JP2870053B2 - Decorative paint composition and its painted product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a paint composition which is newly useful in the paint industry, printing ink industry, and the like, and a coated product thereof. More specifically, it has excellent scratch resistance and secondary workability, comprising specific polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as essential film-forming components. , A coating composition capable of forming a design coating film having both visual and tactile properties,
And its coated articles.

[Conventional technology]

Conventionally, matte coating films composed of various elastic or non-elastic resin particles and a synthetic resin binder are already well known and used as a design imparting coating material. Matte coating films using resin particles are particularly inferior in soft feel (soft touch) and scratch resistance, while coating films using elastic resin particles are more inexpensive than those using non-elastic resin particles. Although they are excellent in terms of feel and scratch resistance, they cannot be said to be sufficient in terms of swelling or dissolving with a solvent and outdoor durability.

However, in recent years, in order to improve these disadvantages, for example, JP-A-48-51949, JP-A-62-67003,
It has been reported that polyurethane polyurea particles formed by an interfacial polymerization reaction between a polyisocyanate and a polyamine as disclosed in JP-A-62-149333 or JP-B-63-58610 are used.

However, in the particles obtained by such a method, the formation of the particles is performed by a ureation reaction, and therefore, the particles are formed only by the formation of the outer wall of the particles. If the pigment has a hollow structure or a small pore (microvoid) structure, or if the pigment is included in the particles by such a method,
Inevitably, the pigment must be dispersed using isocyanates or isocyanate prepolymers, and therefore, the management of water and the like in the pigment occurs, which is inconvenient.

In particular, the particles having such a microvoid structure have many uneven holes, and therefore, when a coating film is formed in combination with a synthetic resin binder, the particles have abrasion resistance or scratch resistance (when rubbed with a nail). And the strength tends to be inferior.

By the way, it is known that the above-mentioned disadvantages such as scratch resistance can be improved by imparting strength to the synthetic resin binder itself to be combined with the elastic particles, for example, acrylic resin, polyester resin,
Specific urethane resins, such as melamine resins, phenol resins, epoxy resins, and the like, are known as this type of synthetic resin.

However, an elastic particle-containing coating film using these resins as a binder component generally cannot improve both the abrasion resistance and the soft feeling. Is extremely limited in terms of the composition of the binder itself and the design of the paint itself, and therefore cannot deal with the recent diversification and individualization of designs in various products, so-called fatal Disadvantages.

[Problems to be solved by the invention]

Thus, in the conventional design imparting coating material,
In any case, since the elastic resin particles in question do not have a sufficient three-dimensional crosslinked structure, they are easily swelled in a solvent, and are not preferable in terms of weather resistance. However, there is still a great problem that the synthetic resin binder to be combined with such elastic particles is extremely limited because of the disadvantage in terms of strength which is important for the property.

Although these problems are still to be solved without being corrected, the present invention aims to solve various problems in the prior art as described above.

Therefore, the problem to be solved by the present invention is, at least, one of them, in particular, abrasion resistance, durability, and visual and tactile properties (hereinafter, both senses are also referred to as a visual feeling). An object of the present invention is to provide a versatile and multifunctional design paint composition and a coated article thereof which are excellent in quality and can be applied to a wide range of uses.

[Means for solving the problem]

Thus, the present inventors have focused on the problems to be solved by the invention as described above, and as a result of intensive studies, it has been found that the outer and inner walls of the particles are sufficiently formed. It is obvious that the coating composition composed of the specific polyurethane polyurea particles having a primary crosslinked structure and the binder resin is excellent in scratch resistance, durability, and tactile sensation. ,in addition,
Various articles coated with such a decorative paint composition on metal materials and processed products thereof, plastics materials and processed products thereof, wood and processed products thereof, leathers, papers, ceramic molded products, and the like become extremely useful. The present invention has been completed by finding out that the present invention is an object.

That is, the present invention basically intends to provide a decorative paint composition comprising a polyurethane polyurea particle having a three-dimensional crosslinked structure and a binder resin as essential film-forming components. And, further, painted with the design paint composition having such a specific configuration, respectively,
An object is to provide various articles such as a metal material or a product thereof, a plastics material or a product thereof, wood or a product thereof, leathers, papers, and ceramic moldings.

