JP5116369B2 - Water-based polyurethane dispersion and water-based dispersion composition for soft-feel coatings using the same - Google Patents

Description

  The present invention relates to an aqueous dispersion for a soft feel paint comprising an aqueous polyurethane dispersion in which the terminal group of the polyurethane main chain is an OH group, obtained from a polycarbonate diol having a specific structure, and the aqueous polyurethane dispersion and an aqueous polyisocyanate dispersion. It relates to a body composition.

  Conventionally, polyurethane resins have been used in a wide range of areas such as synthetic leather, artificial leather, adhesives, furniture paints, and automobile paints, and polyethers and polyesters have been used as polyol components that react with isocyanates. However, in recent years, the demand for resin resistance, such as heat resistance, weather resistance, hydrolysis resistance, weather resistance, and oil resistance, has become more sophisticated, and the touch feeling has been soft, and it has become a soft feel paint like natural leather. The demand for is increasing. As a conventional method for producing an aqueous polyurethane, a prepolymer having an NCO end group is prepared in a solvent, polymerized using a chain extender simultaneously with emulsification in water, and the aqueous polyurethane dispersion is obtained by removing the solvent. I was getting. However, in order to improve resistance, it is necessary to introduce a crosslinked structure using a crosslinking agent. However, since the primary molecular weight of polyurethane is long, it is difficult to achieve both a high level of resistance requirement and a soft feel. It was.

  The present invention provides a coating film that has a good balance of physical properties such as coating film hardness, flexibility, acid resistance, alkali resistance, alcohol resistance, oil resistance, and abrasion resistance, and is soft and feels like natural leather. An object of the present invention is to provide an aqueous dispersion composition for soft feel paints that can be formed.

  As a result of intensive studies, the present inventors combined an aqueous polyurethane dispersion and an aqueous polyisocyanate dispersion in which the terminal group of the polyurethane main chain obtained from a polycarbonate diol having a specific structure is an OH group, The present inventors have found that a soft feel paint that is soft and feels like a natural leather and has an excellent balance with coating film resistance can be obtained.

（ｃ）カルボキシル基及び／又はスルホン基含有ポリオールもしくはその塩。 That is, the present invention includes the following aspects.
(1) (A) The aqueous polyurethane dispersion contains a polyurethane obtained by reacting the following components (a), (b) and (c), and the end group of the polyurethane main chain is an OH group: An aqueous dispersion composition for soft feel paints, comprising an aqueous polyurethane dispersion having a number average molecular weight of 800 to 25000, and (B) an aqueous polyisocyanate dispersion as essential components.
(A) At least one aliphatic and / or alicyclic organic diisocyanate compound selected from hexamethylene diisocyanate, isophorone diisocyanate, dodecanedioisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate .
(B) It consists of repeating units of the following formulas (1) and (2), and the ratio of (1) and (2) is (1) / (2) = 80/20 to 20/80 (molar ratio). An aliphatic polycarbonate diol having a hydroxyl group as a terminal group.

(C) A carboxyl group and / or a sulfone group-containing polyol or a salt thereof.

( 2 ) The aqueous dispersion composition for soft feel paints as described in (1) above, wherein the aqueous polyisocyanate dispersion is a self-emulsifying aqueous polyisocyanate dispersion.

  Use of an aqueous polyurethane dispersion obtained from a polycarbonate diol having a specific structure according to the present invention, an aqueous polyurethane dispersion in which the terminal group of the polyurethane main chain is an OH group, and an aqueous dispersion composition for soft feel paints obtained from an aqueous polyisocyanate dispersion Provides a soft-feel coating with a soft, natural leather-like feel that has excellent physical properties such as coating hardness, flexibility, acid resistance, alkali resistance, alcohol resistance, oil resistance, and wear resistance. can do.

