5) to (8), and the molar ratio of the two types of selected repeating units is in the range described below, and the terminal The curable composition for water-based paints according to (1) or (2), wherein the group is a hydroxyl group:
(A) Two types of repeating units selected are represented by (Formula 5) and (Formula 6), (number of moles of formula 5) / (number of moles of formula 6) = 80/20 to 30/70, An aliphatic polycarbonate diol having a hydroxyl group as a terminal group,
(B) The two types of repeating units selected are represented by (formula 6) and (formula 8), (number of moles of formula 6) / (number of moles of formula 8) = 95/5 to 30/70, An aliphatic polycarbonate diol having a hydroxyl group as a terminal group,
(C) The two types of repeating units selected are represented by (formula 7) and (formula 8), (number of moles of formula 7) / (number of moles of formula 8) = 80/20 to 30/70, An aliphatic polycarbonate diol having a terminal hydroxyl group.

  According to the present invention, the physical strength of the coating film such as the scratch resistance and abrasion resistance of the coating film, and the physical property balance of the chemical resistance of the coating film such as acid resistance, alkali resistance and alcohol resistance, In addition, it is possible to provide a curable composition for water-based soft-feel coatings that enables formation of a coating film having a soft touch feeling.

  Hereinafter, the present invention will be described in detail.

The polyisocyanate compound monomer used in the aqueous polyurethane dispersions (A) and (B) of the present invention is a monomer having two or more isocyanate groups in one molecule. Specific examples thereof include diphenylmethane diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate (TDI), hexamethylene diisocyanate, trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 2,6-diisocyanate methylcaproate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4 (or 2,6) -diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), dodecane Isocyanurate-type polyisocyanates derived from aromatic, aliphatic and alicyclic isocyanates such as diisocyanates and dicyclohexylmethane diisocyanates, or a mixture of these isocyanates alone or in mixture Low molecular weight polyester resin (oil-modified type) having a functional group that reacts with a let type isocyanate and these diisocyanates and ethylene glycol, polyether polyol (polyethylene glycol, polypropylene glycol, etc.), caprolactone polyol, polycarbonate polyol or isocyanate group Random adducts with acrylic copolymers, etc., or
Isocyanates containing 2-hydroxypropyl (meth) acrylate and hexamethylene diisocyanate equimolar adducts, vinyl monomers having isocyanate groups and copolymerizable unsaturated groups such as isocyanate ethyl (meth) acrylate as essential components And a copolymer having a group.

  In particular, from the viewpoint of weather resistance, aliphatic and / or alicyclic diesters such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dodecane diisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate. Isocyanates and polyisocyanates derived therefrom are desirable.

  Further, these polyisocyanates are blocked with known blocking agents such as lower alcohols such as butanol and 2-ethylhexanol, methyl ethyl ketone oximes, lactams, phenols, imidazoles, and active methylene compounds. Isocyanates can be used. These polyisocyanate compounds are Sumidur 44S, 44V70 (both made by Sumika Bayer Urethane), dismodule HL (made by Sumika Bayer Urethane), which is a copolymer of TDI and HDI, and various duranates made by Asahi Kasei Chemicals, namely duranates. 24A-100, Duranate 22A-75PX, Duranate 18H-70B, Duranate 21S-75E, Duranate THA-100, Duranate TPA-100, Duranate MFA-75X, Duranate TSA-100, Duranate TSS-100, Duranate TSE-100, Duranate D-101, Duranate D-201, Duranate P-301-75E, Duranate E-402-90T, Duranate E-402-90T, Duranate E 405-80T, Duranate ME20-100, Duranate 17B-60PX, Duranate TPA-B80X, Duranate MF-B60X, Duranate E-402-B80T, Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100 , Duranate WT30-100, Duranate MHG-80B and the like.

  Next, the polycarbonate diol used in the production of the water-based polyurethane dispersion of the present invention is obtained by using two or more kinds of diols by various methods described in Schell, Polymer Review, Vol. 9, pages 9 to 20 (1964). It is a copolymerized polycarbonate diol synthesized from monomers.

  The polycarbonate diol used in the present invention includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol as diol monomers. 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2,3-butanediol, 1,5-hexane Diol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexane Sanji ol, 1,4 consists of two or more kinds of repeating units selected from dimethanol or the like, the end group is an aliphatic polycarbonate diol which is a hydroxyl group.

  However, the present inventors have studied various polycarbonate diols in this application, and as a result, by using a carbonate diol having a specific structure, it is excellent in the balance between physical strength such as abrasion and chemical resistance and softness of the coating film. It was found that a paint was obtained.

  That is, preferably, a repeating unit composed of two or more kinds of repeating units selected from 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-hexanediol, and 1,6-hexanediol. The aliphatic polycarbonate diol is characterized in that the terminal group is a hydroxyl group.

  More preferably, the two types of repeating units selected are 2-methyl-1,3-propanediol and 1,4-butanediol, and (number of moles of 2-methyl-1,3-propanediol) / ( The number of moles of 1,4-butanediol) = 80/20 to 30/70, and the terminal group is an aliphatic polycarbonate diol having a hydroxyl group, or two kinds of repeating units selected are 1,4- Butanediol and 1,6-hexanediol, (number of moles of 1,4-butanediol) / (number of moles of 1,6-hexanediol) = 95/5 to 30/70, and end groups are It is an aliphatic polycarbonate diol which is a hydroxyl group, or two types of repeating units selected are 1,5-hexanediol and 1,6-hexanediol, The number of moles of diol) / (number of moles of 1,6-hexanediol formula 16) was = 80 / 20-30 / 70, and terminal group is an aliphatic polycarbonate diol is a hydroxyl group.

  The ratio of 2-methyl-1,3-propanediol and 1,4-butanediol, which are repeating units constituting the polycarbonate diol, is (number of moles of 2-methyl-1,3-propanediol) / (1,4 -The number of moles of butanediol) = 80/20 (molar ratio) or less is preferred because the flexibility of the resulting coating film is not impaired. The ratio of 2-methyl-1,3-propanediol and 1,4-butanediol, which are repeating units constituting the polycarbonate diol, is (number of moles of 2-methyl-1,3-propanediol) / (1 , 4-butanediol mole number) = 30/70 (molar ratio) or more, the flexibility of the resulting coating film is not impaired, and the oil resistance and wear resistance are not deteriorated. preferable. More preferably, the ratio of 2-methyl-1,3-propanediol and 1,4-butanediol constituting the polycarbonate diol is (number of moles of 2-methyl-1,3-propanediol) / (1,4- Number of moles of butanediol) = 75/25 to 35/65 (molar ratio), more preferably, (number of moles of 2-methyl-1,3-propanediol) / (number of moles of 1,4-butanediol) = 70 / 30-40 / 60 (molar ratio).

  Furthermore, the ratio of 1,4-butanediol and 1,6-hexanediol, which are repeating units constituting the polycarbonate diol, is (number of moles of 1,4-butanediol) / (number of moles of 1,6-hexanediol). ) = 95/5 (molar ratio) or less, the flexibility of the resulting coating film is preferably not impaired. The ratio of 1,4-butanediol and 1,6-hexanediol, which are repeating units constituting the polycarbonate diol, is (number of moles of 1,4-butanediol) / (number of moles of 1,6-hexanediol). ) = 30/70 (molar ratio) or more, the flexibility of the resulting coating film is not impaired, and oil resistance and abrasion resistance are not deteriorated, which is preferable. The ratio of 1,4-butanediol and 1,6-hexanediol constituting the polycarbonate diol is more preferably (number of moles of 1,4-butanediol) / (number of moles of 1,6-hexanediol) = 94. / 6 to 35/65 (molar ratio), more preferably (molar number of 1,4-butanediol) / (molar number of 1,6-hexanedioe) = 93/7 to 40/60 (molar ratio) It is.

  Furthermore, the ratio of 1,5-pentanediol and 1,6-hexanediol, which are repeating units constituting the polycarbonate diol, is (number of moles of 1,5-pentanediol) / (number of moles of 1,6-hexanediol). ) = 80/20 (molar ratio) or less, the flexibility of the resulting coating film is not impaired, which is preferable. The ratio of 1,5-pentanediol and 1,6-hexanediol, which are repeating units constituting the polycarbonate diol, is (number of moles of 1,5-pentanediol) / (number of moles of 1,6-hexanediol). ) = 30/70 (molar ratio) or more, the flexibility of the resulting coating film is not impaired, and oil resistance and abrasion resistance are not deteriorated, which is preferable. More preferably, the ratio between 1,5-pentanediol and 1,6-hexanediol constituting the polycarbonate diol is (number of moles of 1,5-pentanediol) / (number of moles of 1,6-hexanediol) = 75. / 25 to 35/65 (molar ratio), more preferably, (number of moles of 1,5-pentanediol) / (number of moles of 1,6-hexanediol) = 70/30 to 40/60 (molar ratio) It is.

  In the present invention, the number average molecular weight of the polycarbonate diol is preferably 500 to 4000, more preferably 600 to 3000, and still more preferably the number average molecular weight 700 to 2500. If the number average molecular weight is 500 or more, the flexibility of the coating film does not decrease. In addition, if the number average molecular weight is 4000 or less, the prepolymer viscosity before being dispersed in water does not increase and handling problems do not occur, and the softness and resistance of the formed coating film are sufficient. preferable.

  It is desirable that the polymer end groups of the polycarbonate diol used in the present invention are substantially all hydroxyl groups.

