JP2005297200A - Coated body having good tactile feeling and design property and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coated body stably and surely exhibiting such good tactile feelings as wet touch and smooth touch, and various design properties such as a very soft elastic feeling, a rather rigid elastic feeling and a leather-like embossed pattern, on substrates of any kinds and shapes, and a method for manufacturing the same. <P>SOLUTION: The coated body having good tactile feeling and design properties made by forming an undercoat foamed layer and a topcoat layer on a substrate and having a mean deviation of the surface mean friction coefficient of 0.0025-0.0100, and a method for manufacturing the same, are provided. The undercoat foamed layer is an undercoat formed elastic layer formed by coating with a polyurethane dispersion, a foam stabilizer, a foaming agent and an extender pigment and curing the coating. The topcoat layer is a topcoat layer formed by coating with a main agent comprising a hydrophilic polyurethane polyol, a curing agent comprising a hydrophilic polyisocyanate, and a filler, and curing the coating. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a coated body having a touch feeling such as a moist feeling and a smooth feeling, a very soft elasticity, a hard elasticity, and the like, and an excellent design, and a method for producing the same.

As a method for enhancing the texture of vehicle interior materials, interior building materials, etc., for example, a method of flocking the surface of a base material such as an interior material or attaching a back skin is known.
However, these methods increase costs, man-hours, and the like, and do not provide an excellent touch and appearance.

Therefore, for example, the following method has been proposed in order to form a pleasant touched body.
That is, a resin-based treatment agent containing microcapsules is gravure-printed on the surface of a sheet made of a thermoplastic resin, and this is heated to soften the expansion of the microcapsules and the resin, thereby forming fine irregularities on the sheet surface. A method is known (for example, refer to Patent Document 1).
In addition, microcapsules are dispersed in a vinyl chloride resin paste, this paste is printed on the backing material by gravure printing, etc., and this is heated to gel the paste and simultaneously expand the microcapsules to create a suede-like appearance A method for obtaining a decorative sheet exhibiting the above is known (for example, see Patent Document 2).
Furthermore, after applying an undercoating paint containing microcapsules on the substrate, curing the paint, applying an overcoating paint, and then heating to expand the microcapsules to form a coating film with a concavo-convex pattern There is a known method (see, for example, Patent Document 3). As a preferred undercoat that can be easily cured at a temperature lower than the expansion temperature of the microcapsule and does not contain a solvent that may damage the outer shell of the microcapsule, an acrylic-epoxy aqueous emulsion paint, a urethane aqueous emulsion paint Acrylic ultraviolet curable paints are exemplified, and melamine-alkyd-based, acrylic-based enamel paints, etc. are mentioned as top coats that are preferable in appearance.

Japanese Patent Laid-Open No. 2-76735 Japanese Unexamined Patent Publication No. 62-28481 JP-A-2-303573

However, in the method disclosed in Japanese Patent Application Laid-Open No. 2-76735 (Patent Document 1), the expansion of the microcapsule and the softening of the thermoplastic resin serving as the base material are simultaneously advanced by heating. The softened resin is attracted to form irregularities, and the appearance and feel are hard.
Further, in the method disclosed in Japanese Patent Application Laid-Open No. Sho 62-28481 (Patent Document 2), since the layer containing the expanded microcapsule is the surface layer of the sheet, the microcapsule is detached from the sheet surface during actual use. There are things to do. In addition, since the sheet surface does not slide well, a part of the microcapsule may be damaged when it is rubbed in contact with another article. Furthermore, since the paste containing the microcapsules is printed on the backing material, the printing machine is likely to be clogged, and the printed surface may be uneven. Repairing this clogging requires a lot of labor.
Furthermore, in the method disclosed in JP-A-2-303573 (Patent Document 3), the microcapsules can be prevented from being damaged or dropped by the top coating, but the surface slippage is not good. The capsule may be damaged or fall off.

  The present invention solves the above-mentioned problems of the prior art and provides a feeling of moistness, smoothness, etc. to any type and shape of the substrate, a very soft elasticity, a hard elasticity, and leather. It aims at providing the coating body which expressed various design characteristics, such as a wrinkle, stably and reliably, and its manufacturing method.