The present invention will be described in detail below.
The organic polyisocyanate compound used in the production of the aqueous polyurethane dispersion of the present invention includes tolylene diisocyanate, diphenylmethane diisocyanate, diisocyanate cyclohexane, tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate. , 2,6-diisocyanate methylcaproate, isophorone diisocyanate, methylcyclohexane-2,4- (or 2,6-) diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), aromatic, aliphatic, alicyclic Group organic diisocyanates, or multimers containing polyfunctional isocyanate groups such as burettes and isocyanurates, Or these isocyanate is individual or a mixture is mentioned.
In particular, from the viewpoint of weather resistance, aliphatic and / or alicyclic diisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dodecane diisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate are preferable.

Next, the polycarbonate diol used for the production of a normal aqueous polyurethane dispersion includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2,3-butanediol, 1,5-hexanediol, 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-dodecane Diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and other diols Made of polycarbonate diol, and the like.
However, as a result of studying the use of various polycarbonate diols for the purposes of the present invention, the present inventors have found that the end groups of the polyurethane main chain obtained from the polycarbonate diol having the structure specified in (b) above are OH groups. It has been found that by combining a certain water-based polyurethane dispersion and a water-based polyisocyanate dispersion, a soft feel paint having a soft, natural leather-like feel and excellent balance with coating film resistance can be obtained.

That is, the polycarbonate diol having the structure specified in (b) is composed of repeating units of the following formulas (1) and (2), and the ratio of (1) and (2) is (1) / (2) = 80 / It is 20-20 / 80 (molar ratio), and is an aliphatic polycarbonate diol characterized in that the terminal group is a hydroxyl group.

  The polycarbonate diol used in the present invention is synthesized from 1,5-pentanediol and 1,6-hexanediol by various methods described in Schell, Polymer Review Vol. 9, pages 9-20 (1964). Is a copolymerized polycarbonate diol. When the ratio of (1) in the copolymerization ratio of the repeating units represented by the above formulas (1) and (2) constituting the polycarbonate diol exceeds (1) / (2) = 80/20 (molar ratio) Since the soft feeling of the obtained coating film is impaired, it is not preferable. Further, even when the ratio of (1) in the copolymerization ratio of the repeating units constituting the polycarbonate diol is less than (5) / (6) = 20/80 (molar ratio), the soft feeling of the obtained coating film is only impaired. In addition, oil resistance and wear resistance are also deteriorated. The ratio of (1) and (2) which are repeating units constituting a more preferable polycarbonate diol is (1) / (2) = 70/30 to 30/70 (molar ratio), more preferably (1) / (2 ) = 60/40 to 40/60 (molar ratio).

  The polycarbonate diol used in the present invention is a copolymerized polycarbonate diol synthesized from 1,5-pentanediol and 1,6-hexanediol, but other low molecular weight diols are copolymerized as long as the characteristics are not impaired. It can contain as. Other diols that can be specifically used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, -Methyl-1,3-propanediol, neopentyl glycol, 2,3-butanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8- Examples include octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. The proportion of these diols is the total of 1,5-pentanediol and 1,6-hexanediol As a percentage of Bruno merge ol, less than 40 wt%, preferably less than 20 wt%, more preferably less than 10 wt%.

In the present invention, the number average molecular weight of the polycarbonate diol is 500 to 10,000, preferably 1000 to 5000, and more preferably 1500 to 3000. When the number average molecular weight is less than 500, the flexibility of the coating film is lowered and the soft feeling may be significantly impaired. Further, when the number average molecular weight exceeds 10,000, the reaction with the isocyanate during the production of the polyurethane whose terminal group of the polymer main chain is an OH group becomes slow, and not only does the production take a long time, but the resulting polyurethane This is not preferable because the viscosity of the resin becomes high and dispersion in water becomes difficult.
It is desirable that the polymer terminals of the polycarbonate diol used in the present invention are substantially all hydroxyl groups.

  In the present invention, in addition to 1,5-pentanediol and 1,6-hexanediol, a compound having 3 or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, penta By using a small amount of erythritol, glycerin or the like, a bifunctional polycarbonate diol is produced during the production of a polycarbonate polyol polyfunctionalized to have an average number of hydroxyl groups of 2 or more in one molecule and a polyurethane having a polymer main chain terminal group having an OH group. In addition to trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, glycerin and other trifunctional polyol monomers copolymerized, the polymer main chain terminal group having an average number of OH groups of 2 or more in one molecule Also included are polyurethanes in which is an OH group.