In particular, the polyurethane polyurea particles having the three-dimensional cross-linking structure are an organic phase in which isocyanate groups are blended in excess of hydroxyl groups, and can form a three-dimensional cross-linking structure by reaction. An organic phase and an interfacial polymerization reaction between an equivalent amount or less of a polyamine with respect to an excess of isocyanate groups in the organic phase, and that obtained through a urethanation reaction inside the particles, Is characterized in that it contains and contains a pigment therein, and that the particles have a specific film property of 50 to 500 kgf / cm ² as their initial elastic modulus.

Here, first, the polyurethane polyurea particles having three-dimensional crosslinks used in the present invention are obtained from, for example, a polyisocyanate compound, a polyhydroxy compound, and a polyamine. Any of those known per se can be used, but among them, particularly representative ones may be used, and tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane −4,4 ′
-Diisocyanate, hydrogenated diphenylmethane-4,4'-
Diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, 1,3-bis (α, α-dimethyl isocyanatomethyl) benzene, cyclohexyl-1,4- Aliphatic, aromatic or cycloaliphatic di-isomers such as diisocyanate, oxadiazinetrione diisocyanate, isophorone diisocyanate or triphenylmethane diisocyanate.
Or triisocyanate monomers; or various modified polyisocyanates such as tri- or more functional polyisocyanurate-type polyisocyanate or burette-type polyisocyanate based on these various monomers; At least one of monomers or modified polyisocyanates and one of various polyhydroxy compounds such as polyhydric alcohols, polyester polyols, polycarbonate polyols, polybutadiene polyols or polypentadiene polyols;
Urethane-modified polyisocyanate prepolymers having an isocyanate group at the end obtained by a urethanization reaction with at least one kind thereof.
More than one kind may be used in combination.

In order for the obtained polyurethane polyol urea particles (hereinafter, also referred to as polymer particles) to be particularly excellent in toughness, the number average molecular weight of the polyisocyanate compound is in the range of 200 to 10,000, preferably 300
Those within the range of 77,000, more preferably within the range of 500 to 5,000 are desirable.

In addition, the above-mentioned organic phase may contain a urethane-modified polyisocyanate compound obtained by a reaction of polycaprolactone polyester polyol and diisocyanate in all polyisocyanate compounds in an amount of 10% by weight or more, preferably 20% by weight or more. If this is the case, the toughness of the polymer particles will be further improved.

In designing the polyisocyanate compound,
In particular, in consideration of weather resistance and the like, the type of the isocyanate monomer unit should be limited to aliphatic and / or alicyclic type, and such a usage is recommended.

On the other hand, together with the polyisocyanate compound, a polyhydroxy compound as a component constituting the organic phase,
It is a very important component for compensating for the lack of internal cross-linking due to the formation of the walls of the polymer particles and further improving the mechanical strength of the particles, but such polyhydroxy compounds are known per se. Some of them can be used, but among them, if only typical ones are exemplified, they belong to any of the following groups.

a) ethylene glycol, propylene glycol, 1,
3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxytyl) cyclohexane, bisphenol A , Hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, hexanetriol, tris (2-hydroxyethyl) isocyanurate Or polyhydric alcohols such as pentaerythritol; b) polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene tetramethylene glycol, polyoxypropylene tetramethylene glycol or polyoxyethylene polyoxypropylene. Polyether glycols such as polyoxytetramethylene glycol; c) various polyhydric alcohols as described above and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl. Modified polyether polyols obtained by ring-opening polymerization with glycidyl ether and the like; d) Polyester polyols obtained by co-condensing at least one of various polyhydric alcohols and polycarboxylic acids as described above. If only typical examples of polycarboxylic acids mentioned here are given, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citracone Acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2, 4-cyclohexanetricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

e) Lactones obtained by a polycondensation reaction between at least one of the above-mentioned various polyhydric alcohols and various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Polyester polyols or lactone-modified polyester polyols obtained by a polycondensation reaction of various polyhydric alcohols and polycarboxylic acids with various lactones as described above, respectively, as described above; f) Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, and glycidyl esters of monobasic acids and / or polybasic acids are used as polyester polyols. At least one of them at the time of preparation G) polyester polyamide polyols, polycarbonate polyols, polybutadiene polyols, polypentadiene polyols, castor oil, castor oil derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, or hydroxyl group-containing acrylic copolymers, etc. It is.

Of course, these polyhydroxy compounds as shown in (a) to (g) may be used alone or in combination of two or more, but their number average molecular weight is 200 to 100,
000, preferably 300 to 7,000
More preferably, those falling within the range of 500 to 5,000 are suitable for sufficient crosslinking inside the polymer particles.