  The polycarbonate diol is copolymerized within a range in which a compound having three or more hydroxyl groups per molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc. is not gelled, if necessary. It can also be used as a polyfunctionalized polycarbonate in which the average number of hydroxyl groups in one molecule is greater than 2. When the average hydroxyl group number of the polyfunctionalized polycarbonate is too high, an effect of improving the resistance is recognized, but it is not preferable because the obtained coating film may become hard.

  The polycarbonate diol used in the present invention can contain other low molecular weight diol as a copolymerization component as long as its characteristics are not impaired. Specific examples of other diols that can be used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, -Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2,3-butanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecadiol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like, and the ratio of these diols is occupied by all monomer diols. As a percentage that is less than 40 wt%, preferably less than 20 wt%, more preferably less than 10 wt%.

  The carboxyl group and / or sulfone group-containing polyol or salt thereof used in the present invention provides water-based polyurethane having an OH group as the terminal group of the polymer main chain in water and imparts dispersion stability of the water-based polyurethane dispersion. It is a component used for introducing a carboxylate group or a sulfonate group for the purpose of. Examples of the carboxyl group-containing polyol include 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid (DMBA), 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, and the like. Is mentioned. Examples of the sulfone group-containing polyol include sulfonic acid diol {3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid} and sulfamic acid diol {N, N-bis- (2-hydroxylalkyl) sulfamine. Acid} and its alkylene oxide adducts. Examples of salts of these carboxyl group and / or sulfone group-containing polyols include ammonium salts and amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propylamine, and octylamine). Salts, secondary monoamines (dimethylamine, diethylamine and dibutylamine) salts, tertiary monoamines (aliphatic tertiary monoamines such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine; N-methyl) Heterocyclic tertiary monoamines such as piperidine and N-methylmorpholine; benzyldimethylamine, α-methylbenzyldimethylamine; and aromatic ring-containing tertiary monoamines such as N-dimethylaniline) salts], alkali metals (sodium Potassium and lithium cations) salts, and combinations of two or more of these.

  Among these carboxyl salts and / or sulfonates, preferred are amine salts, more preferred are aliphatic tertiary monoamine salts, and particularly preferred are triethylamine salts.

  When the carboxyl group and / or sulfonic acid group-containing polyol is not a salt but a carboxyl group and / or sulfone group-containing polyol, the carboxylate is obtained by neutralizing the carboxyl group and / or the sulfone group using a neutralizing agent. Group and / or sulfonate group.

  Examples of the neutralizing agent include alkaline compounds that form the cations mentioned as the counter ion. For example, ammonia, amine [primary amine having 1 to 12 carbon atoms (primary monoamine such as methylamine, ethylamine, propylamine and octylamine), secondary monoamine (dimethylamine, diethylamine and dibutylamine), tertiary monoamine ( Aliphatic tertiary monoamines such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; benzyldimethylamine, α -Methylbenzyldimethylamine; and aromatic ring-containing tertiary monoamines such as N-dimethylaniline)], alkali metals (sodium, potassium and lithium cations), alkali metal hydroxides, and two or more of these Use and the like.

  Of these, preferred are amines, more preferred are aliphatic tertiary monoamines, and particularly preferred is triethylamine.

  As for the usage-amount of a carboxyl group and / or a sulfone group containing polyol, it is preferable that a carboxyl group and / or a sulfone group contain in the quantity of 1 mass%-25 mass% with respect to the weight of a polyurethane resin. More preferably, it is 1.2-20 mass%. If the carboxyl group and / or the sulfone group is 1% by mass or more, sufficient emulsion stability is obtained, which is preferable. Moreover, if it is 25 mass% or less, the water resistance of the film obtained is sufficient.

  Examples of other copolymerizable monomers used in the present invention include compounds having two or more hydroxyl groups per molecule, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2- Butanediol, 1,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2,3-butanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11- Undecadiol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol Other diols, trimethylol ethane, trimethylol propane, hexane triol, pentaerythritol, glycerol, and the like.

  Among them, by copolymerizing trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, glycerin and the like in a range that does not gel, it is possible to obtain a urethane having a branched structure. By copolymerizing trifunctional polyol monomers such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, glycerin, etc. in addition to the bifunctional polycarbonate diol during the production of polyurethane having an OH group at the end group, It is possible to obtain a polyurethane in which the terminal group of the polymer main chain having an average number of OH groups of 2 or more is an OH group.

  In the present invention, as a matter of course, an appropriate surfactant such as a higher fatty acid, a resin acid, an acidic fatty alcohol, a sulfuric ester, a higher alkyl sulfonate, an alkyl sulfonate is added at an addition level that does not impair the physical properties such as water resistance. In combination with anionic surfactants typified by aryl, sulfonated castor oil, sulfosuccinic acid ester, etc. or nonionic surfactants typified by known reaction products of ethylene oxide and long-chain fatty alcohols or phenols Emulsion stability may be maintained. Among these, preferable surfactants are nonionic surfactants.

  Moreover, in order to promote reaction in a urethanation reaction, you may use the catalyst used for a normal urethane reaction as needed. Examples of the catalyst include amine catalysts such as triethylamine, N-ethylmorpholine and triethylenediamine; tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin octylate; titanium-based catalysts such as tetrabutyl titanate.

  The method for producing an aqueous polyurethane dispersion in which the terminal group of the polymer main chain is not OH group according to the present invention can be obtained, for example, by the following method. Containing two or more isocyanate groups in one molecule in the presence or absence of an organic solvent containing no active hydrogen-containing group in the molecule (for example, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.) An organic polyisocyanate and a polycarbonate diol having a specific structure and / or a carboxyl group and / or a sulfone group-containing polyol or a salt thereof, NCO group / OH group ratio (molar ratio) so that the terminal group of the polymer main chain becomes an NCO group And react by a one-shot method or a multistage method to synthesize a polyurethane prepolymer. If necessary, a tin-based catalyst, a titanium-based catalyst, or the like may be added during synthesis.

  After neutralizing the polyurethane prepolymer with a neutralizing agent as necessary, water is added dropwise to the resultant reaction solution where the reaction solution is vigorously stirred. After the completion of the dropwise addition of water, a chain extender such as diamine and diol is subsequently dropped to increase the molecular weight, and the aqueous polyurethane dispersion is obtained by removing the solvent. It is also possible to add the obtained prepolymer solution into strongly stirred water, and subsequently drop a chain extender, and then remove the solvent to obtain an aqueous polyurethane dispersion.

  In the process of dispersing urethane in water, it is possible to disperse in water after protecting the NCO group at the molecular end with a blocking agent. Moreover, in order to improve the dispersion stability to water, you may use surfactant as needed.

  In addition, neutralization of the carboxyl group and / or the sulfone group with the neutralizing agent may be used for prepolymer synthesis after neutralizing the carboxyl monomer and / or the sulfone group-containing polyol monomer. Further, the method of dispersing the polyurethane in water may be appropriately selected so that the particle size and particle size distribution of the finally obtained aqueous polyurethane dispersion can be easily controlled.

  The method for producing an aqueous polyurethane dispersion in which the terminal group of the polymer main chain is an OH group according to the present invention can be obtained, for example, by the following method. Containing two or more isocyanate groups in one molecule in the presence or absence of an organic solvent containing no active hydrogen-containing group in the molecule (for example, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.) An organic polyisocyanate (a), a polycarbonate diol (b) having a specific structure, a carboxyl group and / or a sulfone group-containing polyol or a salt thereof (c) are mixed with NCO so that the terminal group of the polymer main chain becomes an OH group A group / OH group ratio (molar ratio) is determined and reacted by a one-shot method or a multistage method to synthesize a polyurethane whose terminal group of the polymer main chain is an OH group. If necessary, a tin-based catalyst, a titanium-based catalyst, or the like may be added during synthesis.

  The polyurethane is neutralized with a neutralizing agent as necessary, and then the resulting reaction solution is vigorously stirred, and water is added dropwise. After completion of the addition, the solvent is removed to remove the OH group terminal. An aqueous polyurethane dispersion is obtained. It is also possible to add the obtained polyurethane solution to strongly stirred water and remove the solvent to obtain an aqueous polyurethane dispersion in which the terminal groups of the polymer main chain are OH groups. .

  In the step of dispersing urethane in water, a surfactant may be used as necessary in order to improve dispersion stability.

  The neutralization of the carboxyl group and / or the sulfone group with the neutralizer may be used for polymer synthesis after neutralizing the carboxyl group and / or the sulfone group-containing polyol monomer. Further, the method of dispersing the polyurethane whose terminal group of the polymer manager is an OH group in water may be appropriately selected so that the particle size and particle size distribution of the finally obtained aqueous polyurethane dispersion can be easily controlled. .

  Moreover, in order to promote reaction in a urethanation reaction, you may use the catalyst used for a normal urethane reaction as needed. Examples of the catalyst include amine catalysts such as triethylamine, N-ethylmorpholine and triethylenediamine; tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin octylate; titanium-based catalysts such as tetrabutyl titanate.

  The number average molecular weight of the polyurethane whose terminal group of the polymer main chain of the present invention is an OH group is preferably 800 to 50,000. If the number average molecular weight is 800 or more, the stability of the emulsion is not impaired. Moreover, if a number average molecular weight is 50000 or less, a curing reaction rate with an aqueous curing agent will not be slowed.

