JPH05320574A - Coating composition with designability - Google Patents

Abstract

PURPOSE:To provide a new coating composition capable of giving coating films with excellent delusteredness and scratch resistance, etc., comprising a polycarboxylic acid (salt) and a coating film-forming component composed of a specific polyurethane-polyurea crosslinked particles and a binder resin. CONSTITUTION:The objective composition comprises a coating film-forming component composed of (A) polyurethane-polyurea crosslinked particles having three-dimensional crosslinked structure and (B) a binder resin (e.g. polyurethane resin, alkyd resin) and (C) a polycarboxylic compound and/or a salt thereof. It is recommended that the component A be prepared by the following process: a polyisocyanate compound is incorporated with a polyhydroxyl compound so as to be excess in the NCO groups relatively to the OH groups to prepare a hydrophobic organic phase followed by finely dispersing this organic phase in an aqueous phase along with addition of a polyamine at a level equivalent to or less than the NVO groups in the organic phase to make an urea-forming reaction at the interface of the particles and simultaneous to make a urethanation in the polymer particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new and useful design coating composition in the field of coating industry, printing ink industry and the like. More specifically, the present invention comprises specific polyurethane polyurea crosslinked particles having a three-dimensional crosslinked structure and a binder resin as essential film forming components, and also comprises polycarboxylic acid compounds. Further, the present invention relates to a coating composition which has a matting property and a scratch resistance and is capable of forming a design coating film having both visual and tactile properties.

[0002]

2. Description of the Related Art Conventionally, a matte coating film composed of various elastic or inelastic resin particles and a synthetic resin binder has been well known and has been used as a design imparting coating material. However, the matte coating film using non-elastic resin particles is particularly inferior in soft touch (soft touch) and scratch resistance, while the coating film using elastic resin particles is non-elastic resin particles. However, they are not satisfactory in terms of touch and scratch resistance, but they are not satisfactory in terms of swelling or dissolution by a solvent and outdoor durability.

However, in recent years, in order to improve these various drawbacks, for example, JP-A-48-51949 and JP-A-SHO-6 are used.
The use of polyurethane polyurea crosslinked particles formed by an interfacial polymerization reaction of polyisocyanate and polyamine as disclosed in JP-A-2-67003, JP-A-62-149333 or JP-B-63-58610. A report is being made.

However, the particles obtained by such a method are all particles which are formed by the ureation reaction, and are therefore limited to merely forming the outer wall of the particles. Has a hollow structure or a small pore (micro void) structure, or if the pigment is to be encapsulated in the particles by such a method, the pigments must be dispersed using isocyanates or isocyanate prepolymers. Therefore, the water content in the pigment must be controlled, which is inconvenient.

In particular, since the particles having such a microvoid structure have many non-uniform holes, when a coating film is formed by combining them with a synthetic resin binder, scratch resistance or scratch resistance (with nails) is obtained. It tends to be inferior in strength because it is difficult to get scratches when rubbed).

On the other hand, a matte coating film composed of various elastic or inelastic resin particles and a synthetic resin binder is a particle itself when the concentration of the particles in the elastic or inelastic resin particle-containing coating film is high. Is highly likely to appear on the surface of the coating and exhibits a high level of matteness. Conversely, if the concentration of particles is low, the particles themselves are less likely to appear on the surface of the coating, and the effect of matteness is small. However, it also has the drawback of easily causing uneven gloss and reducing the commercial value of the coated object. Therefore, it cannot cope with the recent diversification of designs and individualization of various products. There are, so to speak, fatal drawbacks.

[0007]

As described above, in the conventional design-imparting coating material, since the elastic resin particles in question do not have a sufficient three-dimensional crosslinked structure, they swell in the solvent. It is easy, and is not preferable in terms of weather resistance. Further, since it has a hollow structure, it is also disadvantageous in strength, which is important for scratch resistance, and when the particle concentration in the coating film is low, The major problem remains that the high-level matte effect, which is one of the characteristics of the decorative coating composition, is lowered and uneven glossiness is likely to occur.

[0008]

The inventors of the present invention have focused their attention on the problems to be solved by the invention as described above and have made diligent studies. As a result, the outer wall and the inner wall of the particles are sufficiently formed. And specific polyurethane polyurea crosslinked particles having a three-dimensional crosslinked structure,
It was found that a coating composition comprising a binder resin as a coating film forming component and further containing a polycarboxylic acid compound and / or salts of the carboxylic acid is extremely highly practical. Then, the present invention was completed.