Further, in order to obtain tough polymer particles, it is preferable to use a polyester polyol, in particular, a polyester polyol obtained by a polycondensation reaction with a lactone such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. It is desirable to use lactone-based polyester polyols.

In the present invention, the ratio between the isocyanate group equivalent of the polyisocyanate compound and the hydroxyl group equivalent of the polyhydroxy compound is 1: 0.1 to 1: 0.9, preferably 1: 0.
The composition ratio is such that these two components are mixed so as to be in the range of 1 to 1: 0.8, more preferably 1: 0.1 to 1: 0.7, and that the mixture of both components itself can be three-dimensionally crosslinked. And should be.

That is, when these mixtures are completely urethanized, the mixture must be in a gel state, and must be formulated so that fluidity cannot be obtained even by heating or diluting the true solvent.

The above two conditions for designing the organic phase are indispensable conditions for obtaining an internal crosslinked state that cannot be obtained only by the interfacial polymerization reaction by the addition of a polyamine described later, and are the basic requirements of the present invention. One.

In this case, in order to make the interfacial polymerization effective and effective, an excess of isocyanate groups in the above-mentioned range is necessary, and such a range is set so that the outer wall of the particles is formed quickly.

Further, in the present invention, the toughness and solvent resistance of the whole particle, which cannot be obtained by the conventional technique, are improved by three-dimensionally proceeding the urethanization reaction inside the particle.

Due to the design of the three-dimensional urethanization reaction inside the polymer particles, the polyisocyanate compound and / or the polyhydroxy compound having three or more functional groups are contained in the total amount of the polyisocyanate compound and the polyhydroxy compound contained in the organic phase. 0.1 mol% or more, preferably 0.2 mol%
As described above, more preferably, by adding 0.3 mol% or more, a good three-dimensional crosslinked state inside the particles can be obtained.

As the polyisocyanate groups in the organic phase are consumed as the interfacial polymerization reaction with the polyamine described below progresses, the equivalent ratio between the isocyanate groups and the hydroxyl groups in the polymer particles approaches, and the crosslink density inside the polymer particles decreases. The properties further increase with the progress of the urethanization reaction, and various properties such as toughness and durability of the polyurethane polyurea particles used in the present invention are further improved.

As the pigment to be included in the present invention, known and commonly used organic pigments, inorganic pigments, extender pigments, and the like are used. Among them, only typical representative pigments are mentioned. Insoluble azo pigments such as Gin Yellow, Hansa Yellow and Lake Red 4R; soluble azo pigments such as Lake Red C, Carmine 6B and Bordeaux 10; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; bases such as rhodamine lake and methyl violet lake Acid dyeing lakes such as quinoline lake and fast sky blue; mordant pigments such as alizarin lake; anthraquinones; vat pigments such as thioindigo and perinone; pigments such as synchasia red B Quinacrid System pigment; Djiokisajin pigments such as the Djiokisajin-Baiore'; other condensed azo pigments such as Kuromofutaru. Examples of the inorganic pigment,
Chromates such as graphite, zinc chromate and molybdate orange; ferrocyan compounds such as navy blue; metal oxides such as titanium white, zinc white, mapico yellow, iron black, red iron oxide and chromium oxide green; cadmium yellow, cadmium red and Sulfide selenides such as mercury sulfide; sulfates such as barium sulfate and lead sulfate; silicates such as calcium silicate and ultramarine; carbonates such as calcium carbonate and magnesium carbonate; phosphates such as cobalt violet and manganese purple; Metal powders such as aluminum powder, gold powder, silver powder and brass powder; pearl pigments and the like; as extender pigments, precipitated barium sulfate, barium carbonate, powder, gypsum, alumina white, clay, silica, silica white, Talc, calcium silicate and sedimentable Such as magnesium and the like, such as carbon black which does not belong to both inorganic and organic pigments may be used.

These pigments are one of the polyhydroxy compounds described above.
With the seeds or more, they are kneaded uniformly in advance and used as a mill base.If necessary, the pigments are subjected to a scientific surface treatment before or during kneading, or two or more pigments are combined or kneaded, or Additives such as a pigment dispersant and a color-separation inhibitor known and commonly used in the paint and printing ink industries can also be used in combination. The kneading is performed using a known and commonly used dispersing machine such as a ball mill, a pebble mill, a sand mill, an attritor, a roll mill, a high-speed impeller disperser and a high-speed stone mill, and if necessary, an organic solvent inert to a hydroxyl group or an isocyanate group. May be added to adjust the viscosity of the kneading system. Suitable organic solvents include aromatic or aliphatic hydrocarbons, esters, ethers, and ketones, particularly, benzene, toluene, xylene, cyclohexane, methylcyclohexane, diphenyl ether, and mineral spirit. I have. The ratio of resin and pigment in the mill-base kneading step is 100% of resin solids.
1 to 900 parts by weight, preferably 2 to 8 parts by weight of pigment
100 parts by weight, particularly preferably in the range of 5 to 500 parts by weight, is suitable.