  Further, (c) a carboxyl group and / or sulfone group-containing polyol or salt thereof used in the present invention is obtained by self-emulsifying an aqueous polyurethane whose terminal group of the polymer main chain is an OH group in water, and an aqueous polyurethane dispersion. For the purpose of imparting the dispersion stability of a carboxylate group or a sulfonate group. Examples of the carboxyl group-containing polyol include 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, and the like. It is done. 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) sulfamic 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- Heterocyclic tertiary amines such as methylpiperidine 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, as well as combinations of two or more of these.

Among the salts, preferred are amine salts, more preferred are aliphatic tertiary monoamine salts, and particularly preferred is triethylamine salt.
When the polyol is not a salt but a carboxyl group and / or sulfone group-containing polyol, neutralize the carboxyl group and / or the sulfone group using a neutralizing agent to form a carboxylate group and / or a sulfonate group. Can do.
Examples of the neutralizing agent include alkaline compounds that form the cations mentioned as the counter ion. For example, ammonia, amine [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propylamine and octylamine), secondary monoamines (dimethylamine, diethylamine and dibutylamine), tertiary monoamines ( 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 these Use of two or more types of the like.
Of these, preferred are amines, more preferred are aliphatic tertiary monoamines, and particularly preferred is triethylamine.

Naturally, suitable surfactants such as higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkyl aryl sulfonates, sulfonated castor oil, sulfosuccinates and the like are anionic. Emulsion stability may be maintained by using a surfactant or a nonionic surfactant represented by a known reaction product of ethylene oxide and a long-chain fatty alcohol or phenol. 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, triethylenediamine, etc .; 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 an OH group according to the present invention can be obtained, for example, by the following method.
Contains two or more isocyanate groups in one molecule in the presence or absence of organic solvents that do not contain active hydrogen-containing groups 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, and a carboxyl group and / or sulfone group-containing polyol or salt thereof (c) have an (NCO group / OH group) equivalent ratio of 0.5. In the range of ˜0.99, urethanation reaction is carried out by a one-shot method or a multistage method to synthesize polyurethane having an OH group as a terminal group of the polymer main chain. After neutralization, water is added dropwise to the reaction solution obtained with vigorous stirring, and the solvent is subsequently removed after completion of the addition. More OH group-terminated aqueous polyurethane dispersion is obtained. It is also possible to obtain the OH group-terminated aqueous polyurethane dispersion by adding the obtained reaction liquid to water with stirring and removing the solvent. 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.

When the equivalent ratio of (NCO group / OH group) is less than 0.5, the molecular weight of the polyurethane whose terminal group of the resulting polymer main chain is OH group is too small, and a stable aqueous dispersion may not be obtained. Even if it is obtained, the soft feel coating composition formed from the OH group-terminated water-based polyurethane dispersion and water-based polyisocyanate dispersion as the constituent components is insufficient in flexibility, and a soft hand cannot be obtained. In addition, when the (NCO group / OH group) equivalent ratio exceeds 0.99, the molecular weight of the polyurethane having an OH group as the terminal group of the resulting polymer main chain is excessively increased, and the viscosity of the system is increased. It becomes difficult and undesirable. From such a viewpoint, the number average molecular weight of the polyurethane in which the terminal group of the polymer main chain of the present invention is an OH group is preferably in the range of 800 to 50,000. The amount of the carboxyl group and / or sulfone group-containing polyol is preferably 0.01 to 10% by weight of the carboxyl group and / or the sulfone group with respect to the weight of the polyurethane resin. More preferably, it is 0.1-7 weight%, Most preferably, it is the range of 0.5-5 weight%. When the carboxyl group and / or sulfone group is less than 0.01% by weight, sufficient emulsion stability cannot be obtained, which is not preferable. On the other hand, if it exceeds 10% by weight, the resulting film has insufficient water resistance.
Moreover, only the polycarbonate diol (b) which has an organic polyisocyanate (a) which contains two or more isocyanate groups in 1 molecule, and does not contain a carboxyl group and / or a sulfone group containing polyol (c), and a specific structure. In the same manner as described above, an NCO-terminated prepolymer is used, and a carboxyl group and / or sulfone group-containing polyol (c) is added to the final (NCO group / OH group) equivalent ratio of 0.5 to 0.99. There is also a method in which the reaction is carried out so as to be in the range of