  In order to achieve the above object, the present invention provides a touch-sensitive design property having an average deviation of a surface average friction coefficient of 0.0025 to 0.0100, which is formed by forming an undercoat foam layer and an overcoat layer on a substrate. An undercoat formed by applying and curing an undercoat water-based one-component polyurethane coating composition containing a polyurethane dispersion, a foam stabilizer, a foaming agent, and an extender pigment. It is a foamed elastic layer, and the overcoat layer is composed of a main agent containing a hydrophilic polyurethane polyol and a curing agent containing a hydrophilic polyisocyanate, and is further filled with either or both of the main agent and the curing agent. The touch-sensitive design-coated body, which is a topcoat layer formed by applying and curing a water-based two-component polyurethane coating composition for topcoat containing an agent.

  The present invention also relates to a method for producing a feel-feeling design-coated body having an average surface friction coefficient average deviation of 0.0025 to 0.0100, which is formed by forming an undercoat foam layer and an overcoat layer on a substrate. Then, a water-based one-component polyurethane coating composition for undercoating containing a polyurethane dispersion, a foam stabilizer, a foaming agent, and an extender pigment is applied on a base material, and then a hydrophilic polyurethane polyol without baking and drying. A waterborne two-component polyurethane coating composition for topcoat comprising a main agent containing a hydrophilic polyisocyanate and a curing agent containing a hydrophilic polyisocyanate, wherein either or both of the main agent and the curing agent further contain a filler. It is the said manufacturing method characterized by apply | coating, baking, and drying.

  Further, in the present invention, an average deviation of the surface average friction coefficient formed by forming an undercoat foam layer having a dry film thickness of 50 to 5,000 μm and an overcoat layer having a dry film thickness of 10 to 200 μm on the substrate is 0.0025. A method for producing a feel-feel design-finished coated body having a coating composition of ~ 0.0100, comprising a polyurethane dispersion, a foam stabilizer, a foaming agent, and an extender pigment on a base material. Without being baked and dried, and comprising a main agent containing a hydrophilic polyurethane polyol and a curing agent containing a hydrophilic polyisocyanate, and either or both of the main agent and the curing agent are further The above-mentioned production method is characterized in that a topcoat aqueous two-component polyurethane coating composition containing a filler is applied, baked and dried.

  For the first time according to the present invention, it is possible to stably provide a comfortable feeling such as a moist feeling and a smooth feeling on a substrate of any kind and shape, a very soft elasticity, a hard elasticity, and various designs such as leather wrinkles. And it became possible to provide the coated body which expressed reliably, and its manufacturing method.

The present invention will be described in detail below.
The polyurethane dispersion used in the undercoat aqueous one-component polyurethane coating composition in the present invention includes, for example, (1) a method of forcibly emulsifying an aqueous polyurethane resin with a surfactant, and (2) an oxyethylene skeleton in the resin molecule. It can be obtained by a method of introducing self-emulsifying property or (3) a method of introducing a cationic group or an anionic group into a resin molecule and neutralizing it.
Among these, the polyurethane dispersion obtained by the method (3) is particularly preferable because the cured product has excellent physical properties and the aqueous dispersion has excellent storage stability. Specifically, the organic polyisocyanate (A), the polyol (B) containing at least one kind of polyol having an aromatic ring structure, and the polyol or molecule having an anionic group such as a carboxyl group or a sulfonic acid group in the molecule The polyol (C) having a cationic group in the reaction product is urethanated in a solvent that is inert to the reaction and has a high affinity for water to form a prepolymer, and then the prepolymer is neutralized and chain-extended. A polyurethane dispersion is preferably added.

Examples of the organic polyisocyanate (A) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, and 4,4'-diphenylmethane diisocyanate. 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyl Diphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diiso Aromatic diisocyanates such as anate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, aromatic polyisocyanates such as polyphenylene polymethylene polyisocyanate, crude tolylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate , Aliphatic diisocyanates such as lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, organic diisocyanate such as alicyclic diisocyanate such as tetramethylxylene diisocyanate, and biuret modification of the organic diisocyanate Body, uretdione modified body, carbodiimide modified body, Isocyanurate modified products, uretonimine modified product, a mixture of these modified products thereof. Of these, aliphatic diisocyanates are preferred because of their excellent weather resistance.
These can be used alone or in admixture of two or more.

  These organic polyisocyanates (A) are preferably 0.8 to 3 times equivalent, more preferably 1 to 2 times the total of polyol (B), polyol (C) and the active hydrogen of the chain extender described below. Used to be equivalent. If the amount of the organic polyisocyanate (A) used is less than 0.8 times equivalent, excess polyol or the like will remain, and if it is more than 3 times equivalent, a large amount of urea bonds will be formed when water is added. In any case, there is a risk of deteriorating the characteristics.