The mill base thus obtained, the polyhydroxy compound and the polyisocyanate compound are blended within the above-described various ranges of the present invention, and uniformly mixed to form the hydrophobic organic phase (1). The ratio of the pigment contained in 1) is 0.5 to 20 with respect to 100 parts by weight of the total resin solids.
0 parts by weight, preferably 1 to 150 parts by weight, particularly preferably 2 parts by weight
-100 parts by weight are preferred.

This hydrophobic organic phase (1) is finely dispersed in an aqueous phase (2), and one of the excess isocyanate groups contained in the organic phase is removed.
0.2 to 1.0 equivalent of polyamine per equivalent, preferably 0.3 equivalent
To 1.0 equivalent, more preferably 0.4 to 0.9 equivalent, to carry out a ureation reaction at the particle interface, and to carry out a urethanation reaction inside the polymer particles to obtain extremely tough pigmented polyurethane polyurea particles. Can be

Suitable polyamines to be used in the present invention are known and commonly used diamines, polyamines or mixtures thereof. Among them, 1,2-ethylenediamine, bis- (3-aminodiamine) are mentioned, if only typical ones are mentioned. Propyl) -amine, hydrazine, hydrazine-2-ethanol, bis- (2-methylaminoethyl) -methylamine, 1,4-diaminocyclohexane, 3-amino-1
-Methylaminopropane, N-hydroxyethylethylenediamine, N-methyl-bis- (3-aminopropyl) -amine, tetraethylenediamine, hexamethylenediamine, 1-aminoethyl-1,2-ethylenediamine, bis- (N, N '-Aminoethyl) -1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, phenylenediamine, toluylenediamine, 2,4,6-triaminotrienetrihydrochloride, 1,3,8-triethyl Amino naphthalene, isophorone diamine, xylylenediamine, hydrogenated xylylenediamine, 4,4'-diaminodiphenylmethane or hydrogenated 4,4'-diaminodiphenylmethane, or derivatives of these polyamine monomers, and the like. Aliphatic from the point of view And / or the use of alicyclic systems is desirable.

In the present invention, the organic phase dispersed in the aqueous phase is non-reactive, and a hydrophobic organic solvent may be added as necessary to reduce the viscosity and improve the dispersibility in the aqueous phase. . In this case, the amount of the organic solvent is suitably 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less in the whole organic phase. Suitable organic solvents include aromatic or aliphatic hydrocarbons, esters, ethers, and ketones, particularly, benzene, toluene, xylene, cyclohexane, methylcyclohexane, diphenyl ether, and mineral spirit. I have. These organic solvents may be removed by a treatment such as heating or pressure reduction during or after the formation of the polymer particles, if necessary.

The aqueous phase in which the organic phase is dispersed is polyvinyl alcohol,
It contains 0.2 to 20% by weight of at least one selected from various protective colloids such as hydroxyalkyl cellulose, carboxyalkyl cellulose, gum arabic, polyacrylate, polyacrylamide, polyvinylpyrrolidone, and ethylene maleic anhydride copolymer. The aqueous phase may contain 0.2 to 10% by weight of a nonionic, anionic or cationic surfactant.

The present invention is characterized in that the urethanization reaction is positively performed inside the polymer particles, but as is well known, the urethanization reaction between a hydroxyl group and an isocyanate group is particularly effective when the isocyanate group is a fatty acid. When the reaction is based on an aromatic group or an alicyclic system, the reaction rate tends to be slow as compared with the ureation reaction with an amino group. As is well known, the reactivity between water and isocyanate is extremely slow as compared to the reactivity with hydroxyl groups, and the penetration of water into the interior of particles is negligible due to the isolation effect of the outer wall formed by the addition of polyamine. , Raise the reaction temperature,
By taking time, the object of the present invention to carry out the urethanation reaction in the particles is achieved.However, the present inventors have conducted repeated studies to improve the above reaction conditions, and as a result, have found that cobalt naphthenate is , Zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin diacetate One or more of a variety of organometallic catalysts, such as dibutyltin dilaurate, tin octanoate or potassium oleate, may be added to a hydrophobic organic phase at 5
It has been found that toughness of the crosslinked polymer particles can be formed in a very short time by the addition of -10,000 ppm, preferably 10-5,000 ppm. These organometallic catalysts promote the reaction between isocyanate groups and hydroxyl groups extremely effectively.