That is, the present invention basically comprises a polyurethane polyurea crosslinked particle having a three-dimensional crosslinked structure and a binder resin as a film forming component, and further comprises a polycarboxylic acid compound and / or a salt of the carboxylic acid. (Hereinafter, these are also collectively referred to as polycarboxylic acid compounds.) The present invention is intended to provide an extremely practical practicable design coating composition.

In particular, the polyurethane polyurea cross-linked particles having a three-dimensional cross-linking structure are an organic phase in which isocyanate groups are blended in excess of hydroxyl groups, and the three-dimensional cross-linking structure is formed by reaction. What is obtained through an interfacial polymerization reaction between an organic phase that can be formed and a polyamine having an equivalent amount or less with respect to an excess of isocyanate groups in the organic phase, and a urethanization reaction inside the particles, The particles are characterized in that they contain a pigment inside and are encapsulated therein.

The polyurethane polyurea crosslinked particles having three-dimensional crosslinks used in the present invention are obtained, for example, from a polyisocyanate compound, a polyhydroxyl compound and a polyamine. As such an isocyanate compound, any of those known per se may be used, but to mention only representative ones among them, tolylene diisocyanate, hydrogenated tolylene diisocyanate, Diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl-1,4-disocyanate, isophorone diisocyanate 1,4-tetra Ji diisocyanate, 1,
6-hexamethylene diisocyanate, naphthalene-
Aliphatic, aromatic or alicyclic di- or triisocyanates such as 1,5-diisocyanate, p-phenylene diisocyanate, dibenzyl diisocyanate, diphenyl ether diisocyanate, m- or p-tetramethylxylene diisocyanate or triphenylmethane triisocyanate・ Monomers;

Alternatively, various modified polyisocyanates such as tri- or more functional polyisocyanurate type polyisocyanates or burette type polyisocyanates based on these various monomers; or various monomers and modified compounds as listed above. Terminal isocyanate group obtained by urethanization reaction of one or more kinds of polyisocyanates and one or more kinds of various polyhydroxy compounds such as polyhydric alcohol, polyester polyol, polycarbonate polyol, polybutadiene polyol or polypentadiene polyol Examples of the urethane-containing polyisocyanate prepolymers include urethane, which may be used alone or in combination of two or more kinds.

Here, in order that the obtained polyurethane polyurea crosslinked particles (hereinafter, also referred to as polymer particles) have particularly excellent toughness, the number average molecular weight of the polyisocyanate compound is 200 to 10 1,000
The range of 300 to 7,000 is preferable, the range of 300 to 7,000 is more preferable, and the range of 500 to 5,000 is more preferable.

In designing the polyisocyanate compound, when weather resistance and the like are taken into consideration, the type of isocyanate monomer unit should be limited to an aliphatic type and / or an alicyclic type, and such usage is recommended. To be done.

On the other hand, together with the polyisocyanate compound, the polyhydroxy compound, which is an essential component constituting the organic phase, compensates for the lack of internal cross-linking due to the formation of the wall portion of the polymer particle, and the mechanical property of the polymer particle. The polyhydroxy compound is an extremely important component for further improving the strength, and as the polyhydroxy compound, any of those known per se can be used.

Of these, if only representative examples are given, 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 (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin Or polyhydric alcohols such as hexanetriol;

B) various types of polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol. Polyether glycols;

C) various polyhydric alcohols as listed above and various (cyclic) such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. ) Modified polyether polyols obtained by ring-opening polymerization with an ether bond-containing compound;

D) Polyester polyols obtained by cocondensation of one or more of the various polyhydric alcohols listed above with polyhydric carboxylic acids, the succinic acid, adipic acid, sebacic acid, azelaine. Acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,
4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid, etc. Polyols obtained by using representative polycarboxylic acids; or

E) Polycondensation reaction of one or more of various polyhydric alcohols as listed above with various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. A lactone-based polyester polyol obtained by:

Lactone-modified polyester polyols obtained by the polycondensation reaction of various polyhydric alcohols, polycarboxylic acids, and various lactones as listed above, respectively; or

F) various bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic and / or polybasic acids. Epoxy-modified polyester polyols obtained by using one or more epoxy compounds in combination during the synthesis of polyester polyols;

Further, g) polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or For example, a hydroxyl group-containing silicone resin.

The polyhydroxy compounds shown in (a) to (g) may of course be used alone or in combination of two or more, but the number average molecular weight thereof is 20.
Within the range of 0 to 10,000, preferably 300 to
Within the range of 7,000, more preferably from 500 to
The range of 5,000 is also suitable for sufficient crosslinking inside the polymer particles.