As an NCO group blocking agent used in the present invention,
Oxime type: For example, formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc.
Active methylene type: Malonic acid diester (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, sec-butyl methyl malonate , Ethyl sec-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methyl malonate, dibenzyl malonate, diphenyl malonate, benzyl ethyl malonate, ethyl phenyl malonate, t-butyl malonate Phenyl, isopropylidene malonate, etc.), acetoacetate (methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n acetoacetate -Butyl, acetoacetic acid - butyl acetoacetate benzyl, phenyl acetoacetate).
Phenol type: phenol, cresol, ethylphenol, butylphenol, etc.
Mercaptans: butyl mercaptan, dodecyl mercaptan, etc.
Acid amide type: acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam and the like.
Acid imide type: succinimide, maleic imide and the like.
Imidazole series: imidazole, 2-methylimidazole and the like.
Urea type: urea, thiourea, ethylene urea, and the like.
Amine type: diphenylamine, aniline, carbazole and the like.
Imine type: ethyleneimine, polyethyleneimine, etc.
Bisulfite type: sodium bisulfite and the like.
Pyrazole type: pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole and the like.
Triazole type: 1,2,4-triazole and the like.
Of these, oxime, active methylene and pyrazole are preferred, and specific preferred examples include acetoxime, methyl ethyl ketoxime, malonic diester, acetoacetate, pyrazole and the like. In particular, from the viewpoint of low-temperature curability, a malonic acid diester, an acetoacetic acid ester, and a pyrazole mixed system are preferable, a malonic acid diester and an acetoacetic acid mixed system are more preferable, and a malonic acid diester is more preferable. Among the malonic acid diesters, diethyl malonate is preferable from the viewpoint of industrial availability.

  In the present invention, the mixing ratio of the polyurethane aqueous dispersion (A) whose molecular end group is not OH group and the polyurethane aqueous dispersion (B) whose molecular end group is OH group is (A) / (B) = 0.2. To 5 (however, the mass ratio of non-volatile content) is preferable. More preferably, (A) / (B) = 0.3-3. If the ratio of (A) / (B) is 0.2 or more, the soft feeling of the coating film is not impaired. Moreover, if the ratio of (A) / (B) is 5 or less, the tolerance is sufficient.

The blending ratio of the aqueous polyurethane dispersion (B) to the water-dispersed curing agent (C) of polyisocyanate is determined from the viewpoint of coating film performance by the OH group contained in the polyurethane aqueous dispersion (B) molecule and the polyisocyanate. The ratio of NCO groups contained in the water-dispersible curing agent (C) molecule of Nart is preferably NCO / OH = 2.5 to 0.9 (however, the molar ratio of functional groups). More preferably,
NCO / OH = 2.2 to 1.2. If NCO / OH is 2.5 or less, there is no possibility of problems in heat resistance and the like. Moreover, if NCO / OH is 0.9 or more, the curing reaction proceeds sufficiently, and there is no possibility that the coating film strength and resistance are impaired.

  The polycarbonate diol used in the polyurethane aqueous dispersion (A) in which the molecular end group is not an OH group and the polyurethane aqueous dispersion (B) in which the molecular end group is an OH group in the present invention may be the same. Different ones may be used.

  The component (C) used in the present invention is a water-dispersed curing agent of a polyisocyanate compound containing at least two isocyanate groups in the molecule.

  The polyisocyanate compound used in the present invention can be used as it is or with a nonionic and / or ionic surfactant, but from the viewpoint of water dispersibility, it is nonionic and / or ionic. A water-dispersible polyisocyanate compound modified with a hydrophilic group such as a surfactant is preferably used. As such a water-dispersible polyisocyanate compound, any compound obtained by introducing a hydrophilic group by a conventionally known method can be used without particular limitation. For example, a reaction product of an alkoxy polyalkylene glycol and a polyisocyanate compound, or nonionic properties A reaction product of a vinyl polymer containing a group and an isocyanate-reactive group (such as a hydroxyl group) and a polyisocyanate compound, an emulsifier obtained by reacting a dialkanolamine, a polyisocyanate compound and a polyisocyanate compound A reaction product etc. can be mentioned. Among these, a reaction product of an alkoxy polyalkylene glycol and a polyisocyanate compound is particularly preferable because of excellent water dispersibility.

Examples of the polyisocyanate compound used in the water-dispersed curing agent in the present invention include 1,4-diisocyanate butane, ethyl (2,6-diisocyanate) hexane, 1,6-diisocyanate hexane, 1,9-diisocyanate nonane, , 12-diisocyanate dodecane, aliphatic diisocyanates such as 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanate hexane; 1,3,6-triisocyanate hexane, 1,8-diisocyanate-4 Aliphatic triisocyanates such as isocyanate methyl octane and 2-isocyanatoethyl-2,6-diisocyanate hexane; 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 1,3- or 1,4-diisocyanate cyclohexane 3, 5, 5 Cycloaliphatic diisocyanates such as trimethyl-1-isocyanate-3- (isocyanatomethyl) cyclohexane, 4,4′-diisocyanate dicyclohexylmethane, 2,5- or 2,6-diisocyanatomethylnorbornane; 2,5- or 2,6 -Alicyclic triisocyanates such as bis (isocyanatemethyl) -2-isocyanatopropylnorbornane; 1,3-diisocyanatexylylene (1,3-bis (isocyanatemethyl) benzene), 1,3-bis (isocyanatemethyl)- Aralkylene diisocyanates such as 2,4,5,6-tetramethylbenzene; 1,4- or 1,3-diisocyanate benzene, 1,3- or 1,4-diisocyanate-2-methylbenzene, bis (isocyanate phenyl) Methane, 1,5 Aromatic diisocyanates such as diisocyanate naphthalene, 4,4-diisocyanate phenyl, 4,4′-diisocyanate-3,3′-dimethyldiphenyl, 3-methyl-4,4′-diisocyanate diphenylmethane, 4,4′-diisocyanate diphenyl ether; Aromatic triisocyanates such as tris (isocyanatephenyl) methane and tris (isocyanatephenyl) thiophosphate; and diisocyanates or polyisocyanates having a uretdione structure obtained by cyclizing and dimerizing the isocyanate groups of the diisocyanate or triisocyanate; Polyisocyanate having an isocyanurate structure obtained by cyclization and trimerization of the isocyanate groups of the diisocyanate or triisocyanate. A polyisocyanate having a burette structure obtained by reacting the isocyanate group of the diisocyanate or triisocyanate with water; having an oxadiazine trione structure obtained by reacting the isocyanate group of the diisocyanate or triisocyanate with carbon dioxide Polyisocyanate; polyisocyanate obtained by reacting the above diisocyanate or triisocyanate with a compound containing active hydrogen such as polyhydroxy compound, polycarboxy compound, polyamine compound, and the like. These may be used alone or in combination of two or more. Can be used.

  Examples of the hydrophilic group introduced into the polyisocyanate compound of the present invention include polymethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monolauryl ether, polyethylene glycol phenyl ether, Polyethylene glycol alkyl phenyl ether, polyethylene glycol phenyl phenyl ether, polyethylene glycol styryl phenyl ether, polyethylene glycol naphthyl ether, polyoxyethylene-oxypropylene (random and / or block) glycol monomethyl ether, polyoxyethylene-oxytetramethylene random and / or Or block It can be exemplified glycol polybutylene glycol monomethyl ether. As these alkoxy polyalkylene glycols, those having a molecular weight of preferably from 100 to 5,000, more preferably from 300 to 2,000 can be suitably used.

  Specific examples of the water-dispersed curing agent of the polyisocyanate compound include Desmodur series DA-L, DN, XP2410, XP2565, XP2671 (manufactured by Bayer), Bayhydrur series 304, 305, 3100, XP2655, 401-70. 5140, BLXP2669, BLXP2706, VPLS2150BA, VPLS2240, VPLS2306, VPLS2310, XP2451, XP2487 / 1, XP2547, XP2655, XP2700, etc., as well as various Duranate (registered trademark) manufactured by Asahi Kasei Chemicals, namely Duranate WB40-B40, 40 Available as 80D, Duranate WT20-100, Duranate WT30-100, etc.

  Among the water-dispersed curing agents of the polyisocyanate compound, aliphatic or alicyclic diisocyanates or triisocyanates, aralkylene diisocyanates, or polyisocyanates derived from them are preferable in terms of weather resistance and pot life. . Further, as the polyisocyanate compound, those having a structure such as burette, isocyanurate, urethane, uretdione, and allophanate in the molecule are preferable. Those having a burette structure are excellent in adhesion, those having an isocyanurate structure are excellent in weather resistance, and those having a urethane structure using an alcohol compound having a long side chain are excellent in elasticity and extensibility. In addition, those having a uretdione structure or an allophanate structure are characterized by low viscosity.

  The curable composition for water-based paints of the present invention includes a curing accelerator (catalyst), a filler, a flame retardant, a dye, an organic or inorganic pigment, a mold release agent, a fluidity modifier, and a plasticizer depending on various applications. Antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, colorants, solvents and the like can be added.

  Examples of the curing accelerator include monoamine triethylamine, N, N-dimethylcyclohexylamine, diamine tetramethylethylenediamine, other triamines, cyclic amines, alcohol amines such as dimethylethanolamine, ether amines, and the like. . Examples of the metal catalyst include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octylate, dibutyltin dilaurate, tin octylate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, Commonly used materials such as zinc octylate, zinc neodecanoate, phosphine, and phospholine can be used.

  Fillers and pigments include woven fabric, glass fiber, carbon fiber, polyamide fiber, mica, kaolin, bentonite, metal powder, azo pigment, carbon black, clay, silica, talc, gypsum, white alumina, barium carbonate, resin fine particles Commonly used ones can be used.

  Among them, it is more preferable to use resin fine particles and a matting agent in order to obtain the intended soft feel and high-quality appearance.