The addition of the above-mentioned organometallic catalyst to the organic phase prior to water dispersion (fine dispersion) increases the viscosity of the organic phase and decreases the dispersibility in the aqueous phase. Is not practical, and addition of the organometallic catalyst after the addition of the polyamine is difficult due to the state in which the outer wall of the polymer particles is being formed. Since the effect of accelerating the urethanization reaction inside the polymer particles tends to be reduced, the timing of adding the organometallic catalyst is determined during the water dispersing step of dispersing the organic phase in the aqueous phase. Alternatively, it is most appropriate between the dispersing step and the middle of the step of adding the polyamine.

Next, as the binder resin described above, basically,
Any material can be used as long as it can form a coating film. Therefore, any one may be used. However, if only typical ones are exemplified, polyurethane resin, acrylic resin, alkyd resin, polyester resin, melamine resin,
Urea resins, epoxy resins, polyamide resins, vinyl acetate resins, vinyl chloride resins or various synthetic resins such as fluororesins, or various rubbers such as natural rubber or synthetic rubber, and further, Various natural polymer compounds such as cellulose and the like may be used alone or in combination of two or more.

Furthermore, it goes without saying that each of the above-mentioned resins may be used in the form of an aqueous solution or an aqueous dispersion.

When to sufficiently achieve the object of the present invention, as one of the film characteristics of the binder resin, the use of such things as fall within the initial elastic modulus of the resin is 50~500kgf / cm ² preferably .

The term "initial elastic modulus" as used herein refers to a value defined by a value obtained by dividing the tensile strength (kg) of the test film at the time of 1% deformation by the cross-sectional area (cm ² ) of the sample. The film is prepared by the following method and measured.

That is, first, a solution containing the test binder resin is applied on the support so that the dry film thickness becomes 100 μm, and the temperature is within a range (20 to 200 ° C.) at which the binder resin film can be formed. Then, the coating thus obtained is peeled from the support to prepare a test piece having a target width of 10 mm and a length of 40 mm. It is determined by performing a tensile test on a Tensilon tensile tester at 20 ° C. at a tensile speed of 20 mm / min.

As described above, the initial elastic modulus of the binder resin used in the present invention, particularly desirable 50~500kgf / cm ² becomes the range, in the case of less than 50 kgf / cm ² is inevitably obtained designability it like abrasion resistance of the coating film becomes inferior, while, in the case of those too large values exceed 500 kgf / cm ² is absolutely, since such soft feel and secondary workability is inferior, either Is also not preferred.

The mixing ratio between the polyurethane polyurea particles and the binder resin in the present invention is based on the total volume of these two components, and is calculated as a solid content of each component.
Binder resin: polymer particles = 25 to 75: 75 to 25 (volume percentage ratio) is appropriate.

If the solid content volume of the binder resin is less than 25%, cracks tend to occur in the coating film, while if it is more than 75%, it becomes difficult to become a matte coating film. In any case, it is not preferable.

The decorative coating composition of the present invention contains, in addition to the polyurethane polyurea particles and the binder resin described above, ordinary pigments, dyes, ultraviolet absorbers, smoothing agents (smoothing agents), precipitation inhibitors, respectively. Alternatively, of course, various additive components such as a thixotropic agent may be added and mixed.

Therefore, in particular, in coloring the composition of the present invention, it is, of course, recommended to use the polymer particles in a form containing a pigment in advance as it is, but within a range that does not impair the features of the present invention. Alternatively, the addition of a pigment or a dye to the coloration without departing from the object of the present invention may have no problem at all.

Thus, the decorative coating composition of the present invention, if necessary, may be diluted with a solvent or water or the like that can be diluted with the binder resin, and then brush-coated, roll-coated, flow-coated, spray-coated or dipped-coated. Various substrates can be coated by a known and commonly used coating method such as the above.