  Furthermore, the water-based polyisocyanate dispersion (B) used in the present invention is a hydrophilic polymer obtained by introducing a nonionic hydrophilic group-containing compound into a hydrophobic polyisocyanate obtained from an organic polyisocyanate containing two or more isocyanate groups in one molecule. Self-emulsifiable polyisocyanate with excellent water dispersion stability obtained by mixing an ionic surfactant with a hydrophilic polyisocyanate, a hydrophobic polyisocyanate, a hydrophilic polyisocyanate having an oxyethylene group, and an isocyanate group Water-dispersible polyisocyanate composition comprising a solvent inert to water, or hydrophobic polyisocyanate obtained from organic diisocyanate oxime, active methylene, phenol, mercaptan, acid amide, acid imide, imidazole System, urea system, a A compound having a nonionic hydrophilic group necessary for imparting water-dispersibility with a blocking agent such as an amine-based, imine-based, bisulfite-based, pyrazole-based, triazole-based compound, and the like, and Examples thereof include blocked aqueous polyisocyanate dispersions obtained by reacting a compound having a polyethylene oxide chain or a compound having an ionic hydrophilic group such as hydroxycarboxylic acid and hydroxysulfonic acid.

Hydrophobic polyisocyanates obtained by using one or more organic diisocyanates as described above, which are constituents of the aqueous polyisocyanate dispersion (B), include burette, isocyanurate, urethane, Those having a structure such as uretdione and allophanate can be mentioned. Those having a burette structure are excellent in adhesion, those having an isocyanurate structure are excellent in weather resistance, 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.
Examples of the compound used for hydrophilizing the hydrophobic polyisocyanate include polyoxyethylene compounds having an active hydrogen-containing group. In view of water dispersion stability, polyethylene glycol monomethyl ether is particularly preferable.

Further, among the ionic surfactants used for improving the water dispersion stability, examples of the anionic surfactant include ammonium alkylbenzenesulfonate, sodium alkyldisulfate, sodium alkyldiphenyl ether disulfonate, and dialkylsulfosuccinic acid. Sodium etc. are mentioned. Examples of the cationic surfactant include alkyl trimethyl ammonium bromide, alkyl pyridinium bromide, imidazolinium laurate and the like.
Examples of the compound having an active hydrogen at one end and an ionic hydrophilic group include the carboxyl group and / or sulfone group-containing polyol as described above or a salt (c) thereof.

Examples of the blocking agent include the following compounds.
Oxime-based; 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 t-butyl, benzyl acetoacetate, phenyl acetoacetate and the like).

Phenolic; phenol, cresol, ethylphenol, butylphenol, etc.
Mercaptan type; 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-based, active methylene-based, and pyrazole-based are preferable, and specific preferable examples include acetoxime, methyl ethyl ketoxime, malonic acid diester, acetoacetate ester, pyrazole and the like. In particular, from the viewpoint of low-temperature curability, a malonic acid diester, an acetoacetic 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.