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

In the present invention, the ratio of the isocyanate group equivalent of the polyisocyanate compound and the hydroxyl group equivalent of the polyhydroxy compound is 1: 0.1 to 1: 1.
0.9, preferably 1: 0.1 to 1: 0.
Within the range of 8, more preferably 1: 0.2 to 1:
Used within a range of 0.7 to mix these two components,
Moreover, it is important to make the composition of the mixture of these two components per se three-dimensionally crosslinkable.

That is, when it is desired to completely urethanize such a mixture, it is necessary to make the composition such that it becomes a gel and fluidity is no longer obtained even by heating or diluting the true solvent.

In designing the above-mentioned hydrophobic organic phase, the above-mentioned two conditions are essential for obtaining an internal cross-linking state which cannot be obtained only by the interfacial polymerization reaction by adding the polyamines described below, This is one of the basic requirements of the present invention.

In this case, in order to make the interfacial polymerization reaction reasonably effective, it is necessary to have an excess of isocyanate groups in the above-mentioned range, and such a range is designed so that the outer wall of the particle is promptly formed. is there.

Further, in the present invention, the urethanization reaction inside the particles is allowed to proceed three-dimensionally,
Improvements in toughness, solvent resistance, etc. of the entire particles, which cannot be obtained by conventional techniques, are being attempted.

In designing the three-dimensional urethanization reaction inside the particles, the total amount of the polyisocyanate compound and the polyhydroxy compound contained in the organic phase is a polyisocyanate compound and / or polyhydroxy compound having a functionality of 3 or more. 0.1 mol% or more, preferably 0.2
By containing at least mol%, more preferably at least 0.3 mol%, a good three-dimensional crosslinked state inside the particle can be obtained.

The isocyanate group of the polyisocyanate compound in the organic phase is consumed as the interfacial polymerization reaction with the polyamine compound described later progresses, so that the equivalent ratio of the isocyanate group and the hydroxyl group in the particles approaches each other. The crosslinking density inside the particles increases with the progress of the urethanization reaction, and various properties such as toughness and durability of the polyurethane polyurea crosslinked particles of the present invention are further improved.

The pigment contained in the polyurethane polyurea crosslinked particles of the present invention is a known and commonly used organic pigment,
Inorganic pigments and extender pigments are used, but among them, if only representative ones are given,

First, as organic pigments, "Bentzin Yellow", "Hansa Yellow" and "Rake Red 4R"
Insoluble azo pigments such as; Rake Red C, Carmine 6B, and Bordeaux 10 soluble azo pigments;
Copper phthalocyanine meter pigments such as phthalocyanine blue and phthalocyanine green; basic dyed lakes such as rhodamine lake and methyl violet lake;
Acid dyed lakes such as quinoline lake and fast sky blue; Mordant pigments such as alizarin lake; Anthraquinone pigments; Venturi pigments such as thioindigo pigments and perinone pigments; Quinacudrin pigments such as "Cincacia Red B"Pigments; dioxazine-based pigments such as dioxazine and violet; condensed azo-based pigments such as chromophthal;

Next, as inorganic pigments, chromates such as yellow lead, zinc chromate and molybdate orange; ferrocyan compounds such as navy blue; titanium white, zinc white, mapico yellow iron black, red iron oxide and chromium oxide green. Metal oxides, sulfides such as cadmium yellow, cadmium red, and mercury sulfide, selenium compounds; sulfates such as barium sulfide and lead sulfate; silicates such as calcium silicate and ultramarine; carbonates such as calcium carbonate and magnesium carbonate; Cobalt violet and manganese purple; and other phosphates, aluminum powder, gold powder, silver powder, iron powder, and metal powder such as brass powder; and pearl pigments.

Next, as extender pigments, precipitated barium sulfate, barium carbonate, flour, gypsum, white alumina,
Examples thereof include clay, silica, talc, calcium silicate, and precipitable magnesium carbonate. Carbon black that does not belong to both inorganic pigments and organic pigments can also be used.

These pigments are kneaded with one or more of the above-mentioned polyhydroxy compounds to be used as a mill base. If necessary, the pigments may be chemically surface-treated or kneaded before or during use. It is also possible to combine two or more kinds of pigments or to use additives commonly used in the coating industry and the printing ink industry, such as dispersants and color separation inhibitors.

The kneading is carried out by using a known conventional disperser 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, which is inert to hydroxyl groups and isocyanate groups depending on the required system. There is no problem in adjusting the viscosity of the kneading system by adding a different organic solvent.

As the organic solvent that can be used, those mentioned when adjusting the viscosity of the organic phase at the time of polymer synthesis can be used.

The ratio of the resin to the pigments in the mill-base kneading step is 1 to 900 parts by weight, preferably 2 to 800 parts by weight, particularly preferably 5 to 500 parts by weight, based on 100 parts by weight of the resin solid content. The appropriate range is parts by weight.