That is, the composition of the present invention obtained as described above, for example, ABS resin, AS resin, polyester resin,
Various plastics such as polyphenylene oxide resin, polyurethane resin, polycarbonate resin, polyamide resin (among others, nylon), PS resin, polypropylene resin, acrylic resin, vinyl chloride resin or epoxy resin; steel plate, zinc iron plate, zinc plating Various metal materials such as steel plate, tin plate, copper plate, aluminum plate or zinc plate; various wood materials such as rosewood, ebony, rosewood, teak, oak, china, cherry or lauan; fine paper, coated paper, kraft paper or Various papers such as roll paper; natural leather or various leathers such as synthetic leather such as urethane, nylon or vinyl chloride; or glass such as soda-lime glass or borosilicate glass, ceramic, gypsum board or mortar And various ceramic moldings In terms of materials, as well as by application, wooden articles such as woodwork / furniture products or wooden floors; electric products such as electric appliances or their parts; automobile-related articles such as automobile parts; Building-related materials such as building materials; paper products such as wallpaper, decorative paper or printing paper; office-related products such as office equipment; food-related products such as furniture; toddler-related products such as toys; or glass products Is applied directly or via a primer or the like.

[Action]

The coating film obtained by using the decorative paint composition of the present invention configured as described above is uniformly arranged although the surface of the coating film has irregularities due to the polymer particles wrapped with the binder resin. There is a strong tendency to exhibit a complete matte effect and to have a suede-like characteristic visually.

Further, the decorative coating composition of the present invention comprising polyurethane polyurea particles, and a binder resin having an action of covering the polymer particles and binding between the polymer particles, has a tough coating film. Although Aru Te which can form, among other things, initial elastic modulus has a particular value of 50~500kgf / cm ^2, deformed by a so-called external force easily, which is one of the film characteristics of the binder resin itself When a binder resin having a thickness within the above range is used, a coating film structure capable of absorbing and radiating external energy given to the coating film against abrasion, abrasion or scratch is obtained.

Further, the polyurethane polyurea particles having a three-dimensional crosslinked structure containing a pigment substantially function as a colorant and exert an effect as a colorant, and moreover, the pigment itself is the polymer itself. Almost no pigment is present on the surface of the particles, and the pigment is exclusively contained inside the polymer particles or in the coating.

〔The invention's effect〕

As described above, the decorative coating composition of the present invention and the coated product are both composed of polyurethane polyurea particles having a three-dimensional crosslinked structure, and a binder resin,
In particular, all of the articles coated with the composition of the present invention have an extremely high-grade, high-grade matte coating film formed from the place where the polymer particles protrude from the particle surface. You can do it.

In addition, since the polymer particles themselves have a three-dimensional crosslinked structure, the decorative coating composition of the present invention and the coated product thereof have solvent resistance, abrasion resistance, scratch resistance, and resistance to scratching. It is capable of forming a coating film having excellent effects such as scratch resistance and durability, and in particular, by limiting the coating film characteristics of the binder resin, such a characteristic effect was further enhanced. It can form a coating film,
In addition, a coating film having excellent soft touch (soft touch) can be formed.

〔Example〕

Next, the present invention by reference examples, examples and comparative examples,
This will be described more specifically. In the following, all parts and percentages are by weight unless otherwise specified.

In addition, each raw material component used will be described in advance as follows.

Among them, first, the polyisocyanate compound is as follows.

That is, "Varnock DN-950" [a hexamethylene diisocyanate adduct-type polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Incorporated; number average molecular weight = 640, number of functional groups: 3, isocyanate group content in terms of solid content = 16.8% The solid content of PI-1 was used in the following.
Abbreviated.

Furthermore, although 1,6-hexamethylene diisocyanate was used, it is abbreviated as HDI below.

Next, the polyhydroxy compound is as follows.

That is, a polyester polyol having a hydroxyl value of 187 obtained by co-condensation of neopentyl glycol and adipic acid was used. Hereinafter, this is abbreviated as PO-1.

Further, a polycaprolactone polyester diol having a hydroxyl value of 187 obtained by a polycondensation reaction of neopentyl glycol and ε-caprolactone was also used, and is hereinafter abbreviated as PO-2.

Further, the polyamine is as follows.

That is, although ethylenediamine was used, it is abbreviated as EDA hereinafter.

In addition, 1,6-hexamethylenediamine was also used,
Hereinafter, this is abbreviated as HMDA.

Reference Example 1 (Preparation Example of Polyurethane Polyurea Particles) 300 parts of a 0.2% aqueous solution of "PVA-217" (partially saponified product of polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) was placed in the flask of 1, and this was added to the flask. While the aqueous phase was used, 55.7 parts of PI-1, 9.3 parts of HDI, and 30 parts of PO-1 were mixed in another container to obtain an organic phase.