As the water-based polyisocyanate dispersion (B) used in the present invention, Duranate WB40-100, Duranate WB40-80D manufactured by Asahi Kasei Chemicals, Burnock DNW-5000, Burnock DNW-5010, Burnock DNW-50 manufactured by Dainippon Ink and Chemicals, Inc. 5100, Barnock DNW-5200, Barnock DNW-6000, Bayhydur-VP LS2032, Bayhydur-VP 2050 manufactured by Bayer, and Rhodocoat WT2102 manufactured by Rhodia.
The mixing ratio of the aqueous polyurethane dispersion (A) and the aqueous polyisocyanate dispersion (B) is OH / NCO = 2/1 to 1/3 (equivalent ratio), more preferably OH / NCO = 1 / 0.8 to 1/2 (equivalent ratio). If the NCO group is less than 0.5 equivalent with respect to 1 equivalent of OH group, coating properties having sufficient resistance cannot be obtained, and if it exceeds 3 equivalents, problems such as heat resistance of the coating may occur, which is not preferable. .

The soft feel coating composition of the present invention includes a curing accelerator (catalyst), a filler, a flame retardant, a dye, an organic or inorganic pigment, a release agent, a fluidity modifier, a plasticizer, An oxidizing agent, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a colorant, a solvent 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 materials such as can be used. Among them, resin fine particles are more preferable in order to obtain the intended soft feel.
A matting agent such as silica may be used in combination for gloss adjustment. Specific examples of the matting agent include AcemattHK series, AcemattOK series, AcemattTS series (all manufactured by Degussa).
As the mold release agent, fluidity adjusting agent, and leveling agent, silicone, aerosil, wax, stearate, polysiloxane such as BYK-331 (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 or substituted aromatic esters, hypophosphorous acid derivatives, phenylsulfonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diester. Phosphites such as phosphites and dialkylbisphenol A diphosphites; phenol derivatives, especially hindered phenol compounds, choethers, dithioates; compounds containing sulfur such as mercaptobenzimidazoles, thiocarbanilides, thiodipropionates Tin compounds such as tin malate and dibutyltin monoxide can be used.
These may be used alone or in combination of two or more.
As a coating method of the aqueous dispersion composition for soft feel paints of the present invention, the components (A) and (B) are mixed immediately before coating and then applied to a substrate by spraying, rolling, brushing, or the like. Is used. A method in which the components (A) and (B) are mixed in advance and applied is also possible. In the latter, when using a hardening | curing agent, the method of adding a hardening | curing agent just before use is preferable.
The aqueous dispersion composition for soft feel paints of the present invention can be preferably used for home appliances, OA products, automobile interior parts, leather surface treatments, 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. Evaluation of physical properties of the coating film in the following examples and comparative examples was performed according to the following test methods.
<Test method>
1. Coating hardness
The Double-Pendulum Damping test method was used. With the glass plate (standard plate), the time until the swing angle of the pendulum was attenuated from 5 ° to 2 ° was set to 440 ± 6 seconds (t ₀ ). Further, to prepare a coating onto a glass plate to measure the time (t ₁₎ until vibration angle of the pendulum on a coating film decreased to 2 ° from 5 °. The coating film hardness evaluation results were expressed as coating film hardness (X) = (t ₁ ) / (t ₀ ). The larger the value, the harder the coating surface.
2. Abrasion resistance According to the method of JIS-K-5600-5-8, it measured using the Taber type abrasion tester. 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.

3. Soft feeling The soft feeling was evaluated based on the touch when the surface of the coating plate was touched by hand. Judgment results were expressed in the following notation.
○: Good soft feeling △: Relatively good soft feeling ×: Not felt soft Acid resistance Under the condition of temperature 20 ° C., the coated plate was immersed in a 0.1N sulfuric acid aqueous solution for 24 hours, and then the surface state of the film was visually judged and evaluated according to the following criteria.
◎: No change ○: Almost no change △: Partially deteriorated ×: Significant deterioration

5. Alcohol resistance After immersing the coated plate in a 50% ethanol aqueous solution for 4 hours under the condition of a temperature of 20 ° C., the surface condition of the film is visually determined, Evaluation based on the criteria.
6). 3. Alkali resistance After immersing the coated plate in a 0.1N NaOH aqueous solution for 2 hours under the condition of a temperature of 55 ° C., the surface condition of the film was visually determined, Evaluation based on the criteria.
7). Oil resistance Under the condition of a temperature of 20 ° C., 0.1 g of oleic acid was deposited on the coated plate, and after 4 hours, the surface state of the film was visually judged. Evaluation based on the criteria.