  The resin fine particles used in the present invention include cross-linked acrylic fine particles, polyester urethane resin, cross-linked polyurethane fine particles, etc., but the obtained coating film has acid resistance, alkali resistance, alcohol resistance, oil resistance, heat resistance, heat resistance, and the like. In order to improve abrasion, urethane-based fine particles that are three-dimensionally cross-linked are preferable.

  The average particle diameter of the polyurethane fine particles used in the present invention is 2 to 20 μm. If the average particle diameter is 2 μm or more, the gloss of the resulting coating film is not increased, a high-quality feeling is obtained, and a soft feeling is also obtained, which is preferable. If the average particle diameter is 20 μm or less, the wear properties of the resulting coating film are not lowered, and the soft feeling of the surface is not impaired, which is preferable. A more preferable average particle diameter is 4 to 15 μm, and further preferably 5 to 10 μm.

  The addition amount of the polyurethane fine particles is 3 to 30% by mass of the total solid content contained in the coating composition. If the content of the polyurethane fine particles is 3% by mass or more, a soft feeling of the obtained coating film can be obtained, and if the content of the polyurethane fine particles is 30% by mass or less, the resulting coating film has an abrasion property. Since it does not deteriorate extremely, it is preferable. The amount of the polyurethane-based fine particles added is preferably 5 to 20%, more preferably 8 to 15% by mass.

  Specific examples of the polyurethane-based fine particles include Art Pearl series (trade name, manufactured by Nippon Negami Kogyo Co., Ltd.), Dimic Beads (trade name, manufactured by Dainichi Seika), and the like.

In the present invention, a silica-based matting agent is used to further improve the strength, blocking property and scratch resistance of the coating film surface obtained, and to adjust the coating film gloss.
Usable silica mats include finely divided silica, colloidal silica and the like.

  The average particle size of the matting agent particles used is 0.1 to 10 μm. If the average particle diameter is 0.1 μm or more, the gloss of the resulting coating film is not excessively high, and a soft feeling is also obtained, which is preferable. On the other hand, if the average particle diameter is 10 μm or less, it is preferable because the wearability of the resulting coating film is not lowered and the transparency of the coating film is not impaired. A more preferable average particle diameter is 0.2 to 8 μm, and further preferably 0.5 to 5 μm.

  The addition amount of the silica-based matting agent particles in the present coating composition is 3 to 30% by mass of the total solid content contained in the coating composition. When the content of the silica-based matting agent particles is 3% by mass or more, a soft feeling of the obtained coating film is obtained, and when the content of the silica-based matting agent particles is 30% by mass or less, it is obtained. This is preferable since the wear resistance of the coating film does not extremely deteriorate. The amount of silica-based matting agent particles added is preferably 5 to 20% by mass, more preferably 8 to 15% by mass.

  Specific examples of matting agents include Degussa AcemattOK, TS, OP series, Fuji Silysia Chemical Co., Ltd. Cicilia, Silo Hovic, Cyros Sphere series, Fuso Chemical Co., Ltd. Quatron series, ) Tokuyama Fine Seal, Tosoh Silica Co., Ltd. Nipsil Series, Mizusawa Chemical Co., Ltd. Mizukasil Co., Ltd. (all are trade names).

  Moreover, about a matting agent and a resin bead, you may use together one or more types of matting agents and a resin bead as needed.

  As the release agent, fluidity adjusting agent, and leveling agent, silicone, aerosil, wax, stearate, polysiloxane such as BYK-307,348 (manufactured by BYK Chemical Co., Ltd.), and the like are used.

  As the additive used in the present invention, at least an antioxidant, a light stabilizer and a heat stabilizer are preferably used. These antioxidants include phosphoric acid, phosphorous acid aliphatic, aromatic or alkyl substituted aromatic esters, hypophosphorous acid derivatives, phenylsulfonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphine. Phosphines, phosphorus compounds such as dialkyl bisphenol A diphosphites; phenol derivatives, particularly hindered phenol compounds, choethers, dithioates; compounds containing sulfur such as mercaptobenzimidazoles, thiocarbanilides, thiodipropionates; tin malates Tin compounds such as dibutyltin monoxide can be used.

  These may be used alone or in combination of two or more.

  The curable composition for water-based paints used in the present invention can be used by adding an organic solvent that acts as a film-forming aid. The organic solvent that acts as a film-forming aid is distributed in the polymer particles and / or in the aqueous phase, improves the film-forming property, swells the particle surface, and promotes the crosslinking reaction with the crosslinking agent. The surface tension of water can be reduced, the dispersibility of the pigment and the wettability of the curable composition for water-based paints with respect to the substrate can be improved, and the workability of coating and the substrate adhesion can be improved.

  In the present invention, particularly representative organic solvents that can be suitably used include 3-methoxybutanol, 3-methoxy-3-methylbutanol, ethylene glycol monoethyl ether, ethylene glycol mono (n- or iso) propyl ether, Ethylene glycol mono (n-, iso or tert-) butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono (n- or iso) propyl ether, propylene glycol mono ( n-, iso or tert-) butyl ether, mono (di) ethylene glycol dimethyl ether, mono (di) ethylene glycol diethyl Examples include ether, mono (di) ethylene glycol dibutyl ether, dimethylformamide, N-methylpyrrolidone or ethylene glycol methyl ether acetate, CS-12 (manufactured by Chisso), diisopropyl glutarate, diisopropyl adipate, and the like. . Among these, aprotic solvents such as mono (di) ethylene glycol dimethyl ether, mono (di) ethylene glycol diethyl ether, mono (di) ethylene glycol dibutyl ether do not react with isocyanate groups and have low odor. In addition, it is useful not only as a film-forming aid but also as an antifreezing agent, and also has good affinity for a polyisocyanate compound and enables more uniform crosslinking, so that it can be used effectively.

  As a coating method of the curable composition for water-based soft feel paints of the present invention, for example, the following method is used. That is, the polyurethane aqueous dispersion (a) and the polyurethane aqueous dispersion (b) are stirred and mixed, and if necessary, additives such as a matting agent and resin beads are uniformly dispersed. A water-dispersible curing agent (c) of Nart is mixed and uniformly dispersed to prepare a curable composition for paint. The curable composition for coating is applied to a substrate by spraying, rolls, brushing or the like. The curing agent (c) is preferably added immediately before use.

  The aqueous dispersion composition for soft feel paints of the present invention can be preferably used for home appliances, OA products, toys, automobile interior parts, leather surface treatment, woodworking surface treatment, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example etc., this invention is not limited at all by these examples. In the following examples and comparative examples, various physical properties of the polyurethane film were measured according to the following test methods.
<Test method>
1. Soft feeling The soft feeling was evaluated based on the feeling when the surface of the coating plate was touched by hand. Judgment results were expressed in the following notation.

○ (good): good soft feeling △ (possible): relatively good soft feeling × (impossible): no soft feeling.
2. Liquid resistance 1) Acid resistance: The appearance of the coating film after visual immersion in a 0.1N H ₂ SO ₄ aqueous solution at room temperature for 24 hours is visually determined.

◎ (excellent): no change in appearance ○ (good): almost no change in appearance △ (possible): very small blister × (impossible): clear blister 2) Alkali resistance: immersed in 0.1N NaOH aqueous solution at room temperature for 24 hours Visual judgment of the appearance of the subsequent coating film.

◎ (excellent): No change in appearance ○ (good): Almost no change in appearance △ (possible): Very small bulge x (impossible): Clear bulge 3) Ethanol resistance: Immerse in 50% EtOH aqueous solution at room temperature for 4 hours Visual judgment of the appearance of the subsequent coating film.

◎ (excellent): no change in appearance ○ (good): almost no change in appearance △ (possible): very small bulge × (impossible): clear bulge Scratch resistance: scratched with a nail to visually determine the degree of damage to the coating film.