The polyol (B) contains at least one kind of polyol having an aromatic ring structure. The content is preferably such that the amount of the polyol having an aromatic ring structure is 10% by mass or more, and more preferably 50% by mass or more in all polyol components.
Examples of the polyol having an aromatic ring structure include low molecular weight polyols having an aromatic ring such as hydroquinone, resorcin, ethylene oxide and / or propylene oxide adduct of bisphenol A, or ethylene oxide and / or propylene oxide using these as initiators. Added polyether polyols: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, Low content of hexamethylene glycol, hydroquinone, resorcin, hydrogenated bisphenol A, ethylene oxide and / or propylene oxide adducts of bisphenol A, etc. Polyols or polyether polyols obtained by adding ethylene oxide and / or propylene oxide using these as initiators, and aromatics such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid A condensate with a polybasic acid selected from at least one of polyvalent carboxylic acids, or a condensate with these polyvalent carboxylic acids and other polybasic acids such as succinic acid, glutaric acid, adipic acid, and sebacic acid. A certain polyester polyol etc. are mentioned. These can be used alone or in admixture of two or more. Among these, it is preferable to use an aromatic ring-containing polyol obtained by using only an aromatic polyvalent carboxylic acid because an excellent storage stability of the aqueous dispersion can be obtained.

In addition, a polyol other than a polyol having an aromatic ring structure can be used in combination as the polyol (B). Examples of such a polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, Low molecular polyols such as 3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, ethylene oxide and / or propylene oxide adduct of hydrogenated bisphenol A, polyethylene Glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, and the like, and ethylene oxide and / or propylene with the low molecular polyol as an initiator. Polyether polyols obtained by adding oxides, the low molecular polyol and succinic acid, glutaric acid, adipic acid, polyester polyol which is a condensate of a polybasic acid or carbonate such as sebacic acid, polycarbonate polyols, polycaprolactone.
These can be used alone or in admixture of two or more.

  Among the polyols (C), examples of the polyol having an anionic group such as a carboxyl group or a sulfonic acid group in the molecule include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylol. Examples include valeric acid and 1,4-butanediol-2-sulfonic acid. Examples of the polyol having a cationic group in the molecule include methyldiethanolamine, butyldiethanolamine, triethanolamine, and triisopropanolamine. These can be used alone or in admixture of two or more. Among these, a polyol having a carboxyl group is preferable because an aqueous polyurethane resin excellent in dispersibility can be obtained.

  Although the usage-amount of a polyol (C) is based also on the kind of polyol and polyisocyanate to be used, it is 0.5-50 mass% normally with respect to all the reaction components which comprise a water-based polyurethane resin, Furthermore, 1-30. It is preferable that it is mass%. When the amount of the polyol (C) used is less than 0.5% by mass, the storage stability of the aqueous dispersion is poor, and when it exceeds 50% by mass, the properties may be adversely affected.

  Examples of the solvent that is used to produce a polyurethane dispersion and that is inert to the above reaction and has a high affinity for water include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone. . These solvents are usually used in a range of 10 to 100% by mass with respect to the total mass of the raw materials used for producing the prepolymer.

In addition, as a neutralizing agent for neutralizing the prepolymer, when the prepolymer is anionic (when a polyol having an anionic group such as a carboxyl group or a sulfonic acid group in the molecule is used as the polyol (C)) And when the prepolymer is cationic (when a polyol having a cationic group is used as the polyol (C)). When the prepolymer is anionic, for example, organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, triethanolamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, ammonia, etc. These are used in an amount sufficient to neutralize anionic groups such as carboxyl groups or sulfonic acid groups. Further, when the prepolymer is cationic, for example, formic acid, oxalic acid, phosphoric acid, boric acid, hydrochloric acid, carbonic acid, acetic acid, dimethylolpropionic acid and the like can be mentioned, and these neutralize the cationic group of the polyol. A sufficient amount is used.
These can be used alone or in admixture of two or more.

Examples of the chain extender that extends the prepolymer include, for example, polyols such as ethylene glycol and propylene glycol, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diaminodiphenylmethane, and diaminocyclohexylmethane. And amines such as piperazine, 2-methylpiperazine, isophoronediamine, melamine, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, and the like.
These can be used alone or in admixture of two or more.
The amount of these chain extenders used is usually 0.5 to 10% by mass based on the prepolymer, although it depends on the molecular weight of the target aqueous polyurethane resin.