The mill base thus obtained and a polyhydroxyl compound and a polyisocyanate compound are
As described above, the components are mixed within various ranges of the present invention and uniformly mixed to form the hydrophobic organic phase (1). The ratio of the pigments contained in the hydrophobic organic phase (1) is as follows. 0.5 to 200 parts by weight based on 100 parts by weight of the total resin solid content,
Preferably 1 to 150 parts by weight, particularly preferably 2 to
A range of 100 parts by weight is suitable.

This hydrophobic organic phase (1) is finely dispersed in an aqueous phase, and 0.2 to 1.0 equivalent of polyamine, preferably 1 to 10 equivalents of polyamine per 1 equivalent of excess isocyanate groups contained in the organic phase. 0.3 to 1.0 equivalent, and more preferably,
An extremely tough pigmented polyurethane is obtained by adding it within a range of 0.4 to 0.9 equivalents to carry out a urethanization reaction at a particle interface and a urethanization reaction within a polymer particle. Polyurea crosslinked particles are obtained.

The organic phase mixed on the basis of such a concept design is finely dispersed in the aqueous phase, and the polyamines are added in an amount of 0.4 to 0.4 per equivalent of excess isocyanate group contained in the organic phase. 1.0 equivalent, preferably 0.3-1.0
An equivalent amount, more preferably 0.4 to 0.9 equivalents, is added within a range of 0.4 to 0.9 equivalents to carry out a urethanization reaction at the particle interface and to carry out a urethanization reaction inside the particles, whereby a polyurethane polyurea which is extremely tough Crosslinked particles are obtained.

In the present invention, the polyamines preferably used include known and commonly used diamines, polyamines, or a mixture thereof, but of these, only typical ones are mentioned. Thus, 1,2-ethylenediamine, bis (3-aminopropyl) amine, hydrazine, hydrazine-2-ethanol, bis (2-methylaminoethyl) methylamine,
1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-hydroxyethylenediamine, N-methyl-bis (3-aminopropyl) amine,
Tetraethylenediamine, hexamethylenediamine, bis (N, N'-aminoethyl) -1,2-ethylenediamine,

1-aminoethyl-1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, phenylenediamine,
Toluylenediamine, 2,4,6-triaminotoluentrehydrochloride, 1,3,6-triaminonaphthalene, isophoronediamine, xylylenediamine, hydrogenated xylylenediamine, 4,4'-diaminodiphenylmethane, or water. Addition 4,4'-diaminodiphenylmethane, or various derivatives of these polyamine monomers.

In the present invention, the hydrophobic organic phase dispersed in water is a non-reactive and hydrophobic organic solvent, which is added, if necessary, to lower the viscosity, and the hydrophobic organic phase is added to the aqueous phase. The dispersibility can be improved.

In this case, the appropriate amount of the hydrophobic organic solvent used is 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight based on the total organic phase.

As the hydrophobic organic solvent to be used, aromatic or aliphatic hydrocarbon-based, ester-based, ether-based or ketone-based ones are suitable, among which benzene, toluene, xylene, cyclohexane, methylcyclohexane, Diphenyl ether or mineral spirits are suitable.

If desired, these organic solvents may be distilled off during or after the formation of particles by a treatment such as heating or reduced pressure.

Next, when the thus-prepared organic solvent phase is dispersed in the aqueous phase, the above-mentioned polyurethane polyurea cross-linked particles are prepared by using a polyisocyanate compound by an extremely simple operation. Therefore, although it is possible to obtain polymer particles,
In order to further stabilize the dispersion, it is selected from various protective colloids such as polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose, gum arabic, polyacrylate, polyacrylamide, polyvinylpyrrolidone and ethylene-maleic anhydride copolymer. There is no problem even if one or more kinds of various known or commonly used nonionic, anionic or cationic surfactants are contained in the aqueous phase in an amount of 0.2 to 20% by weight.

In the present invention, inside the particles,
Although it has a characteristic in that it positively causes a urethanization reaction, as is well known, the urethanization reaction of a hydroxyl group and an isocyanate group is particularly effective when the isocyanate group is based on an aliphatic system or an alicyclic system. Has a slow reaction rate as compared with the urea reaction with an amino group.

As is well known, the reactivity of water with isocyanate groups is extremely slow as compared with the reactivity with hydroxyl groups, and due to the sequestration effect of the outer wall formed by the addition of polyamines, it is The object of the present invention of carrying out the urethanization reaction can of course be achieved,
For the purpose of accelerating the reaction between the isocyanate group and the hydroxyl group in the particles extremely effectively, for example,

Cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tetra-n-butyltin, tri-n-butyltin acetate, n-
One or more of various organometallic catalysts such as butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin acetate, dibutyltin dilaurate, tin octenoate or potassium oleate, and a hydrophobic organic phase. For 5 to 10,000
It is desirable to add it in the range of ppm, preferably 10 to 5,000 ppm. By adding the organometallic catalyst, tough crosslinked polymer particles can be formed in an extremely short time.