○ (good): not scratched Δ (possible): scratched slightly × (not possible): apparently scratched Abrasion resistance It measured using the Taber type abrasion tester according to the method of JIS K5600-5-8. The weight before the abrasion test and the change in the weight of the coated film after the abrasion test (500 rotations) were measured and expressed.
<Method for producing polycarbonate diol>
(Production Example 1)
A 2 L separable flask equipped with a stirrer, thermometer, and vacuum jacketed Oldershaw with a reflux head at the top was charged with 382 g of 1,5-pentanediol, 433 g of 1,6-hexanediol, and 650 g of ethylene carbonate, and stirred at 70 ° C. After dissolution, 0.015 g of lead acetate trihydrate was added as a catalyst. The mixture was heated in an oil bath set at 175 ° C., and the reaction was carried out for 12 hr while removing a part of the fraction from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 140 ° C. and a degree of vacuum of 1.0 to 1.5 kPa. Thereafter, the Oldershaw was replaced with a simple distillation apparatus, heated in an oil bath set at 180 ° C., the internal temperature of the flask was reduced to 140 to 150 ° C., the degree of vacuum was reduced to 0.5 kPa, and the diol remaining in the separable flask and Ethylene carbonate was removed. Thereafter, the setting of the oil bath was raised to 185 ° C., and the reaction was further performed for 4 hours while removing the diol produced at an internal temperature of the flask of 160 to 165 ° C. By this reaction, a viscous liquid was obtained at room temperature. The obtained polycarbonate diol (hereinafter referred to as PCD) has an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). there were. This is PCD1.
(Production Example 2)
In Production Example 1, 382 g of 1,5-pentanediol, 433 g of 1,6-hexanediol and 650 g of ethylene carbonate were charged and dissolved by stirring at 70 ° C., and then 0.015 g of lead acetate trihydrate was added as a catalyst. The mixture was heated in an oil bath set at 175 ° C., and the reaction was carried out for 12 hr while removing a part of the fraction from the reflux head at a reflux ratio of 4 at an internal temperature of the flask of 140 ° C. and a degree of vacuum of 1.0 to 1.5 kPa. Thereafter, the setting of the oil bath was raised to 185 ° C., the internal temperature of the flask was changed to 160 to 165 ° C., and the reaction was further performed for 3 hr while removing the diol produced. The obtained PCD had an OH value of 112.2 (molecular weight 1000) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). This is PCD2.
(Production Example 3)
In Production Example 2, after replacing the Oldershaw with a simple distillation apparatus, the setting of the oil bath was raised to 185 ° C., the internal temperature of the flask was changed to 160 to 165 ° C., and the time for removing the diol produced was 1.5 hr. The synthesis was performed in the same manner except that. The obtained PCD had an OH value of 224.4 (molecular weight of 500) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). This is PCD3.
(Production Example 4)
In Production Example 2, after replacing the Older Shaw with a simple distillation apparatus, the oil bath was set to 185 ° C., the flask internal temperature was set to 160 to 165 ° C., and the time for removing the diol produced was 2 hours. Were synthesized in the same manner. The obtained PCD had an OH value of 140.3 (molecular weight 800) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). This is PCD4.
(Production Example 5)
Synthesis was performed in the same manner as in Production Example 1, except that 594 g of 1,4-butanediol and 87 g of 1,6-hexanediol were used instead of 1,5-pentanediol and 1,6-hexanediol. . The obtained PCD had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 1,4-butanediol / 1,6-hexanediol = 90/10 (molar ratio). This is PCD5.
(Production Example 6)
In Production Example 1, the same method except that 330 g of 2-methyl-1,3-propanediol and 330 g of 1,4-butanediol were used instead of 1,5-pentanediol and 1,6-hexanediol. Synthesis was performed. The obtained PCD had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (molar ratio). This is PCD6.
(Production Example 7)
Synthesis was performed in the same manner as in Production Example 1 except that 462 g of 1,4-butanediol and 260 g of 1,6-hexanediol were used instead of 1,5-pentanediol and 1,6-hexanediol. . The obtained PCD had an OH value of 56.1 (molecular weight 2000) and a copolymer composition of 1,4-butanediol / 1,6-hexanediol = 70/30 (molar ratio). This is PCD7.
(Production Example 8)
In Production Example 1, after replacing the Oldershaw with a simple distillation apparatus, the setting of the oil bath was raised to 185 ° C., the flask internal temperature was 160 to 165 ° C., and the time for removing the produced diol was extended to 8 hr. Were synthesized in the same manner. The obtained PCD had an OH value of 28.1 (molecular weight 4000) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). This is PCD8.
(Production Example 9)
In Production Example 2, after replacing the Older Shaw with a simple distillation apparatus, the setting of the oil bath was raised to 185 ° C., the internal temperature of the flask was changed to 160 to 165 ° C., and the time for removing the generated diol was set to 1 hr. Were synthesized in the same manner. The obtained PCD had an OH value of 280.5 (molecular weight 400) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). This is PCD9.
(Production Example 10)
In Production Example 1, after replacing the Oldershaw with a simple distillation apparatus, the setting of the oil bath was raised to 185 ° C., the flask internal temperature was 160 to 165 ° C., and the time for removing the diol produced was extended to 10 hr. Were synthesized in the same manner. The OH value of the obtained PCD was 24.9 (molecular weight 4500), and the copolymer composition was 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). This is designated as PCD10.
<Synthesis method of polyurethane emulsion>
(Synthesis Example 1)
PCD1 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask, number average molecular weight 2000) 200.00 g (0.1 Mol) was weighed and dissolved with 150 g of MEK. A solution obtained by dissolving 13.42 g (0.1 mol) of dimethylolpropionic acid (DMPA) in 50.00 g of MEK and neutralized with 10.63 g of triethylamine (TEA) and 50.46 g (0.3 mol) of hexamethylene diisocyanate (HDI) ) Was added to the flask and an additional 52.65 g of MEK was added and sealed with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was performed at 60 ° C. for 8 hours until no unreacted OH group disappeared to obtain 527.16 g of an NCO-terminated polyurethane prepolymer solution. . The prepolymer solution was set at 30 ° C. and stirred at 250 rpm, and 780 g of distilled water was added dropwise over 30 minutes to emulsify, followed by 3.01 g (0.05 mol) of ethylenediamine (EDA). An aqueous solution dissolved in 10 g of water was added, and a chain extension reaction was performed at 30 ° C. for 1 hour. Further, the dispersion was decompressed to remove MEK, and 1067.5 g of polyurethane emulsion 1 (PUD1) having a nonvolatile fraction of 25.0% was obtained. When the molecular weight (polystyrene conversion) of the obtained polyurethane was measured by GPC, it was number average molecular weight 23000 and weight average molecular weight 86500.

  The mass content fraction of each raw material in the synthesis example is calculated by the following formula and is as follows.

[a]: Carboxyl group and / or sulfonic acid group-containing polyol monomer weight
[b]: Polycarbonate diol weight
[c]: Polyisocyanate compound monomer weight
[d]: Weight of other copolymerizable monomers (TMP, etc.)
Content of a (%) = 100 x [a] / ([a] + [b] + [c] + [d])
Content ratio of b (%) = 100 x [b] / ([a] + [b] + [c] + [d])
c content (%) = 100 x [c] / ([a] + [b] + [c] + [d])
d content (%) = 100 x [d] / ([a] + [b] + [c] + [d])
[c]: HDI / [b]: PCD1 / [a]: DMPA = 19.1 / 75.8 / 5.1 (mass%)
(Synthesis Example 2)
PCD2 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 1000) 180.00 g (0.18 Mol) was weighed and dissolved in 250 g of MEK. Dimethylolpropionic acid ((DMPA) 22.8 g (0.17 mol)) and trimethylolpropane (TMP) 8.94 g (0.067 mol) were added as powders and then hexamethylene diisocyanate (HDI) 50.46 g. (0.3 mol) was added to the flask and sealed with N ₂ gas in a reaction with a reflux condenser, thermometer and stirrer at 60 ° C. over 8 hours until no unreacted NCO groups were present. After performing the urethanization reaction, the prepolymer solution was cooled to 30 ° C. and neutralized with 17.2 g of triethylamine (TEA) while stirring at 100 rpm to obtain 529.4 g of a polyurethane prepolymer solution having an OH group terminal. Subsequently, the prepolymer was stirred at 250 rpm, and 769 g of distilled water was added dropwise in 30 minutes to emulsify. The liquid was heated to 80 ° C., and MEK was removed to obtain 1048.4 g of polyurethane emulsion 2 (PUD2) having a nonvolatile fraction of 25.0%. It was as follows.

HDI / PCD2 / DMPA / TMP = 19.2 / 68.7 / 8.7 / 3.4 (mass%)
(Synthesis Example 3)
In Synthesis Example 1, Synthesis Example 1 except that 66.69 g (0.3 mol) of isophorone diisocyanate (IPDI) was used instead of hexamethylene diisocyanate (HDI), and the reaction temperature and reaction time were changed to 80 ° C. and 6 hours. Synthesis was performed in the same manner to obtain 543.38 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was emulsified and dispersed in the same manner as in Synthesis Example 1, and then subjected to a chain extension reaction with 3.00 g (0.05 mol) of ethylenediamine (EDA), and further MEK was removed to obtain a nonvolatile fraction. 1133.7 g of 25.0% polyurethane emulsion 3 (PUD3) were obtained. When the molecular weight (polystyrene conversion) of the obtained polyurethane was measured by GPC, it was number average molecular weight 23000 and weight average molecular weight 88000.

  The mass content fraction of each raw material in the synthesis example was as follows.

IPDI / PCD1 / DMBA = 23.8 / 71.4 / 4.8 (mass%)
(Synthesis Example 4)
In Synthesis Example 2, polymer was prepared in the same manner as in Synthesis Example 2, except that 66.69 g (0.30 mol) of isophorone diisocyanate (IPDI) was used instead of HDI and the reaction temperature and reaction time were changed to 80 ° C. for 6 hours. Was synthesized. At the time of emulsification, 818 g of distilled water was used, and 1113.6 g of polyurethane emulsion 4 (PUD4) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

IPDI / PCD2 / DMPA / TMP = 24.0 / 64.6 / 8.2 / 3.2 (mass%)
(Synthesis Example 5)
118.4 g (0.059) of PCD1 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50 with a number average molecular weight of 2000) in a separable flask. Mol) was weighed and dissolved with 140 g of MEK. After dissolving 13.41 g (0.10 mol) of dimethylolpropionic acid (DMPA) and 3.65 g (0.027 mol) of trimethylolpropane (TMP) in 50.00 g of MEK, the solution was neutralized with 10.63 g of triethylamine (TEA). The solution and 66.69 g (0.3 mol) of isophorone diisocyanate (IPDI) were added into the flask and sealed with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, urethanization reaction was carried out at 80 ° C. for 6 hours until no unreacted OH group disappeared to obtain 402.78 g of a polyurethane prepolymer solution having an NCO group terminal. . The prepolymer solution was set at 30 ° C. and stirred at 250 rpm, and 595 g of distilled water was added dropwise over 30 minutes to emulsify, followed by 3.01 g (0.05 mol) of ethylenediamine (EDA). An aqueous solution dissolved in 10 g of water was added, and a chain extension reaction was performed at 30 ° C. for 1 hour. Further, the dispersion was decompressed to remove MEK, and 820.8 g of polyurethane emulsion 5 (PUD5) having a nonvolatile fraction of 25.0% was obtained.
The mass content fraction of each raw material in the synthesis example was as follows.