As described above, a method for producing a water-based polyurethane resin from these raw materials is well known, and the order in which these raw materials are charged can be appropriately changed or divided and charged.
The polyurethane dispersion thus obtained is usually adjusted so that the resin solid content is 1 to 90% by mass, more preferably 5 to 80% by mass.

Surfactants for emulsifying water-based polyurethane resins in water include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymeric surfactants, and reactive surfactants. Etc.
Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinone; alkali metal salt of sulfonated paraffin, sulfonated paraffin Alkyl sulfonates such as ammonium salts; Fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abiates; Alkyl aryl sulfonates such as sodium benzene sulfonate and alkali metal sulfates of alkali phenol hydroxyethylene; High alkyl naphthalene sulfonate Naphthalenesulfonic acid formalin condensate; Salt; polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan fatty acid ester; polyoxyethylene sorbitan fatty acid ester; fatty acid monoglyceride; trimethylolpropane fatty acid ester; Examples thereof include condensation products of ethylene oxide with fatty acid amines, amides or acids.
Examples of the cationic surfactant include primary to tertiary amine salts; pyridinium salts; and quaternary ammonium salts.
Examples of the polymer surfactant include polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate; polyhydroxypropyl (meth) ) Acrylate; and a copolymer of two or more kinds of polymerizable monomers which are these polymer constituent units, or a copolymer with other monomers. Moreover, what are called phase transfer catalysts, such as crown ethers, are also useful as those showing surface activity.
These can be used alone or in admixture of two or more.

  In the polyurethane dispersion according to the present invention, other aqueous dispersions and aqueous dispersions, for example, emulsions such as vinyl acetate, ethylene-vinyl acetate, acrylic, acryl-styrene, etc .; styrene-butadiene , Latexes such as acrylonitrile-butadiene and acryl-butadiene; ionomers such as polyethylene and polyolefin; various aqueous dispersions such as polyester, polyamide, and epoxy resin, and aqueous dispersions can be used in combination.

  In the present invention, for the formation of the undercoat layer, a polyurethane dispersion that forms a film having a 100% modulus of 0.1 to 10.0 MPa, an elongation of 200 to 1500%, and a breaking strength of 20 to 100 MPa is preferable. For uses such as interiors, polyester-based or polycarbonate-based polyurethane dispersions capable of forming a film having a 100% modulus of 1 to 5 MPa, an elongation of 400 to 1000%, and a breaking strength of 40 to 80 MPa are preferable.

  In the water-based two-pack type polyurethane coating composition for topcoat in the present invention, the hydrophilic polyurethane polyol contained in the main agent is an intramolecular which can be dispersed, emulsified or dissolved in water by itself or at least in the presence of a surfactant. Is a polyurethane polyol having a hydrophilic group. Specifically, an organic polyisocyanate, a polyol having a hydrophilic group necessary for dispersion, emulsification or dissolution in water in the molecule, or a mixed polyol of this polyol and other polyols (preferably a mixed polyol) Is preferably obtained by reacting with a hydroxyl group-excess condition with respect to an isocyanate group.

  The hydroxyl value of the hydrophilic polyurethane polyol is preferably in the range of 30 to 300, more preferably in the range of 100 to 250. By setting the hydroxyl value of the hydrophilic polyurethane polyol within the above range, desired physical properties such as elasticity and strength can be ensured.

  As said organic polyisocyanate, organic polyisocyanate (A) used when manufacturing the polyurethane dispersion used in the water-based 1-component polyurethane coating composition for undercoat is mentioned.

As the polyol having a hydrophilic group in the molecule, for example, a diol having a carboxyl group in the molecule is preferable because of easy availability of raw materials. Specific examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxypropionic acid, and dihydroxysuccinic acid.
These can be used alone or in admixture of two or more.