That is, these organometallic catalysts can very effectively promote the reaction between the isocyanate group and the hydroxyl group.

The catalyst may be added by adding it to the organic phase prior to water dispersion (fine dispersion).
Alternatively, it is most suitable to carry out in the middle of the step of dispersing the organic phase in water and the step of adding the polyamines.

The addition of the catalyst after adding the polyamines makes it difficult for the catalyst to be taken into the inside of the particles because the outer wall of the polymer particles is being formed.
As a result, the urethane-forming reaction accelerating property inside the particles tends to decrease, which is not preferable.

As described above in detail, as long as the basic requirements of the present invention are satisfied, the polyurethane polyurea crosslinked particles can be obtained by a very simple method, but the resins constituting the organic phase can be obtained. The types of protective colloid and / or surfactant in the dispersion step, the amounts used, or various conditions such as the stirring speed in the dispersion step and the reaction temperature can be freely designed and adjusted.

The average particle size of the polyurethane polyurea crosslinked particles of the present invention is usually 0.1 to 500 microns (μm).
The standard of the particle size varies depending on the application, but the range of 1 to 300 μm is
Particularly, it is more preferable because it is excellent in various properties such as mechanical properties.

Next, the above-mentioned binder resin may basically be any one capable of forming a coating film, and therefore may be of any kind, but of these, particularly representative examples are given. If you keep it on, polyurethane resin,
Various synthetic resins such as alkyd resin, polyester resin, melamine resin, urea resin, epoxy resin, polyamide resin, vinyl acetate resin, vinyl chloride resin, or fluorine resin, or natural rubber or synthetic rubber. , Various rubbers, and further, various natural polymer compounds such as cellulose,
These may be used alone or in combination of two or more,
Of course.

In the present invention, the mixing ratio of the above-mentioned polyurethane polyurea crosslinked particles and the binder resin is based on the total capacity of these two components, and the binder resin: Polymer particles = 25 to 7
The range of 5:75 to 25 (volume% ratio) is suitable.

When the solid content volume of the binder resin is less than 25%, cracks are likely to occur in the coating film, while when it is more than 75%, a matte coating film is inevitably formed. Since it becomes difficult, either case is not preferable.

Next, as the above-mentioned polycarboxylic acid compounds, which are one essential component of the decorative coating composition of the present invention, a high level of matteness is obtained even when the concentration of polymer particles in the coating film is low. It is desirable to use polycarboxylic acid compounds that exhibit the effect of reducing uneven gloss.

As the polycarboxylic acid compounds, only representative ones will be exemplified.
a) First, as the polycarboxylic acid compounds, the main components are unsaturated polycarboxylic acids, respectively, “BYK P-104, BYK P-104S, BYK P-105, B”.
YK-240S or P-405 "[above, product of BYK Chemie Co., Ltd.] or" demol EP "or" demol P "[product of Kao Corp.]; or saturated polycarboxylic acid, respectively, "Disparlon # 1210, # 1220, # 2100, # 21
50 or # 2200 "[above, product of Kusumoto Kasei Co., Ltd.]," Cabon B "," Cabon L-400 ",
"Eleminol MBN-1" or "Sunspear PS-8" [above, Sanyo Chemical Industry Co., Ltd. product], "Floren G-500, G-600, G-630, G-"
660, G-820, AF-1000 or 100
5 ”[above, Kyoeisha Yushi Co., Ltd. products] and the like,

B) Next, as salts of polycarboxylic acids, "lactimone", "lactimon WS", and "antittera" can be used.
203 "," Anttiterra 204 "or" Disper byk "[above, BYK Chemie product] or" Disparon # 1830 "[Kusumoto Kasei product]," Texahol 963 or 963S "[Henkel (stock) ) Products]; or "Nopco K", "Nopco R", "Nopco RF"
"A", "Nopcos Perth 44C", "SN Despersant 5020, 5033, 5045 or 546"
8 "," SN thickener 613C or A-80
8 ”or“ Nopco Santo RFA ”[above, product of San Opco Co., Ltd.] and the like.

Of course, each of the polycarboxylic acid compounds shown in the above a) and b) may be used alone or in combination of two or more kinds. 0.1 to 50% by weight based on the solid content of the polyurethane polyurea crosslinked particles, preferably 0.1.
The range of 5 to 30% by weight is suitable.