IPDI / PCD1 / DMPA / TMP = 33.0 / 58.6 / 6.6 / 1.8 (mass%)
(Synthesis Example 6)
PCD2 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 1000) 200.00 g (0.20 Mol) was weighed and dissolved in 250 g of MEK. After charging 13.41 g (0.10 mol) of dimethylol propionic acid (DMPA) as powder, 44.46 g (0.20 mol) of isophorone diisocyanate (IPDI) was added to the flask and sealed with N ₂ gas. did. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was carried out at 80 ° C. for 6 hours until no unreacted NCO groups disappeared, and then the prepolymer solution was cooled to 30 ° C. and 100 rpm The mixture was neutralized with 10.12 g of triethylamine (TEA) with stirring to obtain 518.0 g of a polyurethane prepolymer solution having an OH group terminal. Subsequently, the prepolymer was stirred at 250 rpm, and 763 g of distilled water was added dropwise in 30 minutes to emulsify. The dispersion was further heated to 80 ° C. to remove MEK, and 1031.0 g of polyurethane emulsion 6 (PUD6) having a nonvolatile content of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

IPDI / PCD2 / DMPA = 17.2 / 77.6 / 5.2 (mass%)
(Synthesis Example 7)
In Synthesis Example 1, 50 g of PCD3 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50 with a number average molecular weight of 500) instead of PCD1 (0.10 mol), instead of hexamethylene diisocyanate (HDI), 78.71 g (0.3 mol) of hydrogenated MDI (H ₁₂ MDI) and 130 g of MEK solvent were used. The synthesis was performed in the same manner as in Synthesis Example 1 except that the time was set to obtain 282.75 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was synthesized by emulsifying and dispersing 415 g of distilled water in the same manner as in Synthesis Example 1, and then dropping an aqueous solution in which 3.01 g (0.05 mol) of ethylenediamine (EDA) was dissolved in 10 g of distilled water. A chain extension reaction was carried out in the same manner as in Example 1, and MEK was further removed to obtain 580.8 g of polyurethane emulsion 7 (PUD7) having a nonvolatile fraction of 25.0%. The mass content fraction of each raw material in the synthesis example was as follows.

H ₁₂ MDI / PCD3 / DMPA = 55.4 / 35.2 / 9.4 (mass%)
(Synthesis Example 8)
PCD1 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask, number average molecular weight 2000) 200.00 g (0.1 Mol) was weighed and dissolved in 210 g of MEK. After charging 6.71 g (0.05 mol) of dimethylol propionic acid (DMPA) as powder, 16.82 g (0.1 mol) of hexamethylene diisocyanate (HDI) was added to the flask, and N ₂ gas was used. Sealed. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted NCO groups disappeared, and then the prepolymer solution was cooled to 30 ° C. and 100 rpm The mixture was neutralized with 5.06 g of triethylamine (TEA) with stirring to obtain 438.6 g of a polyurethane prepolymer solution having an OH group terminal. Subsequently, the prepolymer was stirred at 250 rpm, and 665 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 893.6 g of polyurethane emulsion 8 (PUD8) having a nonvolatile content of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD1 / DMPA = 7.5 / 89.5 / 3.0 (mass%)
(Synthesis Example 9)
In Synthesis Example 1, 80 g of PCD4 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol in a 50/50 molar ratio instead of PCD1 and having a number average molecular weight of 800) (0.1 mol) was used and synthesized in the same manner as in Synthesis Example 1 except that the solvent MEK was 130 g to obtain 284.5 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was subjected to a chain elongation reaction with an aqueous solution in which 420 g of distilled water was added dropwise and emulsified and dispersed in the same manner as in Synthesis Example 1, and then 3.00 g (0.05 mol) of ethylenediamine (EDA) was dissolved in 10 g of water. By carrying out and removing MEK, 587.5 g of polyurethane emulsion 9 (PUD9) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD4 / DMBA = 35.1 / 55.6 / 9.3 (mass%)
(Synthesis Example 10)
PCD1 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 2000) 180.00 g (0.090 Mol) was weighed and dissolved in 210 g of MEK. After charging 11.40 g (0.085 mol) of dimethylolpropionic acid (DMPA) and 4.47 g (0.033 mol) of trimethylolpropane (TMP) in powder form, 25.23 g of hexamethylene diisocyanate (HDI) ( 0.15 mol) was added into the flask and sealed with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted NCO groups disappeared, and then the prepolymer solution was cooled to 30 ° C. and 100 rpm The mixture was neutralized with 8.60 g of triethylamine (TEA) with stirring to obtain 439.7 g of a polyurethane prepolymer solution having an OH group terminal. Subsequently, the prepolymer was stirred at 250 rpm, and 655 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 884.7 g of polyurethane emulsion 10 (PUD10) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD2 / DMPA / TMP = 11.4 / 81.4 / 5.2 / 2.0 (mass%)
(Synthesis Example 11)
In Synthesis Example 1, 200 g of PCD5 (polycarbonate diol obtained by copolymerizing 1,4-butanediol and 1,6-hexanediol at a molar ratio of 90/10, number average molecular weight 2000) instead of PCD1 The synthesis was performed in the same manner as in Synthesis Example 1 except that (0.1 mol) was used, to obtain 527.15 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was subjected to a chain extension reaction with an aqueous solution in which 3.00 g (0.05 mol) of ethylenediamine (EDA) was dissolved in 10 g of water after dropwise addition of distilled water in the same manner as in Synthesis Example 1 and emulsification and dispersion. Further, by removing MEK, 1067.5 g of polyurethane emulsion 11 (PUD11) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD5 / DMPA = 19.1 / 75.8 / 5.1 (mass%)
(Synthesis Example 12)
In Synthesis Example 10, instead of PCD1, PCD5 (polycarbonate diol obtained by copolymerizing 1,4-butanediol and 1,6-hexanediol at a molar ratio of 90/10 with a number average molecular weight of 2000) is 180. Except that 0.000 g (0.090 mol) was used, 884.7 g of polyurethane emulsion 12 (PUD 12 ) having a nonvolatile fraction of 25.0% was obtained in the same manner as in Synthesis Example 10. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD5 / DMPA / TMP = 11.4 / 81.4 / 5.2 / 2.0 (mass%)
(Synthesis Example 13)
In Synthesis Example 1, instead of PCD1, PCD6 (polycarbonate diol obtained by copolymerizing 2-methyl-1,3-propanediol and 1,4-butanediol at a molar ratio of 50/50, has a number average molecular weight. 2000) was used in the same manner as in Synthesis Example 1 except that 200 g (0.1 mol) was used to obtain 527.15 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was subjected to a chain extension reaction with an aqueous solution in which 3.00 g (0.05 mol) of ethylenediamine (EDA) was dissolved in 10 g of water after dropwise addition of distilled water in the same manner as in Synthesis Example 1 and emulsification and dispersion. Further, by removing MEK, 1067.5 g of polyurethane emulsion 13 (PUD13) having a non-volatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD6 / DMPA = 19.1 / 75.8 / 5.1 (mass%)
(Synthesis Example 14)
In Synthesis Example 10, instead of PCD1, PCD6 (polycarbonate diol obtained by copolymerizing 2-methyl-1,3-propanediol and 1,4-butanediol at a molar ratio of 50/50, has a number average molecular weight. Except for using 180.00 g (0.090 mol) of 2000), 884.7 g of polyurethane emulsion 14 (PUD14) having a nonvolatile content of 25.0% was obtained in the same manner as in Synthesis Example 10. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD6 / DMPA / TMP = 11.4 / 81.4 / 5.2 / 2.0 (mass%)
(Synthesis Example 15)
In Synthesis Example 1, 200 g of PCD7 (polycarbonate diol obtained by copolymerizing 1,4-butanediol and 1,6-hexanediol at a molar ratio of 70/30, number average molecular weight 2000) instead of PCD1 The synthesis was performed in the same manner as in Synthesis Example 1 except that (0.1 mol) was used, to obtain 527.15 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was subjected to a chain extension reaction with an aqueous solution in which 3.00 g (0.05 mol) of ethylenediamine (EDA) was dissolved in 10 g of water after dropwise addition of distilled water in the same manner as in Synthesis Example 1 and emulsification and dispersion. Further, by removing MEK, 1067.5 g of polyurethane emulsion 15 (PUD 15 ) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD7 / DMPA = 19.1 / 75.8 / 5.1 (mass%)
(Synthesis Example 16)
Synthesis was performed in the same manner as in Synthesis Example 1 except that 14.81 g (0.1 mol) of dimethylolbutanoic acid (DMBA) was used instead of dimethylolbutanoic acid (DMBA) in Synthesis Example 1, and the NCO group 528.56 g of polyurethane prepolymer solution at the end was obtained. The prepolymer solution was emulsified and dispersed in the same manner as in Synthesis Example 1 except that the amount of distilled water used for emulsification was changed from 780 g to 784 g, and then chained with 3.00 g (0.05 mol) of ethylenediamine (EDA). By carrying out an elongation reaction and further removing MEK, 1072.9 g of polyurethane emulsion 16 (PUD16) having a nonvolatile fraction of 25.0% was obtained. When the molecular weight (polystyrene conversion) of the obtained polyurethane was measured by GPC, it was the number average molecular weight 22000 and the weight average molecular weight 87000.