At 20 ° C., using a homomixer, 7,000 to 7,500
While stirring the aqueous phase at rpm., the organic phase prepared in advance was charged here and stirred for one minute to obtain a dispersion.

Then, this dispersion was transferred to another flask, and 0.1 part of di-n-butyltin dilaurate (DBTDL) was added while stirring at 200 rpm with a paddle-type stirring blade. Two minutes later, a 50% aqueous solution of HMDA was added. 21.7 parts were also added. Room temperature (about 25
° C) for 2 hours, then raise the temperature to 50 ° C, keep it at the same temperature for 1 hour, and keep it at 80 ° C for 2 hours to continue the reaction, and suspend the desired polyurethane polyurea particles. A liquid was obtained.

 The average particle size of the particles was 30 μm.

In addition, the particles are extremely stable without swelling and dissolving in acetone, ethyl acetate, xylene, or the like. Further, the particles may be sufficiently filled inside with a polymer. As a result of observation with an electron microscope, it was confirmed.

Reference Example 2 (Example of Preparing Polyurethane Polyurea Particles Containing Pigment) First, 80 parts of PO-2, "Fast Gen Super.
20 parts of Red (Fastogen Super Red) 7093Y "(a quinacridone organic pigment manufactured by Dainippon Ink and Chemicals, Inc.)
And 25 parts of toluene were mixed and dispersed with a sand grinder for 1 hour to obtain a red mill base. Hereinafter, this is abbreviated as MB-1.

Next, 300 parts of a 0.2% aqueous solution of “PVA-217” was charged into one flask, and the mixture was stirred at 20 ° C. with a homomixer at 7,000 to 7,500 rpm. -1 37.5 parts, PO-1 16 parts, PI-1 30
And 20 parts of HDI were added, and the organic phase was added. Further, 0.2 part of DBTDL was added, and the mixture was stirred for 1 minute to obtain a dispersion.

Thereafter, the dispersion was transferred to another flask, and stirred with a paddle-type stirring blade at 200 rpm.
22.3 parts of a 25% aqueous solution were added.

After maintaining at room temperature (about 25 ° C) for 2 hours, 50 ° C
And kept at the same temperature for 1 hour and further kept at 80 ° C. for 2 hours to continue the reaction.
A suspension of red polyurethane polyurea particles was obtained.

The average particle size of the polymer particles obtained here was 37 μm.

Further, these particles did not swell and dissolve in acetone, and therefore, no outflow of the red pigment was observed in acetone.

Reference Example 3 (Preparation Example of Polyurethane Polyurea Particles for Control) In a flask, a 300% aqueous solution of 0.2% aqueous solution of “PVA-217” was placed.
Parts into an aqueous phase while the organic phase prepared by mixing 42 parts of HDI and 30 parts of PO-1 in a separate container,
At 20 ° C., the aqueous phase was added with stirring using a homomixer at 7,000 to 7,500 rpm. The mixture was stirred for 1 minute to obtain a dispersion.

Then, the dispersion was transferred to another flask, and stirred with a paddle-type stirring blade at 200 rpm.
One part was added, and two minutes later, another 6 parts of a 50% aqueous solution of EDA was added.

Thereafter, the reaction was carried out at 25 ° C. for 2 hours, and then the reaction was continued at 50 ° C. for 1 hour and further kept at 80 ° C. for 2 hours. A suspension of polyurethane polyurea particles for use was obtained.

The average particle size of the polymer particles thus obtained was 25 μm.

The polymer particles were completely dissolved in any solvent such as acetone, ethyl acetate and xylene.

Examples 1 to 5 In combinations as shown in Table 1, 20 parts of polymer particles, 20 parts of binder resin, 0.2 parts of silicone leveling agent, 0.4 parts of polyamide anti-settling agent, Xylene / n-butyl acetate = 50/50 (parts by weight) and 60 parts of a mixed solvent are mixed uniformly, and PVC (pigment volume concentration) is mixed.
Of 50% was prepared.

As one of the coating properties of the composition of the present invention thus obtained, the places where the values of the initial elastic modulus were measured are summarized in the same table.

Comparative Example 1 In a combination as shown in Table 1, 20 parts of polymer particles, 20 parts of a binder resin, 0.2 parts of a silicone-based leveling agent, 0.4 parts of a polyamide-based anti-settling agent, and xylene / A control coating composition was prepared by uniformly mixing 60 parts of a mixed solvent of n-butyl acetate = 50/50 (parts by weight) with a 50% PVC.