Examples of polyols other than the polyol having a hydrophilic group in the molecule include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, hexylene glycol, dimethylol heptane, polyethylene glycol, polypropylene glycol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane Diols, diols such as tricyclodecane dimethanol, hydrogenated bisphenol A, triols such as trimethylolethane, trimethylolpropane, glycerin, tris-2-hydroxyethyl isocyanurate Tetraols such as pentaerythritol and the like. In addition, polyester polyols, acrylic polyols, and the like are also included.
The polyester polyol is generally obtained by polycondensation of a polyol and a polybasic acid. Examples of the polyol include the diol, triol, and tetraol described above. Examples of the polybasic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid and dimer acid, aliphatic unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid and citraconic acid, tetrahydro Alicyclic dicarboxylic acids such as phthalic acid, hexahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, endomethylenetetrahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as pyromellitic acid and tris-2-carboxyethyl isocyanurate can be mentioned.
The acrylic polyol is a copolymer of acrylic monomers having a hydroxyl group. Examples of such acrylic monomers include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate.
These can be used alone or in combination depending on the properties of the coating film required.

In the urethanization reaction between an organic polyisocyanate and a polyol, for example, a tin compound such as dibutyltin dilaurate or an amine compound such as triethylamine can be used as a reaction catalyst.
Examples of the organic solvent that can be used as a solvent in this reaction include acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide, dioxane, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.

The carboxyl group is preferably neutralized and used as a carboxyl base. Examples of the base used for this purpose include ammonia, methylamine, ethylamine, propylamine, butylamine, ethanolamine, propanolamine, diethanolamine, and dimethyl. Examples include amine, diethylamine, triethylamine, and N, N-dimethylethanolamine. These can be used alone or in combination depending on the stability of the resulting hydrophilic polyurethane polyol.
For neutralization, for example, it is preferable to use 0.6 to 1.3 equivalents of a base with respect to 1 equivalent of a carboxyl group in the hydrophilic polyurethane polyol.

  The hydrophilic polyurethane polyol is preferably used as an aqueous dispersion having a concentration of 10 to 80% by mass, and further 20 to 70% by mass.

In the water-based two-component polyurethane coating composition for topcoat in the present invention, the hydrophilic polyisocyanate contained in the curing agent specifically includes an organic polyisocyanate and a polyol having a hydrophilic group in the molecule. Hydrophilic group (bond) -containing polyol or mixed polyol of this polyol and other polyols (preferably hydrophilic bond-containing polyol, more preferably polyether polyol, polyester polyol, polyether ester polyol or mixed polyol thereof) ) And a hydrophilic group-containing isocyanate prepolymer (optionally a hydrophilic group-containing isocyanurate-modified isocyanate) obtained by reacting with a hydroxyl group in an excess of isocyanate groups and optionally in the presence of an isocyanurate-forming catalyst. Prepolymer) is preferred There, dispersed in water in the presence of itself, or at least surfactants, is to emulsify or dissolve.
In the present invention, the hydrophilic polyisocyanate is obtained by urethanizing an organic polyisocyanate and the above-mentioned hydrophilic group (bond) -containing polyol or a mixed polyol of this polyol and other polyols in the presence of an isocyanuration catalyst. A hydrophilic group-containing isocyanurate-modified isocyanate prepolymer obtained by carrying out isocyanuration at the same time is particularly preferred.
As this organic polyisocyanate and polyester polyol, those used in the production of hydrophilic polyurethane polyols can be used.
Examples of the polyether polyol include low molecular weight ones of the above polyols, low molecular weight polyamines and low molecular amino alcohols as initiators, alkylene oxides such as ethylene oxide and propylene oxide, and epoxides and cyclic ethers such as tetrahydrofuran. Examples thereof include those obtained by ring-opening polymerization of a single product or a mixture.
Examples of the polyether ester polyol include a copolyol obtained from the polyether polyol and the polybasic acid. Moreover, what is obtained by reaction with the said polyester polyol, epoxide, and cyclic ether is also mentioned.
Examples of the isocyanurate-forming catalyst include alkali metal carboxylates, alkali metal phenolates, alkali metal alcoholates, and tertiary amine compounds. A cocatalyst such as a phosphite ester and a phosphate ester can be used in combination with the isocyanurate-forming catalyst.
The isocyanuration reaction is stopped at a desired reaction rate with an organic acid, an inorganic acid, or an acid ester thereof.
Any of these may be used alone or in admixture of two or more.

  The ratio of the hydrophilic polyurethane polyol and the hydrophilic polyisocyanate used is preferably such that the equivalent ratio of the isocyanate group of the hydrophilic polyisocyanate to the hydroxyl group of the hydrophilic polyurethane polyol is in the range of 0.8 to 3.0.

  In the water-based one-component polyurethane coating composition for undercoat in the present invention, the foam stabilizer and the foaming agent are used for imparting a good elastic feel to the undercoat foam layer.