  The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD1 / DMBA = 19.0 / 75.4 / 5.6 (mass%)
(Synthesis Example 17)
PCD8 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 4000) 200.00 g (0.05 Mol) was weighed and dissolved with 150 g of MEK. A solution obtained by dissolving 6.71 g (0.05 mol) of dimethylolpropionic acid (DMPA) in 50.00 g of MEK and neutralized with 10.63 g of triethylamine (TEA) and 25.23 g (0.15 mol) of hexamethylene diisocyanate (HDI) ) Was added to the flask, and 25.0 g of MEK was further added, followed by sealing with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was performed at 60 ° C. for 8 hours until no unreacted OH group disappeared to obtain 462.25 g of a polyurethane prepolymer solution terminated with an NCO group. . The prepolymer solution was set at 30 ° C. and stirred at 250 rpm, and 690 g of distilled water was added dropwise in 30 minutes to emulsify, followed by 1.50 g (0.025 mol) of ethylenediamine (EDA). An aqueous solution dissolved in 5 g of water was added, and a chain extension reaction was performed at 30 ° C. for 1 hour. Further, the dispersion was reduced in pressure to remove MEK, and 933.8 g of polyurethane emulsion 17 (PUD17) having a nonvolatile fraction of 25.0% was obtained.

  The mass content fraction of each raw material in the synthesis example was calculated by the following calculation formula and was as follows.

HDI / PCD8 / DMPA = 10.9 / 86.2 / 2.9 (mass%)
(Synthesis Example 18)
In Synthesis Example 2, instead of PCD1, PCD4 (a polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50, a number average molecular weight of 800) is 144. A prepolymer was synthesized by the same method as in Synthesis Example 2 except that 0.0 g (0.18 mol) was used and the MEK solvent amount was 200 g. The amount of distilled water used during emulsification was 661 g. As a result, 904.4 g of polyurethane emulsion 18 (PUD18) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD4 / DMPA / TMP = 22.3 / 63.7 / 10.0 / 4.0 (mass%)
(Synthesis Example 19)
In Synthesis Example 1, 40 g of PCD9 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50 with a number average molecular weight of 400) instead of PCD1 (0.1 mol) was used, and synthesis was carried out in the same manner as in Synthesis Example 1 except that the solvent MEK was 90 g, to obtain 204.5 g of an NCO group-terminated polyurethane prepolymer solution. The prepolymer solution was subjected to a chain extension reaction with an aqueous solution in which 300 g of distilled water was added dropwise and emulsified and dispersed in the same manner as in Synthesis Example 1, and then 3.00 g (0.05 mol) of ethylenediamine (EDA) was dissolved in 10 g of water. By carrying out and removing MEK, 427.5 g of polyurethane emulsion 19 (PUD19) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD9 / DMBA = 48.6 / 38.5 / 12.9 (mass%)
(Synthesis Example 20)
PCD9 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 400) 160.0 g (0.40 Mol) was weighed and dissolved with 230 g of MEK. After charging 26.83 g (0.20 mol) of dimethylol propionic acid (DMPA) as powder, 67.28 g (0.4 mol) of hexamethylene diisocyanate (HDI) was added to the flask, and N ₂ gas was used. Sealed. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted NCO groups disappeared, and then the prepolymer solution was cooled to 30 ° C. and 100 rpm The mixture was neutralized with 20.24 g of triethylamine (TEA) with stirring to obtain 504.34 g of a polyurethane prepolymer solution having an OH group terminal. Subsequently, the prepolymer was stirred at 250 rpm, and 742 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 1016.3 g of polyurethane emulsion 20 (PUD20) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD9 / DMPA = 26.4 / 63.0 / 10.6 (mass%)
(Synthesis Example 21)
PCD8 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 4500) 225.0 g (0.05 Mol) was weighed and dissolved with 150 g of MEK. A solution obtained by dissolving 6.71 g (0.05 mol) of dimethylolpropionic acid (DMPA) in 50.00 g of MEK and neutralized with 10.63 g of triethylamine (TEA) and 25.23 g (0.15 mol) of hexamethylene diisocyanate (HDI) ) Was added to the flask, and 25.0 g of MEK was further added, followed by sealing with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted OH group disappeared to obtain 512.25 g of an NCO-terminated polyurethane prepolymer solution. . The prepolymer solution was set at 30 ° C. and stirred at 250 rpm, and 760 g of distilled water was added dropwise over 30 minutes to emulsify, followed by 1.50 g (0.025 mol) of ethylenediamine (EDA). An aqueous solution dissolved in 10 g of water was added, and a chain extension reaction was performed at 30 ° C. for 1 hour. The dispersion was further reduced in pressure to remove MEK, and 1033.8 g of polyurethane emulsion 21 (PUD21) having a nonvolatile fraction of 25.0% was obtained.

  The mass content fraction of each raw material in the synthesis example was calculated by the following calculation formula and was as follows.

HDI / PCD8 / DMPA = 9.8 / 87.6 / 2.6 (mass%)
(Synthesis Example 22)
PCD10 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask, number average molecular weight 4500) 225.0 g (0.050 Mol) was weighed and dissolved with 230 g of MEK. After charging 3.35 g (0.025 mol) of dimethylol propionic acid (DMPA) as powder, 8.41 g (0.05 mol) of hexamethylene diisocyanate (HDI) was added to the flask, and N ₂ gas was used. Sealed. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted NCO groups disappeared, and then the prepolymer solution was cooled to 30 ° C. and 100 rpm The mixture was neutralized with 2.53 g of triethylamine (TEA) while being stirred at 50 to obtain 469.3 g of an OH group-terminated polyurethane prepolymer solution. Subsequently, the prepolymer was stirred at 250 rpm, and 707 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 946.3 g of polyurethane emulsion 22 (PUD22) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD10 / DMPA = 3.6 / 95.0 / 1.4 (mass%)
(Synthesis Example 23)
In Synthesis Example 22, instead of PCD10, PCD8 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50, number average molecular weight 4000) 200. 424.3 g of an OH group-terminated polyurethane prepolymer solution was obtained in the same manner as in Synthesis Example 22 except that 0 g (0.050 mol) was used and the MEK solvent amount was 210 g. Subsequently, the prepolymer was stirred at 250 rpm, and 632 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 846.3 g of polyurethane emulsion 23 (PUD23) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD10 / DMPA = 4.0 / 94.4 / 1.6 (mass%)
(Synthesis Example 24)
PCD3 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 500) 200.0 g (0.40 Mol) was weighed and dissolved in 260 g of MEK. After charging 26.83 g (0.20 mol) of dimethylol propionic acid (DMPA) as powder, 67.28 g (0.4 mol) of hexamethylene diisocyanate (HDI) was added to the flask, and N ₂ gas was used. Sealed. In a reaction having a reflux condenser, a thermometer, and a stirrer, the urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted NCO groups disappeared, and then the prepolymer solution was cooled to 30 ° C. and 100 rpm The mixture was neutralized with 20.24 g of triethylamine (TEA) with stirring to obtain 574.34 g of an OH-terminated polyurethane prepolymer solution. Subsequently, the prepolymer was stirred at 250 rpm, and 862 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 1176.3 g of polyurethane emulsion 20 (PUD20) having a nonvolatile fraction of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD3 / DMPA = 22.9 / 68.0 / 9.1 (mass%)
(Synthesis Example 25)
PCD3 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 500) 40.0 g (0.08 Mol) was weighed and dissolved with 85 g of MEK. After charging 13.41 g (0.10 mol) of dimethylol propionic acid (DMPA) and 10.7 g (0.08 mol) of trimethylolpropane (TMP) as powder, triethylamine (TEA) 10 while stirring at 100 rpm Neutralized with .12 g, 33.64 g (0.20 mol) of hexamethylene diisocyanate (HDI) was added into the flask and sealed with N ₂ gas. In a reaction having a reflux condenser, a thermometer and a stirrer, the urethanization reaction was carried out at 60 ° C. for 8 hours until there was no unreacted NCO group, and then the prepolymer solution was cooled to 30 ° C. and OH 192.9 g of a polyurethane prepolymer solution at the base end was obtained. Subsequently, the prepolymer was stirred at 250 rpm, and 283 g of distilled water was added dropwise in 30 minutes to emulsify. Further, the dispersion was heated to 80 ° C. to remove MEK, and 390.9 g of polyurethane emulsion 25 (PUD25) having a nonvolatile content of 25.0% was obtained. The mass content fraction of each raw material in the synthesis example was as follows.

HDI / PCD3 / DMPA / TMP34.4 / 40.9 / 13.7 / 11.0 (mass%)
(Synthesis Example 26)
PCD3 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 500) 14.3 g (0.0286 Mol) was weighed and dissolved with 20 g of MEK. After dissolving 13.41 g (0.10 mol) of dimethylolpropionic acid (DMPA) and 6.39 g (0.0476 mol) of trimethylolpropane (TMP) in 50.00 g of MEK, 10.62 g (0.105) of triethylamine (TEA) was dissolved. Mol) and 50.46 g (0.30 mol) of hexamethylene diisocyanate (HDI) were added into the flask and sealed with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted OH group disappeared to obtain 165.18 g of a polyurethane prepolymer solution having an NCO group terminal. . The prepolymer solution was set at 30 ° C. and stirred at 250 rpm, and 245 g of distilled water was added dropwise over 30 minutes to emulsify, followed by 3.0 g (0.05 mol) of ethylenediamine (EDA). An aqueous solution dissolved in 7 g of water was added, and a chain extension reaction was performed at 30 ° C. for 1 hour. Further, the dispersion was decompressed to remove MEK, and 348.2 g of polyurethane emulsion 26 (PUD26) having a nonvolatile fraction of 25.0% was obtained.