The amount of the polycarboxylic acid compound added was 0.
When it is less than 1% by weight, the matting effect due to the addition of the polycarboxylic compound becomes small, while when it is more than 50% by weight, it depends on the polycarboxylic acid compound.
In any case, it is not preferable because stickiness is caused and the touch is easily deteriorated.

In addition to the above-mentioned polyurethane polyurea crosslinked particles, binder resin and polycarboxylic acid compound, the decorative coating composition of the present invention includes ordinary pigments, dyes and ultraviolet absorbers. Of course, various well-known and commonly used additive components such as sedimentation inhibitors and thixotropic agents may be added and mixed.

In order to prepare the decorative coating composition of the present invention containing the above-mentioned polycarboxylic acid compounds, it may be carried out according to a usual coating preparation method. For example, the following is carried out. Can be said to be appropriate.

That is, the polyurethane polyurea crosslinked particles are blended in a binder resin, sufficiently dispersed and stirred by a lab mixer or the like to prepare a target coating composition, and then the coating composition thus obtained. Polycarboxylic acid compounds are added to the product,
The intended design coating composition is prepared by stirring and mixing.

In particular, in coloring the composition of the present invention, of course, it is recommended to use the polymer particles in the form of containing the pigments as they are, but the object of the present invention is to There is no problem with adding pigments, dyes, or the like to the extent of coloring that does not detract from the characteristics of the present invention.

Thus, the decorative coating composition of the present invention is
Known, such as brush coating, coating with a roll coater or a flow coater, or spray coating or dip coating, which can be diluted with the binder resin, if necessary, by diluting with a solvent or water. The equipment can be coated by various conventional coating methods.

[Function] The coating film obtained by using the decorative coating composition of the present invention, which is configured as described above, is a polyurethane polyurea crosslinked in a binder resin by the above-mentioned polycarboxylic acid compound. The wettability and dispersibility of the particles change, and the polyurethane polyurea cross-linked particles are evenly arranged on the surface of the coating film, and the surface of the coating film exhibits unevenness, exhibiting a perfect matting effect. Moreover, there is a strong tendency to have a suede-like characteristic through visual sense.

Further, polyurethane polyurea crosslinked particles,
The decorative coating composition of the present invention composed of a binder resin having a function of coating the polymer particles and binding the polymer particles to each other is capable of forming a tough coating film. When using a binder resin that is easily deformed by external force, a coating film that absorbs external energy given to the coating film and can diverge against scratches, abrasion scratches, scratches, etc. Further, the polyurethane polyurea having a three-dimensional cross-linking structure including a pigment, which has a structure, substantially functions as a colorant and exerts the action and effect as a colorant. The pigments themselves are almost absent on the surface of the polymer particles, and exclusively such pigments are
It is enclosed within the polymer particles or within the coating.

Furthermore, since the designable coating composition of the present invention contains the polycarboxylic acid compounds, the dispersibility of the polymer particles in the binder resin becomes uneven, and the polymer particles are After the coating of the water-based coating composition, the polymer particles are selectively and easily oriented on the surface of the coating film, and even if the concentration of the polymer particles in the decorative coating composition is low, the polymer particles are It becomes the place to orientate intensively.

As a result, the surface of the coating film becomes uneven, and the matteness is dramatically improved. In the conventional case, the low concentration of polymer particles is excellent, which cannot be obtained. It is a place showing matte resistance and scratch resistance.

[0077]

EXAMPLES Next, the present invention will be explained more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is by no means limited to these Examples. . In the following, all parts and% are based on weight unless otherwise specified.

The respective raw material components used in the following will be explained in advance as follows. Among them, the polyisocyanate compound is as follows.

That is, "Bernock DN-901S" (manufactured by Dainippon Ink and Chemicals, Inc., isocyanurate ring-containing polyisocyanate compound obtained using hexamethylene diisocyanate, isocyanurate group content in terms of solid content = 2)
3.5%]; hereinafter, this is abbreviated as PI-1. "Bernock DN-950" [manufactured by Dainippon Ink and Chemicals, Inc., hexamethylene diisocyanate / adduct type polyisocyanate compound; number average molecular weight = 6
40, solid content conversion isocyanate group content = 16.8
%] Solid content was also used, but hereinafter, this is abbreviated as PI-2. Although 1,6-hexamethylene diisocyanate was also used, this is abbreviated as HDI hereinafter.