The foam stabilizer is used for forming an undercoating foamed elastic layer that expresses good elasticity by controlling bubbles generated by the foaming agent precisely and uniformly. Specific examples include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and modified sodium polyacrylate. Among these, anionic surfactants, nonionic surfactants, modified Sodium polyacrylate and a mixture thereof are preferable, and an amide surfactant and a silicone surfactant are particularly preferable. As specific examples, for amide surfactants, trade name: SN foam 200 (manufactured by San Nopco Co., Ltd.) is used. For silicone surfactants, trade names: L-501, L-520, L-540. , L-5320, L-5420 (manufactured by Nippon Unicar Co., Ltd.), F-114, F-121, F-138, F-244, F-305, F-317, F-345 [Shin-Etsu Silicone Co., Ltd. Manufactured).
These can be used alone or in admixture of two or more.

The foaming agent is preferably an azodicarboxylic acid dialkyl ester that decomposes and foams with water, and the alkyl group is preferably a lower alkyl group, a phenyl group, or a benzyl group. The lower alkyl group is particularly preferably a linear or branched group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or a tert-butyl group.
The azodicarboxylic acid dialkyl ester can be produced, for example, by producing hydrazodicarboxylic acid dialkyl ester from hydrazine hydrate and chlorocarbonate, and then oxidizing this with a halogen oxidizing agent or the like.
Examples of other foaming agents include pyrolytic foaming agents such as sodium bicarbonate, ammonium carbonate, azodicarbonamide, azobisisobutyronitrile, N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, etc. And evaporating foaming agents such as aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, fluorinated aliphatic hydrocarbons, carbon dioxide gas, nitrogen gas and the like.
These can be used alone or in admixture of two or more.
For example, it can be used in combination with a foaming method in which carbon dioxide gas is generated by reaction of isocyanate and water.

The foaming agent can be used in combination with its decomposition accelerator, for example, metal oxide, metal carbonate, metal chloride, metal soap, inorganic acid salt, organic tin compound, dibutyltin dilaurate, dibutyltin dimaleate, Calcium-zinc-based, barium-zinc-based PVC composite stabilizers, monovalent and polyhydric alcohols, urea, sulfonic acid metal compounds, sulfinic acid metal compounds, organic and inorganic acidic or alkaline substances can be mentioned. .
These can be used alone or in admixture of two or more.
The decomposition accelerator may be appropriately selected and used according to the type and amount of the foaming agent, the molding method, foaming conditions, and the like.

In the undercoat aqueous one-component polyurethane coating composition in the present invention, examples of the extender pigment include mica, kaolin, zeolite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, Zinc powder, silica such as precipitated silica, inorganic particles such as calcium carbonate and magnesium carbonate, or those whose surfaces are treated with organic substances such as fatty acids, wood flour, walnut flour, rice husk flour, pulp powder, cotton Examples include organic powder granules such as chips, acrylic resins, polyurethane resins, polyethylene resins, cellulose, polyamide, silicone rubber, wool, collagen, and inorganic powder granules are particularly preferable.
These may be used alone or in combination of two or more.

In the undercoat aqueous one-component polyurethane coating composition in the present invention, the foam stabilizer is preferably used in an amount of 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin solid content of the polyurethane dispersion.
The foaming agent is preferably used in an amount of 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin solid content of the polyurethane dispersion.
The extender pigment is preferably used in an amount of 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content of the polyurethane dispersion.

In the topcoat aqueous two-component polyurethane coating composition of the present invention, the filler is used for imparting a good feeling such as a moist feeling and a smooth feeling. Specifically, the filler is preferably a granular material having an average particle size of 50 μm or less, more preferably 1 to 30 μm, or a microcapsule having an average particle size of 10 to 1000 μm, more preferably 10 to 500 μm.
As this powdery granular material, an extender pigment in an undercoat aqueous one-component polyurethane coating composition is preferably exemplified.
As materials for the microcapsule, inorganic materials such as glass and silica, polymethyl methacrylate, vinylidene chloride-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, Examples include organic materials such as polyacrylonitrile, and inorganic and organic composite materials, but organic materials that are easy to obtain an elastic feel are preferable.
These may be used alone or in combination of two or more.

  In this topcoat aqueous two-component polyurethane coating composition, the filler is 1 to 200 parts by mass, and further 10 to 100 parts by mass, based on 100 parts by mass of the total amount (as solid content) of the hydrophilic polyurethane polyol and the hydrophilic polyisocyanate. It is preferable to use a part.