[Synthesis Example 1]
Polycarbonate diol obtained by copolymerizing 75 g of methyl ethyl ketone (MEK) with polycarbonate diol 1 (C5,6-PCDL-1: 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50, Number average molecular weight 1958) 100 g, a solution obtained by neutralizing 3.43 g of dimethylolpropane (DMPA) dissolved in 30 g of MEK with 2.59 g of triethylamine (TEA), 11.37 g of isophorone diisocyanate (IPDI), N ₂ gas Was put into a reactor having a reflux condenser, a thermometer and a stirrer sealed with a urethanization reaction at 80 ° C. for 8 hours until there was no unreacted NCO group, and a polyurethane solution having an OH group terminal was obtained. It was. The OH group-terminated polyurethane solution was set at 40 ° C. and stirred at 250 rpm, and 280 g of distilled water was added dropwise over 20 minutes to obtain an OH group-terminated polyurethane dispersion. Further, the dispersion was heated to 80 ° C., MEK was removed over 3 hours, and an OH group-terminated polyurethane emulsion-1 (PUD-1) was produced. The number average molecular weight of the obtained polyurethane was 7800.
The molar ratio of each raw material in the synthesis example is as follows.
IPDI / PCDL / DMPA / TEA = 2/2/1/1 (molar ratio)

[Synthesis Example 2]
Polycarbonate obtained by copolymerizing polycarbonate diol-2 (C5,6-PCDL-2: 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50 instead of polycarbonate diol-1 An OH group-terminated polyurethane emulsion-2 (PUD-2) was obtained in the same manner as in Synthesis Example 1 except that the number average molecular weight was 1000).
The molar ratio of each raw material in the synthesis example is as follows. The number average molecular weight of the obtained polyurethane was 4700.
IPDI / PCDL / DMPA / TEA = 2/2/1/1 (molar ratio)

[Synthesis Example 3]
Polycarbonate diol-3 (C5,6-PCDL-3: polycarbonate obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol in a 50/50 molar ratio instead of polycarbonate diol-1 An OH group-terminated polyurethane emulsion-3 (PUD-3) was obtained in the same manner as in Synthesis Example 1 except that the number average molecular weight was 800). The number average molecular weight of the obtained polyurethane was 4100.
The molar ratio of each raw material in the synthesis example is as follows.
IPDI / PCDL / DMPA / TEA = 2/2/1/1 (molar ratio)
[Synthesis Example 4]
Except for changing to IPDI / PCDL / DMPA / TEA = 8/7/2/2 (molar ratio), in the same manner as in Synthesis Example 1, OH group-terminated polyurethane emulsion-4 (PUD-4) was obtained. The number average molecular weight of the obtained polyurethane was 25000.

[Synthesis Example 5]
Polycarbonate diol obtained by copolymerizing 75 g of methyl ethyl ketone (MEK) with polycarbonate diol 1 (C5,6-PCDL-1: 1,5-pentanediol and 1,6-hexanediol at a molar ratio of 50/50, Number average molecular weight 1958) 100 g, a solution obtained by neutralizing 3.43 g of dimethylolpropane (DMPA) dissolved in 30 g of MEK with 2.59 g of triethylamine (TEA), 11.37 g of isophorone diisocyanate (IPDI), N ₂ gas Was put into a reactor having a reflux condenser, a thermometer and a stirrer sealed with a urethanization reaction at 80 ° C. for 8 hours until there was no unreacted NCO group, and a polyurethane solution having an OH group terminal was obtained. Obtained. The polyurethane solution having OH group ends was gradually added dropwise to 560 g of distilled water set at 40 ° C. over 20 minutes while stirring to obtain a polyurethane dispersion having OH group ends. Further, the dispersion was heated to 80 ° C., MEK was removed over 3 hours, and an OH group-terminated polyurethane emulsion-5 (PUD-5) was produced. The number average molecular weight of the obtained polyurethane was 7800.
The molar ratio of each raw material in the synthesis example is as follows.
IPDI / PCDL / DMPA / TEA = 2/2/1/1 (molar ratio)