  The mass content fraction of each raw material in the synthesis example was calculated by the following calculation formula and was as follows.

HDI / PCD3 / DMPA / TMP = 59.7 / 16.9 / 15.9 / 7.5 (mass%)
(Synthesis Example 27)
PCD3 (polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol at a 50/50 molar ratio in a separable flask with a number average molecular weight of 500) 20.0 g (0.04 Mol) was weighed and dissolved with 30 g of MEK. After dissolving 5.37 g (0.04 mol) of dimethylolpropionic acid (DMPA) and 10.7 g (0.08 mol) of trimethylolpropane (TMP) in 50.0 g of MEK, 4.05 g (0.04 mol) of triethylamine (TEA) Mol) and 25.23 g (0.15 mol) of hexamethylene diisocyanate (HDI) were added into the flask and sealed with N ₂ gas. In a reaction having a reflux condenser, a thermometer, and a stirrer, urethanization reaction was carried out at 60 ° C. for 8 hours until no unreacted OH group disappeared to obtain 170.61 g of a polyurethane prepolymer solution having an NCO group terminal. . The prepolymer solution was set at 30 ° C. and stirred at 250 rpm, and 260 g of distilled water was added dropwise in 30 minutes to emulsify, followed by 3.0 g (0.05 mol) of ethylenediamine (EDA). An aqueous solution dissolved in 5 g of water was added, and a chain extension reaction was performed at 30 ° C. for 1 hour. Further, the dispersion was reduced in pressure to remove MEK, and 358.6 g of polyurethane emulsion 27 (PUD27) having a nonvolatile fraction of 25.0% was obtained.

  The mass content fraction of each raw material in the synthesis example was calculated by the following calculation formula and was as follows.

HDI / PCD3 / DMPA / TMP = 58.3 / 23.1 / 6.2 / 12.4 (mass%)
Example 1
30 g of PUD 1 synthesized in Synthesis Example 1 and 30 g of PUD 2 having an OH end group synthesized in Synthesis Example 2 were mixed, and further, Duranate WB40-100 (trade name, burette type, NCO content 16. (6 wt%, manufactured by Asahi Kasei Chemicals) 3.47 g and 8.16 g of distilled water for adjusting the concentration were added to prepare a coating solution with a solid content of 25.8%.

  This coating solution was applied on an ABS plate and cured at 80 ° C. for 2 hours to obtain a coated plate having a film thickness of 40 to 50 μm.

The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 2)
A coated plate was prepared in the same manner as in Example 1 using PUD3 and PUD4, and the coating film properties were evaluated. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 3)
In Example 1, the coating properties were evaluated by changing the mixing ratio of PUD1 and PUD2. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
Example 4
In Example 1, the coating properties were evaluated by changing the mixing ratio of PUD1 and PUD2. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 5)
In Example 1, the molar ratio of the NCO group of the curing agent to the OH group of PUD2 was changed to NCO / OH = 2.5 for evaluation. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 6)
In Example 1, the evaluation was performed by changing the molar ratio of the NCO group of the curing agent to the OH group of PUD2 to NCO / OH = 0.9. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 7)
Evaluation was carried out by changing the curing agent of Example 1 to Duranate TPA100 (isocyanurate type, NCO content 23.1 wt%, manufactured by Asahi Kasei Chemicals). The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 8)
A coated plate was prepared in the same manner as in Example 1 using PUD5 and PUD6, and the coating film properties were evaluated. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
Example 9
A coated plate was produced in the same manner as in Example 1 using PUD7 and PUD8, and the coating film properties were evaluated. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 10)
A coated plate was prepared in the same manner as in Example 1 using PUD9 and PUD10, and the coating film properties were evaluated. The composition of the coating liquid and the results of coating film physical properties evaluation are summarized in Table 1.
(Example 11)
A coated plate was prepared in the same manner as in Example 1 using PUD11 and PUD12, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 12)
A coated plate was prepared in the same manner as in Example 1 using PUD13 and PUD14, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 13)
A coated plate was prepared in the same manner as in Example 1 using PUD15 and PUD10, and the coating film physical properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 14)
A coated plate was produced in the same manner as in Example 1 using PUD16 and PUD8, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 15)
A coated plate was produced in the same manner as in Example 1 using PUD17 and PUD8, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 16)
A coated plate was produced in the same manner as in Example 1 using PUD1 and PUD18, and the physical properties of the coating film were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 17)
A coated plate was produced in the same manner as in Example 1 using PUD26 and PUD8, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 18)
A coated plate was produced in the same manner as in Example 1 using PUD1 and PUD24, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 19)
A coated plate was prepared in the same manner as in Example 1 using PUD1 and PUD23, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.
(Example 20)
A coated plate was prepared in the same manner as in Example 1 using PUD19 and PUD20, and the coating film properties were evaluated. Table 2 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

Although the molecular weight of PCD used for PUD was slightly low, almost a good balance between soft feeling and resistance was obtained.
(Example 21)
A coated plate was produced in the same manner as in Example 1 using PUD21 and PUD22, and the coating film physical properties were evaluated. The composition of the coating liquid and the evaluation results of the coating film properties are summarized in Table 3.

Although the molecular weight of PCD used for PUD was slightly high, almost a good balance between soft feeling and resistance was obtained.
(Example 22)
In Example 1, 1 g of urethane beads (DIAPLACOAT, RHU-5070D (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., average particle size = 7 μm) was added, and a coated plate was prepared in the same manner as in Example. The film properties were evaluated, and the composition of the coating solution and the results of the coating properties evaluation are summarized in Table 3.
(Comparative Example 1)
In Example 1, a paint was prepared using only PUD1 without using PUD2, and the coating film was evaluated. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

When PUD1 is used alone, the soft feeling is good, but it is understood that the resistance is insufficient.
(Comparative Example 2)
In Example 1, a coating material was prepared using only PUD2 without using PUD1, and the coating film was evaluated. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

When PUD2 is used alone, the tolerance is good, but the soft feeling is insufficient.
(Comparative Example 3)
In Example 1, the coating properties were evaluated by changing the mixing ratio of PUD1 and PUD2. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

Since PUD1 / PUD2 <0.2 (mass ratio), a sufficient soft feeling was not obtained.
(Comparative Example 4)
In Example 1, the coating properties were evaluated by changing the mixing ratio of PUD1 and PUD2. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

Since PUD1 / PUD2> 5 (mass ratio), sufficient resistance was not obtained.
(Comparative Example 5)
In Example 1, the amount of the curing agent used was increased. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

Since NCO / OH> 2.5 (molar ratio), both soft feeling and resistance were impaired.
(Comparative Example 6)
In Example 1, the amount of curing agent used was reduced. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

Since NCO / OH <0.9 (molar ratio), the degree of crosslinking decreased and the resistance was impaired.
(Comparative Example 7)
A coated plate was prepared in the same manner as in Example 1 using PUD27 and PUD25, and the coating film properties were evaluated. Table 4 summarizes the composition of the coating liquid and the evaluation results of the coating film properties.

  Since the amount of TMP used by PUD25 and PUD27 exceeded 10% by mass, the soft feeling was impaired.

  According to the present invention, the physical strength of the coating film such as the scratch resistance and abrasion resistance of the coating film, and the physical property balance of the chemical resistance of the coating film such as acid resistance, alkali resistance and alcohol resistance, In addition, it is possible to provide a curable composition for water-based soft-feel coatings that enables formation of a coating film having a soft touch feeling.

Claims (1)

The following (A), (B) and (C) are contained as essential components, (A) / (B) = 0.2 to 5 (however, mass ratio of nonvolatile content), and (B) molecules are contained. the ratio of NCO groups NCO / OH = from 2.5 to .9 containing OH groups and (C) molecules (provided that the molar ratio of functional groups) der Ru water based paints curable composition:
(A) An aqueous dispersion of a polyurethane having a carboxyl group and / or a sulfonic acid group-containing polyol or a salt thereof in the molecule, a polycarbonate skeleton, and a molecular end group that is not a hydroxyl group, Before the emulsion dispersion in water, the content of the monomer part of the carboxyl group and / or sulfonic acid group-containing polyol or salt thereof copolymerized with the NCO end group-containing urethane prepolymer is 1% by mass to 25% by mass, polycarbonate diol The content of the polyisocyanate compound monomer is 5% by mass to 94% by mass, the content of the polyisocyanate compound monomer is 5% by mass to 94% by mass, and the content of the other copolymerizable monomer is 0% by mass to 10% by mass. %, An aqueous dispersion of the above polyurethane,
(B) an aqueous dispersion of a polyurethane having a carboxyl group and / or a sulfonic acid group-containing polyol or a salt thereof in the molecule, a polycarbonate skeleton, and a molecular end group being a hydroxyl group, Before emulsifying and dispersing in water, the content of the monomer part of the carboxyl group and / or sulfonic acid group-containing polyol or salt thereof copolymerized with the OH terminal group-containing urethane polymer is 0.5% by mass to 25% by mass, The content of the polycarbonate diol part is 20% by mass to 99% by mass, the content of the polyisocyanate compound monomer part is 0.5% by mass to 79.5% by mass, and the content of the other copolymerizable monomer part is An aqueous dispersion of the polyurethane, which is 0% by mass to 10% by mass,
(C) Water-dispersed curing agent of polyisocyanate compound containing at least two isocyanate groups in the molecule
In the polycarbonate diol, the repeating units are represented by (formula 3) and (formula 4), and (number of moles of formula 3) / (number of moles of formula 4) = 80/20 to 30/70. The curable composition for water-based paints, which is an aliphatic polycarbonate diol having a hydroxyl group as a terminal group .