The measurement results of the initial elastic modulus of the control coating composition thus obtained are as shown in the same table.

Various coating compositions obtained in each of the examples and comparative examples were respectively applied on an iron plate or an ABS plate so that the dry film thickness became 50 μm, and dried and cured at 60 ° C. for 30 minutes. Was performed.

Then, after being left at room temperature for one week, various coating film performances were evaluated.

 The results are summarized in Table 2.

Evaluations of those various performances were made in the following manner.

Appearance-Specular gloss of 60 degrees was measured with a gloss meter, and the matte state of the coated surface was visually judged.

−- Gloss is 2 or less, and the coated surface is uniform and completely matte. ○-Gloss is 2 or less and uneven gloss of the coated surface is recognized. X- Gloss is 2 or less. I touched it with my hand and judged it by the degree of soft touch.

◎-Extremely soft feeling ○-Extremely soft feeling ×-Hard and rigid feeling Scratch resistance-Rub # 000 steel wool with a surface pressure of 30 g / cm ² , and after one hour, visually check the state of the painted surface Judged.

◎ -No traces at all ○ -Slight traces at the mark × -Clear and scratches remain Bendability-Fold the painted tin plate 180 degrees (2mm
φ), the state of the painted surface was visually determined (JIS K-5400
Compliant. ◎-No change is observed x-Cracks are generated in the bent part Solvent resistance-A glass cap containing acetone is always placed on the painted surface so that the acetone is hung on the painted surface.
After standing for 24 hours, the state of the coated surface was visually determined.

−- No change observed x- Coating film dissolved Example 6 As a base material, a galvanized steel sheet having a thickness of 0.3 mm was used,
Using a polycarbonate plate, a rosewood plate, a coated paper, a soda-lime glass plate, and a soft PVC leather, if necessary, pretreating these substrates,
The decorative paint composition obtained in the above was applied so that the dry film thickness became 50 μm, and then each of the coated articles thus obtained was allowed to stand at room temperature for one week, and then the examples 1 to 3 were used. In the same manner as in No. 5, the coating film performance was evaluated. The results are summarized in Table 3.

However, only the coated paper was coated by a roll coater, and the other substrates were all coated by air spray.

As is clear from Tables 2 and 3, the decorative coating composition of the present invention and the coated article thereof are excellent in solvent resistance as well as scratch resistance, as well as in flexibility. It is known that the appearance through the visual sense (matting ability) and the tactile sense through the tactile sense (soft touch) are all excellent.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09D 175/00, 5/28 B27K 5/02

Claims (10)

(57) [Claims] 1. A decorative paint composition comprising polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as a film-forming component. 2. The polyurethane polyurea particles having a three-dimensional cross-linked structure are converted into an organic phase in which a polyisocyanate compound having a stoichiometric excess of isocyanate groups and a polyhydroxy compound are mixed. Moreover, an interfacial polymerization reaction between an organic phase capable of forming a three-dimensional crosslinked structure by a reaction and a polyamine having an equivalent weight or less with respect to a stoichiometric excess of isocyanate groups in the organic phase, The decorative paint composition according to claim 1, which is a polyurethane polyurea particle obtained through a urethanization reaction. 3. A mixture of a polyisocyanate compound and a polyhydroxy compound, wherein the polyurethane polyurea particles having a three-dimensional crosslinked structure contain a pigment and have a stoichiometric excess of isocyanate groups. Between an organic phase capable of forming a three-dimensional crosslinked structure by reaction and a polyamine having an equivalent weight or less with respect to a stoichiometric excess of isocyanate groups in the organic phase. The decorative paint composition according to claim 1, which is a pigmented polyurethane polyurea particle obtained through an interfacial polymerization reaction and a urethanization reaction inside the particle. 4. The binder resin according to claim 1, wherein said binder resin has an initial elastic modulus in a range of 50 to 500 kgf / cm ² .
3. The decorative coating composition according to item 3. 5. A metal material coated with the decorative coating composition according to claim 1 or a product thereof. 6. A plastics material coated with the decorative coating composition according to claim 1 or a product thereof. 7. Wood or a product thereof coated with the decorative coating composition according to claim 1. 8. Leathers coated with the decorative coating composition according to claim 1. 9. Papers coated with the decorative coating composition according to claim 1. 10. A ceramic molded article coated with the decorative coating composition according to claim 1.