Next, the polyhydroxyl compound is as follows. A polycaprolactone polyester polyol having a hydroxyl value of 112.2, which was obtained by a polycondensation reaction of trimethylolpropane and ε-caprolactone, was used, which is hereinafter abbreviated as PΟ-1. A polycaprolactone polyester polyol having a hydroxyl value of 168.5, which was obtained by a polycondensation reaction of trimethylolpropane and ε-caprolactone, was also used, but this is hereinafter abbreviated as PO-2. A polycaprolactone polyester polyol having a hydroxyl value of 187, which was obtained by the co-condensation of neopentyl glycol and adipic acid, was also used, but this is hereinafter abbreviated as PΟ-3.

Further, the polyamines are as follows. Ethylenediamine was used.
Is abbreviated. Although 1,6-hexamethylenediamine was also used, this is abbreviated as HMDA hereinafter.

Synthesis Example 1 (Preparation Example of Polyurethane Polyurea Crosslinked Particles) First, “PVA-205” was placed in a 1-liter flask.
An aqueous phase was prepared by dissolving 2 parts of [partial saponification product of polyvinyl alcohol manufactured by Kuraray Co., Ltd.] in 398 parts of water.

In another container, 80 parts of PI-2 and P
Using 20 parts of O-3, dibutyltin dilaurate (hereinafter referred to as DBTD
Abbreviated as L. 0.01 part of
Added into the organic phase.

At room temperature, using a homomixer, 7.0
00-7500 rpm. While stirring the aqueous phase, the previously prepared organic phase was charged therein and stirred for 1 minute to obtain a dispersion liquid.

Then, this dispersion was transferred to another flask, and was stirred at 200 rpm by a paddler type stirring blade. With stirring, 6.5 parts of a 50% aqueous solution of EDA was added. After being kept at room temperature for 2 hours, the temperature is raised to 50 ° C., the same temperature is kept for 1 hour, and the temperature is kept at 80 ° C. for 2 hours to continue the reaction. A suspension was obtained. The average particle size of the particles thus obtained was 18 μm.

Synthesis Example 2 (Preparation Example of Polyurethane Polyurea Resin Particles Containing Pigment) First, 80 parts of PO-2 and “carbon black MA-
20 parts of 100 "[Mitsubishi Carbon Co., Ltd. product] and 25 parts of toluene are mixed, and the mixture is mixed with a sand grinder.
It was dispersed for 1 hour to obtain a black millbase.
Hereinafter, this is abbreviated as MB-1.

Then, in a 1 liter flask, add "PV
A-205 "was dissolved in 398 parts of water to prepare an aqueous phase.
00-7,500 rpm. While agitating with 37.5 parts of MB-1, PO-
16 parts of 1, 1 part of PI-1 and 20 parts of HDI are mixed and then the previously prepared organic phase is added,
Furthermore, 0.02 part of DBTDL was added and stirred for 1 minute to obtain a dispersion liquid.

Then, this dispersion was transferred to another flask, and 200 rpm.
While stirring with a solution of 19.
0 part was added.

After being kept at room temperature (about 25 ° C.) for 2 hours, the temperature was raised to 50 ° C., the temperature was kept at the same temperature for 1 hour, and then 80 ° C.
The reaction was continued for 2 hours to obtain the desired suspension of pigmented, black polyurethane polyurea crosslinked particles.

The average particle size of the polymer particles obtained here was 22 μm. Further, the particles did not swell and dissolve in acetone, and therefore, the outflow of the black pigment was not observed in the acetone.

The suspensions of the respective polyurethane polyurea crosslinked particles obtained in Synthesis Examples 1 and 2 were sprayed.
It was dried using a dryer to give a fine powder, and polymer particles of 75 μm or more were removed through a 200-mesh sieve.

Further, as the binder resin used in Examples and Comparative Examples as a coating film forming component together with the respective polyurethane polyurea crosslinked particles obtained in Synthesis Examples 1 and 2, the following were used. Is.

Polyester urethane resin "Burnock DS-1600" [polyester polyol manufactured by Dainippon Ink and Chemicals, Inc.]; "Burnock DN-980" (HDI-based isocyanate curing agent manufactured by the same company) compounded in OH / NCO = 1/1 (equivalent ratio).

Acrylic melamine resin “Acridic A-409” [acrylic resin manufactured by Dainippon Ink and Chemicals, Inc.]; “Super Beckamine L
-127-60 "(butylated melamine resin manufactured by the same company) was compounded with acrylic resin / melamine resin = 70/30 (solid content ratio).

Epoxy melamine resin “Epiclon 1050” [Bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.]; “Laccamide T
D-973 "(polyamide resin manufactured by the same as above) was compounded with epoxy equivalent / active hydrogen equivalent = 1/1.

Examples 1 to 4 Polymer particles, a binder resin, and a polycarboxylic acid compound in a combination as shown in Table 1 were further added, and xylene / n-butyl acetate = 50/50.
(Parts by weight ratio) with a mixed solvent, mix evenly,
A decorative coating composition having a nonvolatile content of 40% was prepared.