  The filler can be used by blending with both the main agent and the curing agent, and can also be used by blending with either one.

  The undercoat aqueous one-component polyurethane coating composition or the topcoat aqueous two-component polyurethane coating composition according to the present invention further includes a color pigment, a dye, a dispersion stabilizer, a viscoelasticity adjusting agent, an ultraviolet absorber, an antioxidant, Additives such as a light stabilizer, a fluorescent brightening agent, a leveling agent, an antifoaming agent, a curing catalyst, a film-forming aid, an organic solvent, and a texture agent (eg, silicone oil) can be used.

The touch-sensitive coated body of the present invention is formed by forming an undercoat foam layer and an overcoat layer on a substrate, and the average deviation of the average friction coefficient on the surface is 0.0025 to 0.0100.
The undercoat foam layer is formed by applying the undercoat water-based one-component polyurethane paint composition and then applying the overcoat water-based two-component polyurethane paint composition without baking and drying both layers simultaneously. In this case, the baking and drying conditions are preferably 20 to 100 ° C. for 10 to 180 minutes, and more preferably 60 to 80 ° C. for 10 to 60 minutes.
The touch feeling such as the moist feeling and the smooth feeling of the touch-sensitive design coated body (top coat layer) of the present invention can be expressed numerically by the average friction coefficient (μ) of the dry film and its variation deviation (μ _MD ). it can. In the present invention, the average deviation of the average friction coefficient of the dry film (overcoat layer) is 0.0025 to 0.0100, and if the average deviation of the average friction coefficient is less than 0.0025, it becomes a smooth feel and exceeds 0.0100. It is not preferable because it feels rough. In order to obtain a moist feeling, the dry friction film (overcoat layer) in the present invention preferably has an average friction coefficient of 0.2 or less, and in order to obtain a smooth feeling, the average friction coefficient exceeds 0.2. preferable.

  There is no limitation on the base material, and any type or shape may be used. However, since the undercoat foam layer of the touch-sensitive coated body of the present invention does not necessarily need to be formed by heat curing or thermal expansion, Synthetic resin base materials that are weak against heat can be suitably used as the base material in the present invention. Further, the surface of the substrate may be smooth, or may have been subjected to graining or the like in advance. Furthermore, the base material may be a single layer or may be composed of two or more layers. When it consists of two or more layers, the same material may be sufficient as each layer, and a different material may be sufficient as it. Moreover, each layer may be joined by an adhesive.

Application of water-based one-component polyurethane coating composition for undercoating to base material and water-based two-component polyurethane coating composition for top coating is doctor blade, reverse roll, gravure roll, spinner coat, extruder, spray coat, dip coat, flow It can be performed by a known method such as coating or wire coating. The coating amount is preferably 1 to 300 g / m ² , particularly 1 to 200 g / m ² in terms of solid content of 100% by mass.

In the touch-sensitive design coated body of the present invention, the overcoating film is made thick and the mass of the overcoating film is increased or the resin curing reaction rate of the overcoating film is overcome so as to overcome the force of pushing up the overcoating film by foaming of the undercoating foam layer. By promoting, a smooth coating film appearance can be obtained. On the other hand, making use of the force that pushes up the top coat by foaming the undercoat foam layer, making the top coat as a thin film, reducing the mass of the top coat, or suppressing the resin curing reaction rate of the top coat makes it easy to move the top coat Various leather wrinkle design appearances can be obtained.
Therefore, the undercoat foam layer of the touch-sensitive design-coated body of the present invention has a dry thickness of 50 to 5000 μm, particularly 100 to 2000 μm, and the overcoat layer has a dry thickness of 10 to 200 μm, particularly 20 to 100 μm. Is preferable.
In the tactile sensation coated body of the present invention, each of the undercoat foam layer and the topcoat layer may be composed of one layer, or may be composed of two or more layers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to these and is not interpreted. In the synthesis examples, examples, and comparative examples, “%” represents “% by mass” excluding the elastic deformation ratio.