[Example 1]
As a water-based polyisocyanate dispersion obtained in Synthesis Example 1, as a water-based polyisocyanate dispersion, Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was used and mixed at a ratio of NCO / OH = 1.50 (molar ratio). A coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.
[Example 2]
The PUD-2 obtained in Synthesis Example 2 was mixed as a water-based polyisocyanate dispersion using Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd., at a ratio of NCO / OH = 1.50 (molar ratio). A coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.

[Example 3]
As a water-based polyisocyanate dispersion obtained in Synthesis Example 3, as a water-based polyisocyanate dispersion, Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was used and mixed at a ratio of NCO / OH = 1.50 (molar ratio). A coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.
[Example 4]
The PUD-4 obtained in Synthesis Example 4 was mixed as a water-based polyisocyanate dispersion using Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd., at a ratio of NCO / OH = 1.50 (molar ratio). A coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.

[Example 5]
The PUD-1 obtained in Synthesis Example 1 was mixed with Duranate WT20-100 manufactured by Asahi Kasei Chemicals Corporation as an aqueous polyisocyanate dispersion at a ratio of NCO / OH = 1.50 (molar ratio). A coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.
[Example 6]
As a water-based polyisocyanate dispersion obtained in Synthesis Example 5, as a water-based polyisocyanate dispersion, Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was used and mixed at a ratio of NCO / OH = 1.50 (molar ratio). A coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.

[Comparative Example 1]
Obtained in the same manner as in Synthesis Example 1 except that Carbodiol D-2000 manufactured by Toa Gosei Co., Ltd., which is a homopolymer of 1,6-hexanediol (C6-PCDL), was used instead of PUD-1 as the polycarbonate diol. As a water-based polyisocyanate dispersion, Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was used and mixed at a ratio of NCO / OH = 1.50 (molar ratio) to the OH group-terminated polyurethane emulsion (PUD-6). Then, a coating composition was prepared.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.

[Comparative Example 1]
An OH group-terminated polyurethane emulsion (PUD) obtained in the same manner as in Synthesis Example 1 except that carbodiol D-1000 manufactured by Toa Gosei Co., Ltd., which is C6-PCDL, was used as the polycarbonate diol instead of PUD-2. As a water-based polyisocyanate dispersion, Duranate WB40-100 manufactured by Asahi Kasei Chemicals Co., Ltd. was used and mixed at a ratio of NCO / OH = 1.50 (molar ratio) to prepare a coating composition.
The coating composition was applied to a glass plate, dried at 80 ° C. for 30 minutes, and then cured at 120 ° C. for 90 minutes to obtain a 25 μm thick film.
Each physical property was measured using the obtained film. The results are shown in Table 1.

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

Claims (2)

(A) The aqueous polyurethane dispersion contains a polyurethane obtained by reacting the following components (a), (b) and (c), and the terminal group of the polyurethane main chain is an OH group, An aqueous dispersion composition for soft feel paints, comprising an aqueous polyurethane dispersion having an average molecular weight of 800 to 25000 and (B) an aqueous polyisocyanate dispersion as essential components.
(A) At least one aliphatic and / or alicyclic organic diisocyanate compound selected from hexamethylene diisocyanate, isophorone diisocyanate, dodecanedioisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate .
(B) It consists of repeating units of the following formulas (1) and (2), and the ratio of (1) and (2) is (1) / (2) = 80/20 to 20/80 (molar ratio). An aliphatic polycarbonate diol having a hydroxyl group as a terminal group.

(C) A carboxyl group and / or a sulfone group-containing polyol or a salt thereof. The aqueous dispersion composition for soft feel paints according to claim 1 , wherein the aqueous polyisocyanate dispersion is a self-emulsifying aqueous polyisocyanate dispersion.