Comparative Examples 1 to 4 Further, in the combinations as shown in Table 1, polymer particles, a binder resin, xylene / n-butyl acetate = 50.
A mixed solvent of / 50 (part by weight) was uniformly mixed to prepare a control coating composition having a nonvolatile content of 40%.

The various coating compositions obtained in each of the examples and comparative examples were individually applied onto iron plates so that the dry film thickness was 50 μm, and the conditions as shown in Table 1 were applied. Then, it was dried and cured.

Next, the coating films were left at room temperature for 1 week, and then the coating film performances were evaluated. The evaluation of these various performances was performed in the following manner.

Gloss: A specular gloss of 60 degrees was measured with a photoelectric gloss meter (“Model TC-108D” manufactured by Tokyo Denshoku Co., Ltd.). (Evaluation Criteria) ⊚: The gloss is 2 or less, and the coated surface is uniform and in a completely matt state. ○: The gloss is 2 or less, and the coated surface has uneven gloss. ×: The gloss is 2 Is over

Scratch resistance: # 000 steel wool was rubbed at a surface pressure of 30 kg / cm ² , and 1 hour after that, the state of the coated surface was visually evaluated. (Evaluation criteria) ⊚: No scratches ○: Slight scratches ×: Scratches remain clearly

[0102]

[Table 1]

<< Footnotes in Table 1 >> Compound 1 ... "Lactimon WS" Compound 2 ... "BYK P104" Compound 3 ......... "Anttitera 203"

The curing conditions are as follows. For polyester urethane resin, 30 minutes at 60 ° C. For acrylic / melamine resin, 140 ° C for 30 minutes. For epoxy / polyamide resin, 150 ° C for 30 minutes.
Minutes

[0105]

[Table 2]

[0106]

[Table 3]

<< Footnotes in Table 1 >> Gloss ... 60 degree specular reflectance Gloss unevenness ... Judgment by visual observation ⊙ ∙ Completely disappeared ∙∙∙ Although slightly lost Yes × ………… Remarkably glossy

[0108]

[Table 4]

As is clear from Table 1, the decorative coating composition of the present invention was excellent in that the surface of the obtained coating film was uneven even when the concentration of the polyurethane polyurea crosslinked particles was low. It is known that it exhibits matteness and scratch resistance.

[0110]

INDUSTRIAL APPLICABILITY As described above, the decorative coating composition of the present invention and the coated article thereof are composed of polyurethane polyurea crosslinked particles having a three-dimensional crosslinked structure, a binder resin, and a polycarboxylic acid compound. Which, among other things,
The articles coated with the composition of the present invention are all highly advanced matte coatings having an extremely high-grade feeling since the polyurethane polyurea crosslinked particles (polymer particles) are in a state of protruding onto the surface of the particles. It is also possible to make it a very highly practicable one in the form of formed.

In addition, since the polymer particles themselves have a three-dimensional crosslinked structure, the design coating composition of the present invention has, among others, solvent resistance, abrasion resistance, scratch resistance, It has excellent scratch resistance and durability.

By limiting the polycarboxylic acid compound, which should be said to be a characteristic component of the present invention, a coating film having such a characteristic effect further enhanced can be formed, and moreover, a soft touch is obtained. It can form an excellent coating film.

Claims (3)

[Claims] 1. Polyurethane polyurea crosslinked particles having a three-dimensional crosslinked structure and a binder resin are used as coating film forming components.
Further, a decorative coating composition also comprising a polycarboxylic acid compound and / or a salt of the carboxylic acid. 2. The above-mentioned polyurethane polyurea crosslinked particles are a mixture of a polyisocyanate compound and a polyhydroxy compound in which an isocyanate group is stoichiometrically excessive, and a three-dimensional crosslinked structure is formed by a reaction. The organic phase that can be formed and the polyamine having a stoichiometrically excess amount of isocyanate group equivalent or less, as well as an urethanization reaction inside the particle, which is obtained. Decorative coating composition. 3. The above-mentioned polyurethane polyurea cross-linked particles contain a pigment, and are made into an organic phase in which a polyhydroxy compound and a polyisocyanate compound having a stoichiometrically excessive isocyanate group are mixed. In addition, it is obtained through an interfacial polymerization reaction between an organic phase capable of forming a three-dimensional crosslinked structure by the reaction and a polyamine having a stoichiometrically excess isocyanate group equivalent or less, and a urethanization reaction inside the particle. 2. Pigmented polyurethane polyurea crosslinked particles according to claim 1.
The decorative coating composition described in.