Synthesis example 1
In a reaction vessel equipped with a reflux condenser, a dropping funnel, a gas inlet tube and a thermometer, under a nitrogen stream, 201 g of trimethylolpropane, 184 g of glycerin, 120 g of dimethylolheptane, 134 g of dimethylolpropionic acid, N-methyl-2- Pyrrolidone 500 g was charged and heated to 60 ° C. with stirring. When uniform, 714 g of hexamethylene diisocyanate was added dropwise, and the temperature was raised to 80 ° C. and reacted for 4 hours. Thereafter, the reaction solution was cooled to 30 ° C., and 101 g of triethylamine, 170.5 g of N-methyl-2-pyrrolidone, and 1741.2 g of ion-exchanged water were added while stirring to obtain a hydrophilic polyurethane polyol.
This hydrophilic polyurethane polyol had a nonvolatile content of 35% and a hydroxyl value of 211 (solid content).

Examples 1 to 11 (Formation of undercoat foam layer and topcoat layer)
Undercoat prepared by mixing ingredients other than azodicarboxylic acid dialkyl ester (foaming agent) in Table 1 with a disperser and a high-speed stirrer, adding azodicarboxylic acid dialkyl ester (foaming agent), and further mixing with a high-speed stirrer Coating Composition Nos. 1 to 3 were applied on an ABS resin substrate using an air spray.
Next, after mixing the components other than the curing agent shown in Table 2 with a disperser and a high-speed stirrer (without heating), the curing agent (hydrophilic group-containing isocyanurate-modified hexamethylene diisocyanate-based isocyanate prepolymer (Sumitomo Bayer Urethane ( Co., Ltd., Bihijoule 3100, NCO content 17.3%, non-volatile content 100%)) and further mixed with a high-speed stirrer to prepare a top coating composition No. 4-7 were applied onto the undercoat coating layer using an air spray, left at room temperature (20 ° C) for 10 minutes, and then baked and dried at 80 ° C (material temperature) for 60 minutes to obtain a dried coating film. Formed.
About the obtained dry coating film, the characteristic and coating-film characteristic of the undercoat foaming layer were measured.
These results are shown in Tables 3-5.

[Characteristic test of undercoat foam layer]
About the obtained dried coating film, the foaming state of the undercoat foam layer was determined by visually observing the cross section with an optical microscope. The strength was measured by a JIS K5400 abrasion resistance test. Adhesion with the substrate was measured by a JIS K5400 cross cut test. Alkali discoloration resistance is JIS
It was measured by the K5400 alkali resistance test.

[Film characteristics test]
The surface of the obtained dried coating film was measured using a friction tester (friction: fingerprint type sensor) (manufactured by Kato Tech Co., Ltd., KES-SE), and the average friction coefficient and the average deviation thereof were determined. Moreover, the surface appearance by visual observation and the elasticity and tactile sensation by finger touch were determined for the dried coating film surface.

Claims (3)

On the base material, an undercoat foam layer and an overcoat layer are formed, and the touch-sensitive design body with an average deviation of the surface average friction coefficient of 0.0025 to 0.0100,
The undercoat foam layer is an undercoat foam elastic layer formed by applying and curing an undercoat aqueous one-component polyurethane coating composition containing a polyurethane dispersion, a foam stabilizer, a foaming agent, and an extender pigment, The topcoat layer is composed of a main agent containing a hydrophilic polyurethane polyol and a curing agent containing a hydrophilic polyisocyanate, and either or both of the main agent and the curing agent further contain a filler. The touch-sensitive design-coated body, which is an overcoat layer formed by applying and curing a two-component polyurethane coating composition. A method for producing a touch-sensitive design coated body having an average deviation of a surface average friction coefficient of 0.0025 to 0.0100, which is formed by forming an undercoat foam layer and an overcoat layer on a substrate,
An undercoat aqueous one-component polyurethane coating composition containing a polyurethane dispersion, a foam stabilizer, a foaming agent, and an extender pigment is applied onto a substrate, and then a hydrophilic polyurethane polyol is contained without baking and drying. And a curing agent containing a hydrophilic polyisocyanate, and either or both of the main agent and the curing agent further contain a filler. Baked and dried. An average deviation of the surface average friction coefficient of 0.0025 to 0.0100, which is formed by forming an undercoat foam layer having a dry film thickness of 50 to 5,000 μm and an overcoat layer having a dry film thickness of 10 to 200 μm on the substrate. A method for producing a tactile design paint body,
An undercoat aqueous one-component polyurethane coating composition containing a polyurethane dispersion, a foam stabilizer, a foaming agent, and an extender pigment is applied onto a substrate, and then a hydrophilic polyurethane polyol is contained without baking and drying. And a curing agent containing a hydrophilic polyisocyanate, and either or both of the main agent and the curing agent further contain a filler. Baked and dried.